ICCOSS XXIII, Stellenbosch, South Africa CONTENTS MESSAGE FROM THE CHAIR OF THE ORGANISING COMMITTEE 2 PREVIOUS ICCOSS MEETINGS 3 COMMITTEES 4

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1 CONTENTS MESSAGE FROM THE CHAIR OF THE ORGANISING COMMITTEE 2 PREVIOUS ICCOSS MEETINGS 3 COMMITTEES 4 GENERAL INFORMATION 5 VENUES AND FACILITIES 7 SOCIAL PROGRAM 9 THE LOCALS RECOMMEND 11 SCIENTIFIC PROGRAM 18 ORAL LECTURE ABSTRACTS 26 POSTER ABSTRACTS April,

2 MESSAGE FROM THE CHAIR OF THE ORGANISING COMMITTEE On behalf of the Organising Committee I would like to extend a heartfelt welcome to all our delegates. Thank you for agreeing to participate in the 23 rd International Conference on the Chemistry of the Organic Solid State - after all, you contribute the most towards the success of a conference such as this. The ICCOSS XXIII program will showcase frontier research relating to various aspects of organic solid state chemistry, as well as bring together both young and experienced scientists from around the world to establish fruitful discourse. Since the very first ICCOSS conference in Brookhaven (USA) in 1968 the ICCOSS conference series has become the premier forum for discussing groundbreaking research on the chemistry and physics of organic materials. We are proud to host the first ICCOSS conference to be held on the African continent. The scientific program for ICCOSS XXIII will include invited lectures, contributed lectures and poster sessions. Finally, we hope that you will have a successful week of conferencing, and also that you will enjoy your time in Stellenbosch. Len Barbour Conference Chairman April, 2017

3 PREVIOUS ICCOSS MEETINGS 1. Brookhaven, USA (1968) 2. Rehovot, Israel (1970) 3. Glasgow, Scotland (1972) 4. Bordeaux, France (1975) 5. Brandeis University, Boston, USA (1978) 6. Freiburg, Germany (1982) 7. Crete, Greece (1985) 8. Lyon, France (1987) 9. Como, Italy (1989) 10. Vancouver, Canada (1991) 11. Ramat Rachel, Jerusalem, Israel (1993) 12. Matsuyama, Japan (1995) 13. Stony Brook, USA (1997) 14. Cambridge, UK (1999) 15. Mainz, Germany (2001) 16. Sydney, Australia (2003) 17. Los Angeles, USA (2005) 18. Merida, Venezuela (2007) 19. Sestri Levante, Italy (2009) 20. Bangalore, India (2011) 21. Oxford, UK (2013) 22. Niigata, Japan (2015) 2 7 April,

4 LOCAL ORGANISING COMMITTEE Len Barbour (Chair) Nikoletta Báthori Susan Bourne Mino Caira Marike du Plessis Catharine Esterhyuysen Delia Haynes Tanya le Roex Luigi Nassimbeni Clive Oliver Vincent Smith INTERNATIONAL ADVISORY BOARD Bruce Foxman (USA) Bart Kahr (USA) Bill Jones (UK) Gleb Segeev (Russia) Michael D. Ward (USA) Angiolina Comotti (Italy) Sally Price (UK) Elena Boldyreva (Russia) Len Barbour (South Africa) Pance Naumov (Abu Dhabi) Wais Hosseini (France) Graciela Diaz de Delgado (Venezuela) Roger Bishop (Australia) Mark D. Hollingsworth (USA) Daniel Sandman (USA) Piero Sozzani (Italy) Kenneth D. M. Harris (UK) Keiichiro Ogawa (Japan) Kimoon Kim (Korea) Reginald Tan (Singapore) Joel Bernstein (Israel) Rui Tamura (Japan) Miguel Garcia-Garibay (USA) CONFERENCE SECRETARIAT Retha Venter, Tel: , Fax: Mobile: , April, 2017

5 GENERAL INFORMATION REGISTRATION AND INFORMATION DESK The registration and information desk is located at the front desk of the Wallenberg Centre (see the map on the back cover of this booklet) You may register between 16:30 and 19:00 on Sunday, 2 April, or from 08:00 to 08:15 Monday through Friday. LANGUAGE The official language of the conference is English. AIRPORT TRANSFERS We will endeavour to arrange transportation between Stellenbosch and Cape Town International Airport during the weekends both before, and after the conference. Prior arrangement is necessary for such transfers please consult the staff at the information desk to make the appropriate arrangements. WEATHER The weather in Stellenbosch is variable, with temperatures generally ranging between 15 and 25 C (59 to 77 F) at this time of year. Although not expected, rain showers can occur. Please be prepared for unexpected changes in the weather, especially when dressing for the evening social functions (i.e. bring a warm sweater or jacket). The sun will rise and set at approximately 07:00 and 18:30, respectively. 2 7 April,

6 WATER RESTRICTIONS Please be aware that the Western Cape is experiencing a severe drought at present and government-mandated water restrictions are currently in place. We ask that you try to be water-wise and conserve water whenever possible. CONTACT INFORMATION & EMERGENCY NUMBERS If you encounter any problems during your stay in Stellenbosch, you may contact Len Barbour at +27 (0) University of Stellenbosch Campus Security Report incidents to the Control Room - Tel.: +27 (0) (24h) Ambulance Tel: 999 or Police Emergency Number Tel: April, 2017

7 VENUES AND FACILITIES The conference venue is indicated on the map on the inside cover of this booklet. The conference sessions will take place in the Wallenberg Centre at the Stellenbosch Institute for Advanced Study (STIAS, 10 Marais Street). ORAL PRESENTATIONS All oral sessions will convene in the auditorium in the Wallenberg Centre. The hall is equipped with a projector and a microphone. A technician will be available to assist speakers in loading their presentations. In order to facilitate smooth management of time, we encourage all speakers to submit their files well before their designated sessions, and to ensure that their presentations will display correctly. TEA/COFFEE BREAKS Refreshments will be served in the foyer at designated times. 2 7 April,

8 POSTERS The poster boards will be placed in the basement parking area. Please make sure your posters are up before 14:00 on Monday, 3 April. The posters should remain up for the duration of the conference. Presenters are requested to be present at their posters during the official poster sessions on Monday, 3 April and/or Tuesday 4 April. Even-numbered posters will be presented on Monday, and odd-numbered posters on Tuesday. Light refreshments will be served during the poster sessions. LUNCH A buffet-style lunch will be served in the foyer of the Wallenberg Centre. Delegates are welcome to enjoy their lunch out on the patio (weather permitting) and take advantage of the views overlooking the vineyards and the lovely Stellenbosch Mountain. Stellenbosch is well known for its excellent eateries. Dinner will be for the delegates own expense (except for the conference dinner on Thursday 6 th April). A list of dining recommendations is provided in this book, or you may simply ask one of the locals for some suggestions to suit your flavour and budget. FACILITIES Two desktop computers are available at the front desk for delegates to check their . WiFi will also be available in the Wallenberg Centre (details displayed at the front desk). Alternatively you can connect to the Eduroam facility using your home University credentials April, 2017

9 SOCIAL PROGRAM SUNDAY, 2 APRIL Registration and Welcome Function to take place in the Wallenberg Conference Centre at the Stellenbosch Institute for Advanced Study, which is located at 10 Marais Street (see map). The registration desk will be available from 16:30. From 17:30 you are invited to socialise with the other delegates in the relaxed setting of a cocktail party, also in the Wallenberg Centre. MONDAY, 3 APRIL and TUESDAY, 4 APRIL Poster Sessions to take place in the Basement Parking garage of the Wallenberg Centre from 17:30 19:00. Light refreshments will be served. Poster presenters are requested to be present at their posters during this time: even numbers on Monday, odd numbers on Tuesday. A number of generous sponsors have donated poster prizes, and these will be presented during the conference dinner on Thursday. WEDNESDAY, 5 APRIL Conference excursion buses will depart from STIAS shortly after 12:30. Please be there promptly to avoid being left behind. The optional afternoon activities will begin with a four-course food and wine pairing at a local winery, Clos Malverne. Clos Malverne was established in the 1980s to supply grapes to surrounding wine producers. More recently the estate started producing its own wine, for which it has won a number of awards. Clos Malverne practices a handmade style of winemaking and has adopted sustainable practices. The 2 7 April,

10 Clos Malverne harvests its own fruit and vegetables, ensuring that patrons can enjoy a fresh, seasonal and contemporary meal. Lunch will be followed by a tour of the van Ryn s Distillery, which was awarded the Best Distillery Tour in the world at the 2015 Distillery Experience Awards, and has won the IWSC (International Wine and Spirit Competition) trophy for the Best Worldwide Brandy seven times in the past 12 years. The distillery was established in 1905, and the walls of the building were constructed from rocks gathered from the nearby Eerste River. During your visit you will stroll through the working distillery, catch a glimpse of the age-old art of coopering and end off with a pre-selected tasting. THURSDAY, 6 APRIL Conference Dinner buses will be leaving from Neethling Street (see map) at 17:45. Please arrive promptly in order to avoid delays in leaving. The dinner will take place at Allée Bleue Wine Estate (see The historical estate of Allée Bleue is nestled at the foot of the majestic Drakenstein Mountains in the Franschoek Valley. The scenic estate, with its Cape Dutch ambience, is not only a beautiful venue but is also a working farm with amazing fresh produce including herbs, olives, fruit and award-winning wines. Established in 1690 under the name Mere Rust, Allée Bleue has been brought back to life with great dedication and attention to detail, resulting in a combination of typical South African farming tradition, contemporary lifestyle, art and nature April, 2017

11 THE LOCALS RECOMMEND In order to make your stay in Stellenbosch as enjoyable as possible, we have compiled a list of places to visit for good food, entertainment or arts and culture. If you need any further advice or information, please don't hesitate to ask us.... PLACES TO EAT Stellenbosch has a large number of restaurants, cafés and delis: some excellent and some, well, not so good. With so many options available we thought that a few pointers might be in order. For a town with such a large number of restaurants, most places are surprisingly well patronised and, particularly for dinner, it is worth making a booking. As this is arguably the wine capital of the country, most establishments charge a corkage fee however, this is also worth confirming. So, without further ado, here is a brief list of our recommended eateries. Cafés Café central in Stellenbosch is found along Church and Andringa Streets in the old part of town. There are numerous places to wander past or at which to sit down. Perhaps the most well-known of the cafés in Church Street is Java Café. They serve a wide range of interesting foods and very good coffee. Java is almost always busy, particularly their sidewalk section, with young and old alike enjoying themselves. Another café worth visiting is Basic Bistro, also on Church Street two doors above Java. They offer reasonably priced good food with a decent wine list. Just around the corner in Andringa Street is Man ouche, a 2 7 April,

12 Lebanese style eatery fronted by a very friendly, you guessed it, Lebanese chef. Their hummus and flatbread platters are truly excellent, as are their salads. Next door to Man ouche is Craft, where you can enjoy a combination of craft beer, artisian bread (baked on site) and original wood-fired Flammenkuchen and tapas. If you like tapas, then Steam is definitely worth a visit. Bartinney Wine Bar (Bird st) as well as Bramptons Wine Studio (Church St) are also in close proximity and are extremely popular with the locals. Vide e Café, on the corner of Bird and Church, is also a good option for a light meal and coffee, but their pricing certainly does not cater for poor students. For a decent lunch in very attractive surroundings, try Katjiepiering at the Botanical Gardens. The Blue Crane and the Butterfly has two locations across the street from each other on Dorp Street, and they were voted as serving the best coffee in Stellenbosch. Their menu changes daily and they serve some delightful desserts as well as savoury dishes. There are a number of cafes side-by-side along Ryneveld street: Meraki, Tastebud and Häzz are popular with the locals and one can enjoy a relaxed cup of coffee at one of the streetside tables. For a little bit of everything Dewarenmarkt on Plein St. provides a unique indoor market-like setting with communal tables and a variety of food and drinks. Restaurants There are two pizza places really worth mentioning in Stellenbosch: Gino s in Dorp Street and Col'Cacchio on Plein Street. Gino s is an Italian restaurant with a twist, and is a big favorite with students and academics alike. This popularity is probably due to the affordability of their food April, 2017

13 and the size of the portions an evening at Gino s never seems to disappoint. Their outdoor tables are perfect for summer evenings with a group of hungry friends. If Gino s offers quantity, Col'Cacchio offers quality, with their extensive range of imaginative gourmet pizzas. Also in Dorp Street, almost across from Gino s, is Simply Asia. As the name might suggest, they serve Thai styled Asian foods at a reasonable price. The authenticity of their foods can be vouched for, as their Thai chief can be seen plying his trade from within the restaurant. It might be worthwhile taking your own bottle of wine along though, as their wine list is rather limited. If you like Indian food, Bukhara on the corner of Bird and Dorp is the place to go and their cocktail list is outstanding. For a taste of real South African fare, Twaalf (Afrikaans for twelve) has an impressive menu, all at reasonable prices we recommend that you take your own wine. Find them on the corner of Mark and Dorp streets in the Black Horse Centre. If you are looking for a good piece of South African beef as well as some more exotic game meat, the Hussar Grill or The Fat Butcher (both on Plein street) are good options (with the Hussar being the less expensive choice). For all variety of burgers, Hudsons burger joint is the place to go (Dorp St). The burgers at Steam on Ryneveld are also legendary. Other popular locations include Asta la Pasta (Dorp) and Flame & Ash (cnr Church & Mill St). A bit out of town on the Strand road are the long-time student favorites La Romantica and the franchise Jimmy the Fish (corner of Strand & Blaauwklippen). Both offer good value for money. Watch out though - La Romantica gets very full of hungry patrons, particularly on their Sunday and Monday specials nights. Moving onto the classier side of eating out in 2 7 April,

14 Stellenbosch, de Volkskombuis and its sister restaurant de Oewer (Aan-de-Wagen Road) are perhaps the most beautifully situated restaurants in Stellenbosch. They lie on the banks of the Eerste River, under the shade of giant oak trees. De Volkskombuis offers traditional jazzed up South African food and de Oewer servers more adventurous fusion type modern foods. Wijnhuis on Andringa Street is a classy establishment offering not only mouth-watering food, but also somewhat higher prices. However, their food and wine list are really excellent. You can also taste a variety of wines here. The Big Easy, owned by the wellknown South African Golfer Ernie Els, serves some delicious food and houses an impressive wine list. The 1802 Restaurant, which is part of d' Ouwe Werf Hotel at 30 Church Street, offers a stunning setting (and food to match) if you take a table in their vine-encased courtyard. For those looking for sushi, Genki s in the De Wet Centre just off Plein street comes highly recommended, or you could try Hayashi (Andringa st) who have a wide selection with exceptional prices. Wine estates For those people with access to a car there are always restaurants on wine estates, with gourmet food and superb wines. Highly recommended are Tokara on the Helshoogte pass in the direction of Franschoek, with stunning views over False Bay and the Banhoek valley; the Lord Neethling at Neethlingshof on the M12 in the direction of Kuilsriver and historical Lanzerac on the outskirts of Stellenbosch, all of which offer excellent wine lists in stylish surroundings. A series of inviting restaurants await you on the R44 towards Somerset West, including the award April, 2017

15 winning Terroir on the Kleine Zalze wine estate, Bodega at Dornier with its incredible views over the architectural marvel of their wine-cellar, and 96 Winery Road with a wide selection of the award-winning Ken Forrester wines. For more superb views from your table under the oaks try Morgenhof on the R44 in the direction of Klapmuts (lunches only), or for an unusual lunch or tea with amazing views, try Hillcrest Berry Orchards on the R310 on the way to Franschoek. This list is by no means complete please feel free to consult the organising committee for any further recommendations. Java Café Cnr Church & Andringa Basic Bistro 31 Church Street Man ouche Andringa Street Craft 16 Andringa Street Steam 5 Ryneveld Street Bartinney Wine Bar 5 Bird Street Bramptons Wine Studio 11 Church Street Vide e Café de Wet Centre, cnr Bird & Church Katjiepiering Botanical Gardens, Neethling St The Blue Crane & the Butterfly 146 Dorp St Meraki 42 Ryneveld Street Tastebud 44 Ryneveld Street Häzz 32 Ryneveld Street Dewarenmarkt 16 Ryneveld Street Ginos 63 Dorp Street April,

16 Col'Cacchio Simonsplein Centre Plein St Simply Asia 54 Dorp Street Bukhara Shop 4, Cnr Dorp and Bird Twaalf Market Street Hussar Grill 23 Plein Street The Fat Butcher 1 van Riebeeck Street Hudson s Burger Joint 77 Dorp Street Asta la Pasta Dorp Street Flame & Ash 7 Church Street La Romantica Strand & Blaauwklippen Roads Jimmy the Fish Strand & Blaauwklippen Roads De Volkskombuis Aan de Wagen Rd De Oewer Aan de Wagen Rd Wijnhuis cnr Andringa & Church The Big Easy 94 Dorp Street Restaurant 30 Church Street Genki De Wet Centre Courtyard, Plein Street Hayashi 6 Andringa Street Tokara Helshoogte pass Lord Neethling Neethlingshof estate on M Lanzerac Lanzerac road Terroir Kleine Zalze wine estate off R Bodega Dornier wines, Blaauwklippen road Winery Road Winery Road off R Morgenhof Morgenhof estate, R Hillcrest Berry Orchards R310 to Franschoek April, 2017

17 ... NIGHTLIFE Cubana (Plein Street) is one of the hottest and most recently founded club and lounge places in Stellenbosch very nice with a reasonably priced cocktail bar. The Happy Oak (affectionately referred to as Brazen Head by older students) on Andringa Street is one of the more relaxed watering holes in Stellenbosch, with good food, great people and affordable prices. The Trumpet Tree (Dorp st) is also a popular hangout for the slightly younger crowd. Balboas (Andringa st) is somewhat hidden away but has become a favorite for drinks following a long day, and on Thursdays they have live Blues music to add to the atmosphere. De Akker (Dorp Street) is one of the oldest bars in South Africa, but don t let that put you off as it has a very relaxed bar atmosphere. AandKlas is the place to experience the Stellenbosch local band scene, with affordable food and drink. Mystic Boer & Bohemia (Victoria Street) are for the hippie-type folks interesting people, with affordable food and drinks: definitely a must-see. Those looking for a game of pool can head down to Stones (Drostdy Centre, off Bird Street). In the same quad you will also find Tin Roof as well as Catwalk if you find yourself in the mood for dancing. Catwalk caters to all music tastes and you can even try your hand at Sokkie.... ART AND CULTURE Stellenbosch is well-known as a hub of arts and culture in South Africa, with the Rupert Museum in Stellentia avenue (just off lower Dorp Street) displaying arguably the finest collection of South African art in the country. Other art museums worth visiting are the SASOL Art Museum and University of Stellenbosch Art Gallery. There is also a curated collection of art and sculpture all around the town in Stellenbosch keep your eyes open! 2 7 April,

18 SCIENTIFIC PROGRAM Sunday, 02 April 16:30 19:00 REGISTRATION, The Stellenbosch Institute for Advanced Study 17:30 19:00 OPENING MIXER, Cocktail party at STIAS Monday, 03 April Morning Session 08:00 08:15 REGISTRATION Front Desk 08:15 08:30 OPENING REMARKS AND ANNOUNCEMENTS Len Barbour Session Chair Susan Bourne 08:30 09:10 Jonathan Steed Durham University O-1 Gel-Based Approaches to Novel Solid Forms 09:10 09:40 Dario Braga Università degli Studi di Bologna O-2 From Organic Co-crystals and Ionic Co-crystals to Solid Solutions 09:40 10:00 Cristina Mottilo McGill University O-3 Self-Assembly of Metal-Organic Frameworks from Metal Oxides in Supercritical CO2 10:00 10:30 TEA/COFFEE BREAK 10:30 11:00 Michael McBride Yale University O-4 Understanding Long-Chain Melting Points, Interface Thermodynamics & F.L. Breusch 11:00 11:30 Petra Bombicz Research Centre for Natural Sciences, Hungarian Academy of Sciences O-5 The Way from Isostructurality to Polymorphism. Where are the borders? 11:30 11:50 Matteo Lusi University of Limerick O-6 What Makes Solid Solution Happen? 11:50 12:30 Pierangelo Metrangolo Politecnico di Milano O-7 Halogenation as a New Tool to Control Peptide Self-Assembly 12:30 12:40 Dyanne Cruickshank Rigaku Sponsor presentation 12:40 14:00 LUNCH April, 2017

19 Monday, 03 April Afternoon Session Session Chair Clive Oliver 14:00 14:40 Kenneth Harris Cardiff University O-8 New Experimental Techniques for Exploring Crystallization Pathways and Structural Properties of Solids 14:40 15:10 Mark Hollingsworth Kansas State University O-9 Self-Compression in Channel Inclusion Compounds 15:10 15:30 Dejan-Krešimir Bučar University College London O-10 Engineering Molecular Crystals: Backbreaking yet Gratifying 15:30 15:50 TEA/COFFEE BREAK 15:50 16:10 Agnieszka Janiak Adam Mickiewicz University O-11 Many Faces of Chiral Trianglimine Crystals 16:10 16:30 Jeremy Cockcroft University College London O-12 Short-Range Interactions in 1:1 Adducts Formed by C6F6 16:30 16:50 Savannah Zacharias University of Cape Town O-13 The Role of the Ligand in Formation of Iron(III) Supramolecular Gels 16:50 17:30 Tomislav Friščić McGill University O-14 Discovering and Understanding Mechanochemistry 17:30 19:00 POSTER SESSION Basement Parking Area, Wallenberg Conference Centre 2 7 April,

20 Tuesday, 04 April Morning Session 08:00 08:30 REGISTRATION Front Desk Session Chair Tanya le Roex 08:30 09:10 Panče Naumov New York University Abu Dhabi O-15 Self-Healing Molecular Crystals 09:10 09:40 Satoshi Takamizawa Yokohama City University O-16 Organosuperelasticity: New Physical Element in Chemistry 09:40 10:00 Anna Gudmundsdottir University of Cincinnati O-17 Using LFP to Elucidate Bimolecular Reaction Mechanisms in Crystals 10:00 10:30 TEA/COFFEE BREAK 10:30 11:00 Jason Benedict University at Buffalo SUNY O-18 Designing Low Symmetry Photo-responsive Metal-Organic Frameworks 11:00 11:30 Manuel Fernandes University of the Witwatersrand O-19 Molecular Dynamics from Slow Diffraction Experiments 11:30 11:50 Giancarlo Terraneo Politecnico di Milano O-20 Crystalline Supramolecular Rotors Assembled through Halogen Bonding 11:50 12:30 Kari Rissanen University of Jyväskylä O-21 Organic Materials Based on Very Strong Halogen Bonds 12:30 12:40 Christopher Nickels Form Tech Scientific (FTS) Sponsor presentation 12:40 14:00 LUNCH April, 2017

21 Tuesday, 04 April Afternoon Session Session Chair Nikoletta Bathori 14:00 14:40 Mir Wais Hosseini University of Strasbourg O-22 Perspectives in Molecular Tectonics: From Crystals to Networks of Crystals 14:40 15:10 Fabrizia Grepioni Università degli Studi di Bologna O-23 Tuning Luminescence and Photoreactivity in Organic Co-crystals and Salts 15:10 15:30 Hiroki Takahashi Kyoto University O-24 Preferential Enrichment: Effect of Cocrystallization of Racemic Compounds 15:30 15:50 TEA/COFFEE BREAK 15:50 16:10 Tatyana Shabatina M.V. Lomonosov Moscow State University O-25 Cryochemical Synthesis and Antibacterial Activity of Hybrid Compositions included Ag and Cu Nanoparticles in Nanocrystals of Antibiotics 16:10 16:30 Vjekoslav Štrukil Ruđer Bošković Institute O-26 Evolution of Photoredox Catalysis: Out of the Solvent and Into the Solid State 16:30 16:50 Katharina Edkins Durham University Queen s Campus O-27 Substituent Influence on Self-Assembly of Pharmaceutical Drug Compounds 16:50 17:30 Leonard MacGillivray University of Iowa O-28 Crystalline Materials to Molecules 17:30 19:00 POSTER SESSION Basement Parking Area, Wallenberg Conference Centre 2 7 April,

22 Wednesday, 05 April Morning Session 08:00 08:30 REGISTRATION Front Desk Session Chair Mino Caira 08:30 09:10 Michael Zaworotko University of Limerick O-29 Crystal Engineering of Multi-Component Pharmaceutical Materials 09:10 09:40 Aurora Cruz-Cabeza The University of Manchester O-30 Surface Effects in Polymorphism. When Do They Matter? 09:40 10:00 Kevin Roberts University of Leeds O-31 From Crystallographic Structure to the Surface Properties of Pharmaceutical Materials 10:00 10:30 TEA/COFFEE BREAK 10:30 11:00 Jennifer Swift Georgetown University O-32 Tuning Hydrate Properties Through Doping 11:00 11:30 Joel Bernstein Ben-Gurion University of the Negev; New York University Shanghai O-33 Structural Chemistry, Fuzzy Logic and the Law 11:30 11:50 James Black The University of Manchester O-34 Additive Effects on the Appearance and Kinetics of Polymorphs of p- Aminobenzoic Acid (PABA) 11:50 12:30 Bill Jones University of Cambridge O-35 Aspects of Cocrystal Solid State Chemistry 12:30 18:00 CONFERENCE EXCURSION Lunch will be provided and transport will be arranged April, 2017

23 Thursday, 06 April Morning Session Session Chair Luigi Nassimbeni 08:30 09:10 Christer Aakeröy Kansas State University O-36 The Use of Halogen Bonding and Hydrogen Bonding in Versatile Supramolecular Synthetic Strategies 09:10 09:40 Demetrius Levendis University of the Witwatersrand O-37 Supramolecular Design of Topochemical Solid-State Reactions 09:40 10:00 Dinabandhu Das Jawaharlal Nehru University O-38 Polymorphism and Solvatomorphism of Some Bis-hydrazone Compounds 10:00 10:30 TEA/COFFEE BREAK 10:30 11:00 Valery Gorbatchuk Kazan Federal University O-39 Smart Calixarene Crystals 11:00 11:30 Kinga Suwinska Cardinal Stefan Wyszynski University in Warsaw O-40 Solid State Features of Calixarenes 11:30 11:50 Ryan Groeneman Webster University O-41 Cross-Photodimerization Reactions Utilizing Polyfluorophenyl-Phenyl Interactions 11:50 12:30 Angiolina Comotti University of Milano Bicocca O-42 Molecular Rotors in Porous Supramolecular Architectures 12:30 12:40 Jerry Atwood Editor in Chief, Comprehensive Supramolecular Chemistry, 2 nd Edition (Elsevier) Sponsor presentation 12:40 14:00 LUNCH 2 7 April,

24 Thursday, 06 April Afternoon Session Session Chair Delia Haynes 14:00 14:40 Sarah (Sally) Price University College London O-43 Is the Crystallisation of Pharmaceuticals Controlled by Thermodynamics or Kinetics? 14:40 15:10 Piero Sozzani University of Milano Bicocca O-44 Absorptive Organic and Hybrid Materials for Gases and Polymers 15:10 15:30 Holger Ott Bruker AXS Gmbh O-45 Organics in SC-XRD: from Alpha to (Almost) Omega 15:30 15:50 TEA/COFFEE BREAK 15:50 16:20 Travis Holman Georgetown University O-46 A Plethora of 0D Porous Molecular Solids 16:20 16:50 Consiglia Tedesco Università di Salerno O-47 Selectivity and Structure of Mixed Guest Clathrates 16:50 17:30 Michael Ward New York University O-48 Stopping Crystal Growth in its Tracks: Preventing Pathological Crystallization 18:00 late CONFERENCE DINNER at Alleé Bleue Estate Transport will be arranged April, 2017

25 Friday, 07 April Morning Session Session Chair Catharine Esterhuysen 08:30 09:10 Graeme Day University of Southampton O-49 Energy-Structure-Function Maps and the Discovery of Porous Molecular Crystals 09:10 09:40 Gareth Lloyd Heriot-Watt University O-50 The Solid-State Properties of Gels Formed with Phenylalanine and its Derivatives 09:40 10:00 Yury Morozov M.V. Lomonosov Moscow State University O-51 The Preparation of Nanoparticles and Nanostructures of Steroid Neurohormones 10:00 10:30 TEA/COFFEE BREAK 10:30 11:00 Neil Feeder The Cambridge Crystallographic Data Centre O-52 Towards a Knowledge-Based Crystal Packing Score 11:00 11:30 Rui Tamura Kyoto University O-53 Unique Magnetic Properties of All-Organic Radical Liquid Crystals 11:30 11:50 Bernard Dippenaar University of Stellenbosch O-54 Rationalising the Solid-State Properties of Dithiadiazolyl Radicals Using a Combined Theoretical and Experimental Approach 11:50 12:10 Valentina Santolini Imperial College London, South Kensington Campus O-55 Design Strategies for the Prediction of Porous Organic Cage Topologies 12:10 12:50 Jerry Atwood University of Missouri-Columbia O-56 Exploring New Frontiers in Organic Anhydrates, Hydrates, and Solvates 12:50 13:00 CLOSING REMARKS Len Barbour 2 7 April,

26 O-1 Gel-Based Approaches to Novel Solid Forms Jonathan W. Steed Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK. Web: While the chemical structure of a drug is key to its mode of action in vivo, its solid form is key to its delivery to the bloodstream. Different crystal forms (polymorphs, pseudopolymorphs, salts or co-crystals) have different bioavailability, dissolution rate and solubility characteristics. There have been a number of high profile cases where failure to identify the most stable crystal form of a drug has led to severe formulation problems in manufacture, notably the occurrence of Form II of the anti-hiv drug ritonavir. In our work we exploit weak interactions between drug-like molecules and a pre-formed, locally ordered gel fibril. Crystallization from gels is a classic technique (Figure) but only recently has crystallization from supramolecular organogels been applied to small molecules like drugs.[2] Gel crystallization offers the advantage in which the supramolecular gel turns off convection currents and supresses nucleation. Particular gels can exhibit drug-specific molecular recognition that changes the polymorphic outcome entirely in ways that can be explicitly understood and designed for. The most spectacular example is the crystallization of the olanzapine precursor ROY from a gel which we explicitly designed to have the same peripheral chemical functionality as the ROY molecule itself. ROY-mimetic gels selectively result in the crystallization of the metastable red form of ROY. A range of other gels and crystallization from solution under exactly the same conditions give the thermodynamically stable yellow form. Keywords: gel, polymorphism, crystallization [1] D. K. Kumar, J. W. Steed. Chem. Soc. Rev., 2014, 43, [2] J. A. Foster et al. Chem. Sci., 2017, 8, April, 2017

27 O-2 From Organic Co-crystals and Ionic Co-crystals to Solid Solutions Dario Braga, Fabrizia Grepioni, Lucia Maini Dipartimento di Chimica Giacomo Ciamician, Università degli Studi di Bologna, Via Selmi, 2, Bologna, Italy. The distinction between molecular salts, ionic co-crystals and molecular co-crystals can be rather semantic. These compounds are basically multi-component crystals made of molecules that have their own identity as separate entities. What matters, however, is the difference in solid state properties that might be attained by preparing mixed systems. In this talk I will discuss some examples of the various types of compounds, remarking on the preparation methods and on the differences in structures and properties. More specifically, I will describe co-crystals formed by organic molecules such as barbituric, thiobarbituric and cyanuric acids as well as histidine, piracetam and racetam derivatives with the inorganic MX (M = Li, K, Rb, X = Cl, Br, I) and MX2 salts (M= Ca, Mg, X = Cl, Br, I) yielding ionic co-crystals with changed or improved physico-chemical properties with respect to the organic co-former (melting point, hygroscopicity, crystal morphology, solubility, dissolution rate etc.). In the case of chiral molecules, e.g. histidine, the relationship between enantiopure and racemic co-crystals will be examined. The results obtained in the characterization of solid solutions prepared by mixing isomorphous crystals of quasi isostructural molecules such as barbituric and thiobarbituric acids and the triplet methyl, chloro and bromo benzyl alcohols, will be described. All co-crystals and solid solutions have been characterized via a combination of solid-state techniques, i.e. single crystal and powder X-ray diffraction, variable temperature X-ray diffraction, DSC, TGA and hot-stage microscopy (HSM). Keywords: organic co-crystals, ionic co-crystals, solid solutions [1] D. Braga, F. Grepioni, L.Maini, S. Prosperi, R. Gobetto and M. R. Chierotti, Chem. Commun., 2010, 46, [2] D. Braga, F. Grepioni, L. Maini, D. Capucci, S. Nanna, J.Wouters, L.Aerts and L. Quéré, Chem. Commun., 2012, 48, [3] F. Grepioni, J. Wouters, D. Braga, S. Nanna, B. Fours, G. Coquerel, G.Longfils, S.Rome, L. Aerts and Luc Quéré, CrystEngComm, 2014,16, [4] O. Shemchuk, D. Braga and F. Grepioni, Chem. Commun., 2016,52, [5] D. Braga, L. Degli Esposti, K. Rubini, O. Shemchuk and F. Grepioni, Cryst. Growth Des., DOI: /acs.cgd.6b April,

28 O-3 Self-Assembly of Metal-Organic Frameworks from Metal Oxides in Supercritical CO2 Cristina Mottillo, a,b Joseph Marrett, b CJ Li, a,b and Tomislav Friščić a,b a ACSYNAM, Inc., Montreal, QC, Canada; b Department of Chemistry, McGill University, Montreal, QC, Canada. cmottillo@acsynam.com For twenty years, metal-organic frameworks (MOFs) have been at the forefront of materials science. Their exceptional porosity and tunability have made them principal candidates for applications in gas storage, molecular separation, and catalysis.[1] While improving the functionality and stability of MOFs has seen substantial advancements, conventional routes to produce MOFs are often still solvent- and heat-intensive, in addition to requiring corrosive reagents.[2] The high yields and short reaction times of solid-state methods such as mechanochemistry[3] and accelerated aging[4] have made them greener alternatives to conventional solution-based methods. We now present a new environmentally-friendly methodology for the synthesis of MOFs using supercritical CO 2. The reaction of metal oxides (ZnO, CuO) and organic ligands in supercritical CO 2 affords the rapid (<1 min) self-assembly of MOFs on a gram scale. A systematic study of the effect of reaction conditions on the conversion of metal oxides in supercritical CO 2 and the formation of carbonates as reaction by-products reveals a strong temperature- and pressure-dependence. The rapid formation of MOFs in supercritical CO 2 thus presents a new avenue for the environmentally-friendly synthesis of MOFs, and reveals the surprising activation of metal oxides under supercritical conditions. Keywords: metal-organic frameworks, supercritical carbon dioxide, green chemistry [1] H. Furukawa, K. E. Cordova, M. O Keeffe, and O. M. Yaghi, Science, 2013, 341, [2] N. Stock, and S. Biswas, Chem. Rev., 2012, 112, 933. [3] D. E. Crawford, J. Casaban, R. Haydon, N. Giri, T. McNally, and S. L. James, Chem. Sci., 2015, 6, [4] C. Mottillo, Y. Lu, M.-H. Pham, M. J. Cliffe, T.-O. Do, and T. Friščić, Green Chem., 2013, 15, April, 2017

29 O-4 Understanding Long-Chain Melting Points, Interface Thermodynamics & F. L. Breusch J. Michael McBride a and Steven B. Bertman b a Department of Chemistry, Yale University, New Haven, CT , USA; b Department of Chemistry, Western Michigan University, Kalamazoo, MI , USA. j.mcbride@yale.edu An homologously isomorphous series of compounds can allow determination of local contributions to crystal properties, especially in long-chain compounds where a small unit-cell cross section concentrates the effect. Historically, melting points have contributed little to structural theory, but those of a series of diacyl peroxides allow the measurement of localized structural contributions to solid-state thermodynamics. Dramatic odd-even melting point alternation for terminally brominated homologues is due to a carbonbromine bond perpendicular to a lamellar interface making negative contributions to both the enthalpy and entropy of fusion, lowering the melting point by acting more liquid-like when in the crystal than when in the melt. Group increments in the following table (where the core values are for fusion of unsymmetrized undecanoyl peroxide, and the group increments are for substitution of a single terminal H atom) fit the melting points of 24 homologous peroxides to within an RMS deviation of 0.9 C. [1,2] The work of Friedrich Breusch ( ) provides a treasure trove of accurate melting points for at least 1242 long-chain compounds in 83 homologous series.[3] Cursory inspection of Breusch s results suggests that x-ray diffraction studies could provide valuable insight on determinants of the crystal packing. Why Breusch, a leading biochemist from 1930 to 1953, chose to devote the second half of his research career almost exclusively to synthesizing very pure long-chain homologues for the purpose of measuring their melting points relates to the modernization of Turkey and provides timely lessons about the plight of immigrants and resistance to tyranny. Keywords: interface thermodynamics, odd-even melting-point alternation, isomorphism [1] J. M. McBride, S. B. Bertman, D. Z. Cioffi, B. E. Segmuller, B. A. Weber, Mol. Cryst. Liq. Cryst. 1988, 161, 1. [2] J. M. McBride, S. B. Bertman, Isr. J. Chem. 2017, 57, 137. [3] F. L. Breusch, Fortschr. Chem. Forsch. 1969, 12, April,

30 O-5 The Way from Isostructurality to Polymorphism. Where are the Borders? Petra Bombicz Research Centre for Natural Sciences, Hungarian Academy of Sciences, H-1117 Budapest, Magyar Tudósok körútja 2., Hungary. The deeper and deeper understanding of the relationship between crystal and molecular structure and macroscopic properties contributes to the ability to prepare new crystalline substances with predefined physicochemical properties. It requires the recognition of structural features of materials including polymorphism and isostructurality [1] which are strongly related with intermolecular interactions [2] and crystal symmetries [3]. Fine-tuning of structural properties can be achieved by the application of substituents of different size, placement and functionality or in the case of multi-component systems by the introduction of molecules of different size, shape and chemical composition [1,3]. A firmly gradual transition in crystal packing arrangements can be realised through the chemical change. How far can a crystal structure tolerate small molecular changes without altering? What is the limit of close isostructurality? Is there a clear cut difference between polymorphic structures? The occurrence of common crystal packing patterns amongst polymorphs is frequent. Packing motifs organized by the determining supramolecular interactions may still be preserved in one or two dimensions but the motifs are moved related to each other by crystallographic or non-crystallographic rotations and / or translations. Whether or to what extent two crystals are significantly different, similar or identical? Where is the border between isostructurality and polymorphism? Is there necessarily a strict borderline between isostructurality and polymorphism [4]? How different do two crystal structures need to be to call them really different? How similar do two chemical compounds (conformation, configuration, tautomers) and two systems of supramolecular arrangements need to be to call them identical? Where are the borders between molecular and supramolecular similarity - dissimilarity? Are there only two extremes (structural similarity and dissimilarity) or is there a way in between [4]? Although polymorphism has been a hot topic for a long time, and there is progress in understanding, there are still numerous questions to answer. Keywords: supramolecular interactions, symmetry, crystal engineering [1] P. Bombicz, T. Gruber, C. Fischer, E. Weber and A. Kálmán, CrystEngComm. 2014, 16, [2] G. Resnati, E. Boldyreva, P. Bombicz and M. Kawano, IUCJ, 2015, 2, [3] P. Bombicz P, N.B. Báthori and A. Kálmán, Struct Chem. 2015, 26, [4] P. Bombicz, Cryst. Rev In press April, 2017

31 O-6 What Makes Solid Solution Happen? Matteo Lusi. a a Department of Chemical and Environmental Science, University of Limerick, Limerick, Ireland. matteo.lusi@ul.ie The performances of a crystalline material depend on the way molecular and atomic constituents are arranged in the space (structure) at least as they depend on the identity of those components (chemistry). Hence efficient materials with optimal properties for the intended application require the optimization of both structure and chemistry. In crystalline solid solutions many physicochemical and structural properties vary in continuum with composition so that property control coincides with chemical control. Unfortunately solubility in the solid is much rarer than in the liquid so much so that crystallization is often regarded as a purification technique. Nonetheless the application of simple designing principles can afford stable solid solutions of many organic and metalorganic species. Moreover the use of a variety of synthetic methods can further increase the chances of obtaining the desired mixed crystal. Here archetypal molecules are mixed together to investigate what makes a solid solution happen. Keywords: solid solutions, crystal engineering 2 7 April,

32 O-7 Halogenation as a New Tool to Control Peptide Self-Assembly Pierangelo Metrangolo, a,b Greta Bergamaschi, a Gabriella Cavallo, a Alessandro Gori, c Daniele Maiolo, a Claudia Pigliacelli, b Andrea Pizzi a and Giancarlo Terraneo a a Department of Chemistry, Materials, and Chemical Engineering Giulio Natta, Politecnico di Milano, Via L. Mancinelli 7, Milano 20131, Italy; b HYBER Centre of Excellence, Department of Applied Physics, Aalto University, P.O. Box 15100, FI-02150, Espoo, Finland. Istituto di Chimica del Riconoscimento Molecolare, CNR, Via Mario Bianco 9, Milano 20131, Italy. pierangelo.metrangolo@polimi.it Although many modifications of peptide sequences have been utilized to tune their self-assembly, halogenation has rarely been pursued. The advantage of a strategy based on the introduction of halogen atoms on peptide motifs lies in the fact that halogenation is a minimal structural modification, which, on the other hand, may induce a large difference in the peptide supramolecular behavior as a consequence of the rich variety of noncovalent interactions given by halogen atoms [1]. In this presentation, it will be shown how halogenation strongly influences both solution and solid-state self-assembly behavior of amyloidogenic peptides. We have applied this new supramolecular concept to the augmented fibrillation of amyloidogenic peptides and proteins, such DFNKF (Figure) [2], KLVFF, and hct. Implications of oxidative stress-induced halogenation of proteins are discussed in terms of biomarkers of diseases such as Parkinson and Alzheimer s. The obtainment of a novel unnatural amino acid functioning as strong halogen-bond donor may pave the way to totally new design principles in peptide-based supramolecular self-assembly. P.M. gratefully acknowledges the European Research Council (ERC) for funding the project Folding with Halogen Bonding to PM (FoldHalo, Grant agreement no ). Keywords: halogenation, peptide, self-assembly [1] A. Bertolani, A. Pizzi, L. Pirrie, L. Gazzera, G. Morra, M. Meli, G. Colombo, A. Genoni, G. Cavallo, G. Terraneo and P. Metrangolo, Chem. Eur. J., 2016, 22, DOI: /chem (Hot Paper and Front Cover). [2] A. Bertolani, L. Pirrie, L. Stefan, N. Houbenov, J. S. Haataja, L. Catalano, G. Terraneo, G. Giancane, L. Valli, R. Milani, O. Ikkala, G. Resnati and P. Metrangolo, Nature. Commun., 2015, 6, 7574, DOI: /ncomms April, 2017

33 O-8 New Experimental Techniques for Exploring Crystallization Pathways and Structural Properties of Solids Kenneth D.M. Harris School of Chemistry, Cardiff University, Park Place, Cardiff CF10 3AT, Wales. The lecture will highlight two experimental strategies that we have developed for exploring crystallization pathways and structural properties of solids: (i) in-situ solid-state NMR techniques for understanding the timeevolution of crystallization processes, and (ii) the study of X-ray birefringence and X-ray dichroism for determining the distribution of molecular orientations in materials. Our in-situ solid-state NMR technique [1-5] for studying crystallization pathways exploits the ability of NMR to selectively detect the solid phase in heterogeneous solid/liquid systems of the type that exist during crystallization from solution. We have shown that this technique can establish the sequence of solid phases formed during crystallization processes [1] and can be exploited in the discovery of new polymorphs [2]. Our most recent development is an in-situ NMR technique [3] that yields simultaneous information on the timeevolution of both the solid phase and the liquid phase during crystallization. This new strategy (called "CLASSIC NMR" [3-5]) extends significantly the scope and capability of in-situ NMR for gaining fundamental insights on the evolution of crystallization processes. Following our earlier studies of the phenomenon of X-ray birefringence [6,7], we recently reported [8] a new experimental set-up that allows spatially revolved measurements of X-ray birefringence to be carried out in "imaging mode". In many respects, this technique (called X-ray Birefringence Imaging) represents the X- ray analogue of the polarizing optical microscope. The lecture will describe the results obtained so far using this technique, demonstrating the utility and potential of X-ray Birefringence Imaging as a sensitive technique for imaging the local orientational properties of anisotropic materials [8]. Inter alia, the technique can be applied to characterize changes in molecular orientational ordering associated with solid-state phase transitions and to determine the size, spatial distribution and temperature dependence of domain structures in materials. We are also interested in the opportunity to exploit the related phenomenon of X-ray dichroism [9] as a strategy to explore molecular orientations in solids, and recent results [10] from the application of this technique will also be discussed. Keywords: solid-state NMR spectroscopy, crystallization, X-ray birefringence [1] C.E. Hughes, K.D.M. Harris, J. Phys. Chem. A, 2008, 112, [2] C.E. Hughes, P.A. Williams, T.R. Peskett, K.D.M. Harris, J. Phys. Chem. Lett., 2012, 3, [3] C.E. Hughes, P.A. Williams, K.D.M. Harris, Angew. Chemie Int. Ed., 2014, 53, [4] C.E. Hughes, P.A. Williams, V.L. Keast, V.G. Charalampopoulos, G.R. Edwards-Gau, K.D.M. Harris, Faraday Discuss., 2015, 179, 115. [5] K.D.M. Harris, C.E. Hughes, P.A. Williams, G.R. Edwards-Gau, Acta Crystallogr., 2017, C73, 137. [6] B.A. Palmer, A. Morte- Ródenas, B.M. Kariuki, K.D.M. Harris, S.P. Collins, J. Phys. Chem. Lett., 2011, 2, [7] B.A. Palmer, G.R. Edwards- Gau, A. Morte-Ródenas, B.M. Kariuki, G.K. Lim, K.D.M. Harris, I.P. Dolbnya, S.P. Collins, J. Phys. Chem. Lett., 2012, 3, [8] B.A. Palmer, G.R. Edwards-Gau, B.M. Kariuki, K.D.M. Harris, I.P. Dolbnya, S.P. Collins, Science, 2014, 344, [9] M.-H. Chao, B.M. Kariuki, K.D.M. Harris, S.P. Collins, D. Laundy, Angew. Chemie Int. Ed., 2003, 42, [10] B.A. Palmer, S.P. Collins, J. Hulliger, C.E. Hughes, K.D.M. Harris, J. Am. Chem. Soc., 2016, 138, April,

34 O-9 Self-Compression in Channel Inclusion Compounds Mark D. Hollingsworth, a Bo Wang, a Ilya S. Frantsuzov, a Shane M. Nichols, b Philippe Rabiller, c Céline Mariette, c Laurent Guérin, c and Bertrand Toudic c a Department of Chemistry, Kansas State University, 213 CBC Building, Manhattan, KS U.S.A.; b Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003; c Institute of Physics, University of Rennes 1, Rennes, France. mdholl@ksu.edu High local stress and accommodation of strain are dominant and controlling features of many solid-state reactions and in many mechanically responsive materials. A desirable goal is to find systems in which the effects of this stress are manifested and accommodated in understandable ways. Because of the rigidity of its helical host structure, which enables the stress to be confined to one dimension, urea inclusion compounds (UICs) serve as perfect models to study stress in solid-state reactions. UICs may be classified as either commensurate or incommensurate structures, depending on whether or not the ratio of guest and host repeat lengths along the channel axis (c g/c h) is a rational fraction with a low denominator. Although relatively few incommensurate UICs lock into commensurate phases upon cooling, lock-in accompanied by an elongation of c g raises the question of whether the remaining guest molecules are pushed out the ends of the channel or are compressed by the expanding phase. Using synchrotron-generated X-rays and very large detector distances, we have observed lock-in and selfcompression events in certain UICs. Following a ferroelastic phase transition in which the guest elongates to form a commensurate structure with the host, nucleation and growth of the lock-in phase triggers compression of other regions along the channel axis of the crystal. In one case, the sequence of progressively shorter structures is interrupted by further lock-in transitions, again achieved by elongation of compressed guest structures. These trigger even further compression of other guests along the same channels. Stress-transmission and lock-in behavior may be probed in a variety of ways with molecular analogs of systems undergoing self-compression, mixed crystals containing relaxive impurities, and deuteriumlabeled hosts and guests. Because stress transmission in crystals is ordinarily very complicated, selfcompression events in 1-D crystals may serve as paradigms for solid-state reactions in three-dimensional crystals. Keywords: self-compression, inclusion compound, phase transition April, 2017

35 O-10 Engineering Molecular Crystals: Backbreaking yet Gratifying Dejan-Krešimir Bučar Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, U.K In this contribution, we describe some of the hurdles encountered by our research group when studying each of the aspects of crystal engineering, namely designing, building and using crystal structures. Examples from our research will be used to illustrate the backbreaking nature of the crystal engineering endeavour, as well as the limitations of our current abilities to understand, engineer and maintain molecular crystals. 2 7 April,

36 O-11 Many Faces of Chiral Trianglimine Crystals Agnieszka Janiak a a Department of Chemistry, Adam Mickiewicz University, Umultowska 89B, Poznan , Poland. agnieszk@amu.edu.pl Since the award of the Nobel Prize in Chemistry to Cram, Lehn and Pedersen in 1987, unflagging interest in the chemistry of macrocyclic compounds has been observed. Recently, much effort has been made in the design and synthesis of purely organic macrocycles or cages that possess tunable functionality and the ability to form distinguishable extrinsic and intrinsic porous materials for the purpose of gas storage and separation.[1] Among them are the macrocyclic Schiff bases that offer a great promise for diversity with respect to size, geometry, stereochemistry and functionality. Trianglimine is a cyclic hexaimine of unique triangular molecular shape that has been synthesized through [3+3] cyclocondensation reaction between enantiomerically pure trans-1,2-diaminocyclohexane and terephthaldehyde.[2] The macrocycle obtained in this way possesses a relatively rigid skeleton with a welldefined inner cavity that is ready to include small guest molecules by means of size-shape complementarity. Although, the first structural reports on trianglimine appeared over ten years ago, the structure-property relationship of trianglimine under ambient and high pressure conditions have not yet been examined.[2b] Herein the solid state structures of the inclusion and apohost forms of trianglimine are reported. Aromatic solvents lead to the formation of solvated crystals while aliphatic solvents mostly lead to dimorphic solvent free forms wherein molecules assemble into microporous pillared structure with isolated 1D channels. Although, both apohost forms display similar crystal packing arrangement, only one of them shows a reversible phase transition as well as large thermal expansion while the other does not exhibit any remarkable thermal properties. Furthermore, in the apohost crystals a unique breathing behavior upon adsorption of carbon dioxide is observed. All these structural features will be presented. The work was supported by grant MAESTRO 2012/06/A/ST5/ Keywords: chiral macrocycle, single-crystal to single-crystal transformation, sorption and inclusion properties [1] M.J. Bojdys, T. Hasell, N. Severin, K.E. Jelfs, J.P. Rabe, A.I. Cooper, Chem. Commun., 2012, 48, [2] (a) The chiral trianglimine was synthesized by Dr hab. Marcin Kwit at the Faculty of Chemistry, Adam Mickiewicz University, Poznan, Poland. (b) J. Gawronski, H. Kołbon, M. Kwit, A.Katrusiak, J. Org. Chem, 2000, 65, April, 2017

37 O-12 Short-Range Interactions in 1:1 Adducts Formed by C6F6 Jeremy K. Cockcroft, a Ronen E. Ghosh, a Jacob J. Shephard, a Anjali Singh a and Jeffrey H. Williams b a Department of Chemistry, UCL, Christopher Ingold Laboratories, 20 Gordon Street, London WC1H 0AJ, United Kingdom; b Montpellier, France (formerly at the BIPM, Pavillon de Breteuil, Sèvres, France). j.k.cockcroft@ucl.ac.uk A recent variable temperature X-ray diffraction study has been used to probe the balance between structure and dynamics of the solid adducts of 1,3,5-trimethylbenzene (mesitylene) and hexafluorobenzene[1]. PXRD patterns and DSC traces of near equimolar mixtures reveal two solid-state phase-transitions at K and K. The crystal structures of all three solid phases of this material have been solved by SXD after a serendipitous observation that single crystals could survive (despite twinning in phase II) through both phase transitions down to the lowest temperature phase. In marked contrast to our earlier studies on the adduct formed by benzene and hexafluorobenzene, in which molecules are equispaced along columns and begin to rotate with increasing temperature, there is a distinct pairing of the mesitylene and hexafluorobenzene molecules in all three phases of this adduct. In each phase, there are close-packed parallel columns of alternating C 6H 3(CH 3) 3 and C 6F 6 molecules packed face to face in a staggered conformation with significant interactions between columns. Thermal motions of the molecules can be deduced from an accurate determination of the atomic displacement parameters which provide evidence of librational motion of the mesitylene molecule about its centre of mass in contrast to that the of the hexafluorobenzene molecule (as seen in the Figure below). More importantly, this adduct provides evidence of a significant interaction between the fluorine atoms in C 6F 6 with the methyl-groups in mesitylene. Differences in structure between the three phases illustrate the subtle interplay of quadrupole versus bond-dipole electrostatic interactions with changing temperature. The talk will compare and contrast the behaviour in this system with that exhibited by similar adducts. Keywords: binary adducts, fluorine-methyl interactions, phase transitions [1] J. K. Cockcroft, R.E.Ghosh, J. J. Shephard, A. Singh, J. H. Williams, submitted Nov April,

38 O-13 The Role of the Ligand in Formation of Iron(III) Supramolecular Gels Savannah Zacharias a Susan A. Bourne a and Gaëlle Ramon a a Department of Chemistry, University of Cape Town, Private Bag, Rondebosch 7701, South Africa. zchsav001@myuct.ac.za The field of supramolecular gels is challenging as predicting their formation can be problematic. Due to these challenges they are often discovered in the pursuit of other materials. Since gels have interesting properties they are being investigated for use in future applications, such as drug delivery, crystal growth media and energy capture [1], and because of this they have recently attracted a great deal of attention [2]. Supramolecular gels are soft materials and their study overlaps with that of crystal engineering as the interactions involved in their formation are closely related. In this presentation, the role of the organic ligand in the formation of gels will be explored. A range of small carboxylic acids and solvents were used to investigate their respective roles in gel formation. Systematic study showed that those from ligands with carboxylate moieties in the ortho position passed the inverted vial test [3] most consistently. Gels formed when solvents ethanol (EtOH), propanol, and dimethylformamide (DMF) were used, while benzonitrile and acetonitrile did not form gels. Two supramolecular gels synthesized from iron(iii) salts with trimesic acid and 5-nitroisophthalic acid will be presented. The wet gels proved to be difficult to characterise as most signals (specifically those of infrared spectra) were masked by the solvent and thermogravimetric analysis (TG) indicated that the majority of the gel was solvent. Drying the gels by heating or by freeze drying allowed them to be better characterised. In all cases solvent was still present and TG gave a profile of desolvation and decomposition. Contributions due to the solvent are also present in the infra-red spectra, nevertheless it is possible to see changes in the spectra attributable to the supramolecular interactions involved. There is also evidence of local structure in the powder x-ray diffraction (PXRD) patterns of the dry gels. Microwave plasma atomic emission spectroscopy (MP-AES) was used to determine the percentage of iron(iii) in the dried samples. UV-vis spectroscopy was used to study the sorption behavior of the gels which take up various dyes, such as methyl red and bromocresol green, from solution. This has potential use in the textile industry which produces a large amount of waste each year. Separation of alcohols using the gels was also investigated. Crystals were grown from one of the gels using a pre-described methodology involving degrading the gel using PdCl 2 [4]. Keywords: gel, UV-vis, thermal [1] G. Yu, X. Yan, C. Han and F. Huang, Chem. Soc. Rev., 2013, 42, [2] R. C. T. Howe, A. P. Smalley, A. M. P. Guttenplan, M. W. R. Doggett, M. D. Eddleston, J-C. Tan and G. O. Lloyd, Chem. Commun., 2013, 49, [3] J. W. Steed and J. L. Atwood, Supramolecular Chemistry, 2 nd Ed., 2009, 888. [4] H. B. Aiyappa, S. Saha, B. Garai, J. Thote, S. Kurungot and R. Banerjee, Cryst. Growth Des. 2014, 14, April, 2017

39 O-14 Discovering and Understanding Mechanochemistry Tomislav Friščić Department of Chemistry, McGill University, 801 Sherbrooke St. W. Montreal, Canada. Solid-state reactions, and in particular mechanochemistry,[1] are emerging as increasingly popular alternatives to conventional solution-based or thermochemical synthesis. The advantages of mechanochemistry in chemical synthesis and materials science are many, including short reaction times, access to reactions, molecular targets or extended framework structures that are difficult or even claimed to impossible to make in solution. In contrast to such advantages, which have been demonstrated in the contexts of organic,[2] organometallic[3] and pharmaceutical synthesis,[4] as well as chemistry of metal-organic frameworks (MOFs)[5] and nanomaterials,[6] the mechanisms underlying mechanochemical reactions remain poorly understood. This presentation will outline some of the recent applications of mechanochemistry in reaction discovery,[7] synthesis of previously unreachable molecules,[1] as well as present the recent advances in understanding the underlying mechanisms. In particular, we will describe the group's recent accomplishments in following mechanochemical reaction mechanisms by using in situ reaction monitoring methods based on X-ray diffraction and different spectroscopic methods. This will be combined with a brief outline of using solid-state modelling and calorimetric studies to understand the course of mechanochemical reactions. Keywords: Mechanochemistry, mechanisms, reaction discovery, Green Chemistry [1] J.-L. Do and T. Friščić, ACS Cent. Sci., 2017, 3, 13. [2] G. W. Wang, Chem. Soc. Rev., 2013, 42, [3] N. R. Rightmire and T. P. Hanusa, Dalton Trans., 2016, 45, [4] D. Tan, L. Loots and T. Friščić, Chem. Commun., 2016, 52, [5] C. Mottillo and T. Friščić, Molecules, 2017, 22, 144. [6] K. Korpany, C. Mottillo, J. Bachelder, P. Dong, S. Trudel, T. Friščić and A. S. Blum, Chem. Commun., 2016, 52, [7] D. Tan and T. Friščić, Chem. Commun., 2017, 53, April,

40 O-15 Self-Healing Molecular Crystals Patrick Commins, Marieh B. Al-Handawi and Panče Naumov New York University Abu Dhabi, PO Box , Abu Dhabi, United Arab Emirates. One of the most inevitable limitations of any material that is exposed to mechanical impact is that they are inexorably prone to mechanical damage, such as cracking, denting, gouging or wearing. To confront this challenge, the field of polymers has developed materials that are capable of autonomous self-healing and recover their macroscopic integrity similar to biological organisms. However the study of this phenomenon has mostly remained within the soft materials community and has not been explored by solid-state organic chemists. Having polymers as a source of inspiration, the design of a self-healing crystal required the selection of a chemically reactive reaction system that would be applicable to molecular crystals. Microencapsulate[1] and nanoparticle-based polymers[2] and other multicomponent materials were omitted since they cannot be realized with molecular crystals. Other self-healing polymers that are based on Diels-Alder cycloaddition[3] or ligand exchange reactions[4] were also not applicable since they would require introduction of supramolecular templates.[5] Instead, we drew ideas from dynamic covalent chemistry, which utilizes molecules that undergo rapid reversible bond formations.[6,7] Here we report the first evidence of self-healing in a molecular crystal using crystals of dipyrazolethiuram disulfide.[8] The crystals exhibit about 6.7% healing at ambient conditions, with no other external stimuli other than moderate mechanical compression. We postulate the disulfide shuffling mechanism is responsible for the self-healing property. The crystal structure of contains three different S---S contacts that are proximal and they may be capable of forming new bonds. The radicals proposed for the shuffling mechanism are also observed, and a degree of mass transfer necessary to span the interstitial gaps in between the two interfaces was also found. We now have evidence that other molecular crystals are also be capable of this phenomenon. These findings show that the self-healing property can be extended beyond mesophasic materials and applied towards the realm of ordered solid-state compounds. Keywords: dynamic covalent chemistry, molecular crystals, self-healing [1] R. S. Trask, G. J. Williams, I. P. Bond, J. R. Soc. Interface 2007, 4, 363. [2] J. Y. Lee, G. A. Buxton, A. C. Balazs, J. Chem. Phys. 2004, 121, [3] Y. Zhang, A. A. Broekhuis, F. Picchioni, Macromolecules 2009, 42, [4] Y. Shi, M. Wang, C. Ma. Y. Wang. X. Li. G. Yu, Nano Lett. 2015, 15, [5] T. Friščić, L. R. MacGillivray, Chem. Comm. 2003, [6] Y. Jin, C. Yu, R. J. Denman, W. Zhang, Chem. Soc. Rev. 2013, 42, [7] A. Hermann, Chem. Soc. Rev. 2014, 43, [8] P. Commins, H. Hara and P. Naumov, Angew. Chem. Int. Ed., 2016, 55, April, 2017

41 O-16 Organosuperelasticity: New Physical Element in Chemistry Satoshi Takamizawa a a Graduate School of Nanobioscience, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama, Kanagawa , Japan. staka@yokohama-cu.ac.jp All materials including living things have elasticity and plasticity for shape preservation and shock absorption when recceiving forces. Elastic deformation is shape recoverble with generated recovery force until exceeding the certain limit of strain or force to allow ensuing plastic deformation. (Scheme 1) The special elastic materials are known as so useful. Rubber is most representative with a large strain limit due to the fluidic property. However, typical solids such as metals have a small strain limit in elasticity but a relatively large one in plasticity. It would be amazing if the solid restores its shape after large plastic deformation. Such special elasticity is called "superelasticity" and has been found in a specific kind of metal alloys named "shape-memory alloys (superelastic alloys)," which are utilized as cathethers, stents, orthodonic wires, eyeglass frames, etc.[1] Heavyness, hardness, magnetism, and toxity of metallic materials sometimes cause problems especially for medical usages. Thus, organic substitution has been required while superelastic organic materials have not been obvious over eight decades since superelasticity was first discovered in a Au-Cd alloy in 1932.[2] My group found some organic solids superelastic.[3] Thus, superelasticity has been introduced into chemistry as a new physical element, which can be called "Organosuperelasticity." The first reported compound was a pure organic crystal of terephthalamide, which precisely produces a large motion with high repetition and high energy storage efficiency driven by a small shear stress due to the low density of strain energy related to the low lattice energy. We have succeeded in detemining the superelasticity and alloys-like shape-memory effect in some organic crystals.[4] Considering currently expected applications of superelastic and shapememory alloys, "organosuperelasticity" would have the potential newness to develop the new science of superelastic materials by material diversification and functionalization since chemical design can be effectively applied. Keywords: Organosuperelastcity [1] For example, K. Otsuka and C. M. Wayman, in Shape memory materials, Cambridge University Press, Cabridge, [2] A. Ölander, J. Am. Chem. Soc,1932, 54, 3819 (1932). [3] S. Takamizawa, Y. Miyamoto, Angew. Chem. Int. Ed., 2014, 53, [4] S. Takamizawa, Y. Takasaki, Chem. Sci., 2016, 7, (First published online 19 Nov 2015). 2 7 April,

42 O-17 Using LFP to Elucidate Bimolecular Reaction Mechanisms in Crystals Anna D. Gudmundsdottir, a Dylan Shields a and Sujan Sarkar a a Department of Chemistry, University of Cincinnati, Cincinnati, OH 45220, USA. annag@uc.edu We investigated the photochemistry of series of crystalline naphthoquinone derivatives, and found that they dimerize selectively in the solid-state. Laser flash photolysis of nano-crystalline naphthoquinones verifies that the reactions takes place on the triplet surface of the molecules and in a stepwise manner. In crystal lattices that are perfectly lined up for dimerization, the triplet excited state of the naphthoquinone was observed directly, which decayed to form short lived 1,4-biradicals. In comparison, in crystal lattices which were not well oriented for dimerization, the resulting 1,4-biradicals become long-lived. Thus, correlation of the solid-state kinetics and the X-ray structure of the naphthoquinone derivatives made it possible to elucidate the solid-state mechanisms, and explain how the crystal lattices impedes some bond formation and facilitates others. DFT calculations were used to further support the reactions mechanism. Keywords: laser flash photolysis of nanocrystals, solid state photochemistry, x-ray structures April, 2017

43 O-18 Designing Low Symmetry Photo-Responsive Metal Organic Frameworks Jason Benedict, Eric Sylvester and Travis Mitchell Department of Chemistry, University at Buffalo, SUNY, 771 Natural Sciences Complex, Buffalo, NY , USA. Photochromic technologies have the potential to transform traditionally passive materials into active materials which change their chemical or electronic properties in response to light stimulus. One of the newest emerging applications for photochromic technologies is the development of photo-responsive metalorganic frameworks (MOFs): highly porous crystalline frameworks capable of undergoing structural reorganization upon application of light.[1-4] Despite the crystalline nature of these materials, the photoactive portions of the structures often lack a high degree of structural organization.[5, 6] Our recent efforts to overcome these challenges include the design, synthesis, and characterization of low-symmetry linkers which permute or eliminate common structural motifs that lead to high-symmetry structures. Several new zwitterionic chiral linkers will be presented along with MOFs produced from these ligands. Keywords: Photo-responsive, Metal-organic framework, Zwitterionic materials [1] A. Modrow, D. Zargarani, R. Herges and N. Stock, Dalton Trans., 2011, 40, [2] J. W. Brown, B. L. Henderson, M. D. Kiesz, A. C. Whalley, W. Morris, S. Grunder, H. Deng, H. Furukawa, J. I. Zink, J. F. Stoddart and O. M. Yaghi, Chemical Science, 2013, 4, [3] N. Yanai, T. Uemura, M. Inoue, R. Matsuda, T. Fukushima, M. Tsujimoto, S. Isoda and S. Kitagawa, J. Am. Chem. Soc., 2012, 134, [4] D. G. D. Patel, I. M. Walton, J. M. Cox, C. J. Gleason, D. R. Butzer and J. B. Benedict, Chem. Commun. (Cambridge, U. K.), 2014, 50, [5] I. M. Walton, J. M. Cox, C. A. Benson, D. G. Patel, Y.-S. Chen and J. B. Benedict, New J. Chem., 2016, 40, [6] I. M. Walton, J. M. Cox, T. B. Mitchell, N. P. Bizier and J. B. Benedict, CrystEngComm, 2016, 18, April,

44 O-19 Molecular Dynamics from Slow Diffraction Experiments Manuel A. Fernandes, Sanaz Khorasani, Delbert S. Botes and Demetrius C. Levendis Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, PO WITS 2050, South Africa Reactions in the solid-state offer the unique advantage that the movement of molecules and atoms can be monitored using X-ray diffraction methods. This approach is particularly useful if the reaction occurs in a single crystal which remains intact during the course of the reaction a so called single-crystal-to-single-crystal (SCSC) reaction. However, such reactions are relatively uncommon as the reaction process itself more often than not leads to complete crystal disintegration. One class of compounds which typically remains intact during a solid-state reaction are the charge transfer (CT) complexes of dithiin compounds which undergo solid-state Diels-Alder reaction with anthracene to yield cycloadduct products.[1,2] These reactions typically occur over times scales of minutes to weeks at ambient temperatures. While slow, significant conformational changes and molecular motion often occurs, allowing information about the reaction process to be obtained through laboratory diffraction experiments. Several mechanisms have been proposed to explain how molecular reactions occur in the solid state.[3] Of relevance to this work are the topochemical principle, the concept of a reaction cavity, and the identification of possible reaction affecting feedback mechanisms. In some cases the result can be rather surprising. For example, solid-state reaction in the above crystal structure leads to a synthetic co-crystal where two stacked arrangement of molecules (or a mixture of these) is theoretically possible. In practice only one of these is obtained. In other examples the direction of the reaction can be influenced (and in some cases even inhibited) by altering the substituents on the reacting molecules. In this paper we present some examples of our work on solid-state reactions where feedback mechanisms between molecules during a reaction influence the structure of the final crystal. Keywords: topochemical principle, solid-state reaction, reaction cooperativity [1] S. Khorasani, M.A. Fernandes, Cryst. Growth Des., 2013, 13, [2] S. Khorasani, D. S. Botes, M. A. Fernandes and D. C. Levendis, CrystEngComm, 2015, 17, [3] I. Halasz, Cryst. Growth Des., 2010, 10, April, 2017

45 O-20 Crystalline Supramolecular Rotors Assembled through Halogen Bonding Giancarlo Terraneo, a Luca Catalano, a Salvador Pérez-Estrada, b Pierangelo Metrangolo a and Miguel A. Garcia-Garibay b a Laboratory of Nanostructured Fluorinated Materials (NFMLab), Department of Chemistry, Materials, and Chemical Engineering "Giulio Natta", Politecnico di Milano, via L. Mancinelli 7, Milano, Italy; b Department of Chemistry and Biochemistry, University of California, Los Angeles, California , USA. giancarlo.terraneo@polimi.it. Amphidynamic crystals are materials designed to possess rapidly moving components (rotators) in the solid state.[1] Typically, molecular design in this field has taken inspiration from structures akin to those of macroscopic compasses and gyroscopes to explore and control rotation in the solid state.[2] Rotation in solids has been studied in molecular crystals, inclusion compounds, metal organic frameworks (MOFs), porous molecularly ordered (PMO) silicates, and amorphous solids. [3] In this communication, we report a crystal engineering approach where stators and rotators are assembled in cocrystals resulting in the high-yield synthesis of active supramolecular rotor arrays. Advantages of this strategy originate from its intrinsic flexibility and its modular design, thanks to the wide variety of supramolecular synthons available in the crystal engineering toolbox. Specifically the supramolecular rotors, discussed here, have been assembled through halogen bond. [4] Halogen bond has been recognized to be a strong, directional and tunable non-covalent interaction and could provide an extra value in the design of cocrystals showing dynamic components. We studied molecular motions of a series of halogen-bonded cocrystals involving 1,4-diazabicylo[2.2.2]-octane (DABCO) and several differently functionalized halobenzenes. Crystal structures, dynamic performances and thermodynamic parameters of the halogen bonded supramolecular rotors will be present and discussed highlighting similarities and differences between halogen bonded rotors.[5,6] For example in one system the fast rotation of DABCO follows a six-fold potential energy surface with three lowest energy minima showing a very low activation energy, the lowest reported in the field of amphidynamic crystals. Keywords: Supramolecular rotor, halogen bond, amphidynamic crystal [1] C.S. Vogelsberg and M.A. Garcia-Garibay, Chem. Soc. Rev. 2012, 41, [2] X. Hou, C. Ke, C.J. Bruns, P.R. Mc Gonigal, R. B. Pettman and J.F. Stoddart, Nat. Commun. 2015, 6, [3] For some examples see: (a) A. Comotti, S. Bracco, A. Yamamoto, M. Beretta, T. Hirukawa, M. Tohnai, M. Miyata and P. Sozzani, J. Am. Chem. Soc. 2014, 136, 618; (b) S.L. Gould, D. Tranchemontagne, O.M. Yaghi and M.A. Garcia-Garibay, J. Am. Chem. Soc. 2008, 130, [4] G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A. Priimagi, G. Resnati and G. Terraneo, Chem. Rev. 2016, 116, [5] L. Catalano, S. Pérez-Estrada, G. Terraneo, T. Pilati, G. Resnati, P. Metrangolo and M.A. Garcia-Garibay, J. Am. Chem. Soc. 2015, 137, [6] L. Catalano, S. Perez-Estrada, S.-H. Wang, A.J.-L. Ayitou, S. Khan, G. Terraneo, P. Metrangolo, S. Brown and M.A. Garcia-Garibay J. Am. Chem. Soc. submitted 2 7 April,

46 O-21 Organic Materials Based on Very Strong Halogen Bonds Kari Rissanen a Department of Chemistry, University of Jyväskylä, Survontie 9 B, Jyväskylä, Finland, kari.t.rissanen@jyu.fi In the last 15 years growing attention has been focused to halogen bonding (XB) 1 stimulated by its intriguing properties, such as strong directionality, specificity and strength comparable to hydrogen bonding (HB).[2] Recently, we have applied this long lost brother of hydrogen bonding[3] to very strong (OC) 2N-I N halogen bonds using N-iodosuccinimide (NIS) as the XB donor and hexamethylenetetramine (HMTA) as the XB acceptor,[4-5] where the iodine at the N atom is strongly polarized by the two electron withdrawing carbonyl groups. Inspired by the strong N-I polarization in NIS, and in an endeavour to polarize the N-I bond even further, an analogues N-iodosaccharin (NISac) was used as an alternative XB donor. Using pyridine N- oxides as the XB acceptor led to a new - N-X + - O-N + paradigm for halogen bonding[6] and have yielded extremely strong halogen bonded complexes with very high association constants characterized in either CDCl 3 or acetone-d 6 solution by 1 H NMR titrations and in the solid-state by single crystal X-ray analysis. The obtained halogen bond interactions, R XB, in the solid-state are found to be in the order of strong hydrogen bonds, viz. R XB R HB. The robustness of the - N-X + - O-N + XB motif is evident in the X-ray structure of the XB complex of NIS, where besides the XB formation the co-crystallized water molecule bridges two NIS complexes generating a dimeric assembly held together with concerted XB and HB interactions as shown in figure below. The carbonyl oxygen atoms act as weak HB acceptors indicating tolerance of the XB complex even under moist conditions. Most recently we have managed to create an extremely robust molcular capsules with the help of [N I + N] halogen bonds.[7] Keywords: halogen bond, organic materials, solid state structure [1] G. R. Desiraju, P. S. Ho, L. Kloo, A. C. Legon, R. Marquardt, P. Metrangolo, P. Politzer, G. Resnati, K. Rissanen, Pure Appl. Chem. 2013, 85, [2] E. Arunan, G. R. Desiraju, R. A. Klein, J. Sadlej, S. Scheiner, I. Alkorta, D. C. Clary, R. H. Crabtree, J. J. Dannenberg, P. Hobza, H. G. Kjaergaard, A. C. Legon, B. Mennucci, D. J. Nesbitt, Pure Appl. Chem. 2011, 83, [3] K. Rissanen, CrystEngComm 2008, 10, [4] K. Raatikainen, K. Rissanen, CrystEngComm, 2011, 13, [5] K. Raatikainen, K. Rissanen, Chem. Sci. 2012, 3, [6] R. Puttreddy, O. Jurček, S. Bhowmik, T. Mäkelä, K. Rissanen, Chem. Commun. 2016, 52, [7] L. Turunen, U. Warzok, R. Puttreddy, N. K. Beyeh, C. A. Schalley and K. Rissanen, Angew. Chem. Int. Ed. 2016, 55, in press. DOI: /anie April, 2017

47 O-22 Perspectives in Molecular Tectonics: From Crystals to Networks of Crystals Mir Wais Hosseini Laboratoire de Tectonique Moléculaire, UMR UDS-CNRS 7140, University of Strasbourg, Institut Le Bel, 4, rue Blaise Pascal, Strasbourg, France. Bridging the gap between microscopic (atoms and molecules) and macroscopic (materials) worlds is challenging and requires construction strategies. Both for fundamental and applied sciences, the design of complex molecular systems in the crystalline phase with strict control of order and periodicity at both microscopic and macroscopic levels is of prime importance for developments of new solid state materials and devices. The design and fabrication of complex crystalline systems as networks of crystals displaying task specific properties is a step towards smart materials. Here we report on isostructural and almost isometric molecular crystals of different colours, their use for fabrication of core-shell crystals and their welding, by 3D epitaxial growth, into networks of crystals as single crystalline entities. Welding of crystals by self-assembly processes into macroscopic networks of crystals is a powerful strategy for the design of hierarchically organised periodic complex architectures composed of different subdomains displaying targeted characteristics. Crystal welding, may be regarded as a first step towards the design of new hierarchically organized complex crystalline systems. [1] M. W. Hosseini, CrystEngComm., 2004, 6, 318. [2] M. W. Hosseini, Acc. Chem. Res., 2005, 38, 313. [3] M. W. HOsseini, Chem. Commun., Focus Article, 2005, 582. [4] G. Marinescu, S. Ferlay, N. Kyritsakas, M. W. Hosseini, Chem. Commun., 2013, 49, [5] C. Adolf, S. Ferlay, M. W. Hosseini, J. Am. Chem. Soc. 2015, 137, [6] F. Zhang, C. R. R. Adolf, N. Zigon, S. Ferlay, N. Kyritsaka, M. W. Hosseini, Chem. Commun., 2017, DOI: /C7CC01455D. 2 7 April,

48 O-23 Tuning Luminescence and Photoreactivity in Organic Cocrystals and Salts Fabrizia Grepioni, a Simone d Agostino, a Floriana Spinelli, a Dario Braga, a Barbara Ventura b a Dipartimento di Chimica Giacomo Ciamician, Università degli Studi di Bologna, Via Selmi, 2, Bologna, Italy; b CNR, Bologna, Italy. fabrizia.grepioni@unibo.it Molecular crystal engineering, i.e. the design and synthesis of solid state molecular materials with predefined properties, is used here to exploit non-covalent interactions to pre-arrange buiding blocks in their crystalline state for properties modification and specific applications, all involving the absorption of UV radiation. Depending on the chemical complexity and/or application, crystals of appropriate size and purity are required for characterization, chemical reactivity and applicative processes. Examples will be presented; among them: (i) single crystal to single crystal photodimerization of cinnamic acid derivatives and the effect of crystal size on the solid-state reactivity; (ii) co-crystallization as a tool to switch from fluorescence to phosphorescence in the solid state; (iii) molecular crystals for dye-sensitized solar cells applications. Keywords: co-crystals, luminescence, solid-state photodimerizations [1] B. Ventura, A. Bertocco, D. Braga, L. Catalano, S. d Agostino, F. Grepioni, and P. Taddei, J. Phys. Chem. C, 2014, 118, [2] F. Grepioni, S. d'agostino, D. Braga, A. Bertocco, L. Catalano and B. Ventura, J. Mater. Chem. C, 2015, 3, [3] S. d Agostino, F. Grepioni, D. Braga, and B. Ventura, Cryst. Growth Des., 2015, 15, [4] S. d Agostino, F. Spinelli, E. Boanini, D. Braga and Fabrizia Grepioni, Chem. Comm, 2016, 52, April, 2017

49 O-24 Preferential Enrichment: Effect of Cocrystallization of Racemic Compounds Hiroki Takahashi, a Yuki Numao, b Yousuke Hanakawa, b Junko Motokawa, a Hirohito Tsue a and Rui Tamura a a Graduate School of Human & Environmental Studies, Kyoto University, Kyoto , Japan; b Faculty of Integrated Human Studies, Kyoto University, Kyoto , Japan. takahashi.hiroki.2x@kyoto-u.ac.jp Preferential enrichment (PE) is a unique, chiral symmetry-breaking spontaneous enantiomeric resolution phenomenon that is caused by the polymorphic transition of an incipient metastable polymorphic form into a thermodynamically more stable form during crystallization from the supersaturated solution of a certain kind of racemic crystals (Figure a).[1] We have reported that the 1:1 cocrystal of a racemic compound DL-arginine (Arg) with fumaric acid shows an excellent PE phenomenon under nonequilibrium crystallization conditions starting from the racemic supersaturated solution, whereas PE is not feasible for free DL-Arg.[2] This result indicates that the twocomponent crystal formation contributes to produce the requisite molecular arrangement, which can induce an appropriate phase transition during crystallization to result in the occurrence of excellent PE. Here we report that the 1:1 cocrystal (1 INA) of a racemic propionic acid compound 1 with isonicotinamide (INA) shows an excellent PE (enrichment up to 92 % ee in the mother liquor) whenever the racemic sample is recrystallized from the 4.5 fold supersaturated 2-PrOH solution, whereas free racemic 1 (space group P-1)[3] exhibits a modest PE (up to 23% ee) only when the slightly R or S enriched sample is used for recrystallization. The PE behavior of 1 INA is slightly different from that of the compounds showing PE thus far;[1,2] i) the space group of the stable crystal of 1 INA is not P-1 but P2 1/n, ii) two polymorphs (a- and b-forms) were concomitantly formed during the crystallization of 1 INA, and iii) PE can occur in the low supersaturated solution (1.5 fold vs. solubility at 20 C). We discuss the mechanism of this unique PE phenomenon observed for 1 INA on the basis of the nature of these two polymorphs investigated by XRPD measurement, DSC and in situ ATR-FTIR spectroscopy. Keywords: enantiomeric resolution, polymorphic transition, cocrystals [1] (a) R. Tamura, H. Takahashi, D. Fujimoto and T. Ushio, Top. Curr. Chem., 2007, 269, 53; (b) R. Tamura, R. G. Gonnade and S. Iwama, CrystEngComm, 2011, 13, 5269; (c) S. Iwama, H. Takahashi, H. Tsue and R. Tamura, Cryst. Growth Des. 2015, 15, 3052; (d) Y. Uchida, S. Iwama, G. Coquerel and R. Tamura, Chem. Eur. J., 2016, 22, [2] S. Iwama, K. Kuyama, Y. Mori, K. Manoj, R. G. Gonnade, K. Suzuki, C. E. Hughes, P. A. Williams, K. D. M. Harris, S. Veesler, H. Takahashi, H. Tsue and R. Tamura, Chem. Eur. J., 2014, 20, [3] G. Smith, C. H. L. Kennard, W. L. Duax, C. Dale and D. C. Swenson, Aust. J. Chem., 1982, 35, April,

50 O-25 Cryochemical Synthesis and Antibacterial Activity of Hybrid Compositions Included Ag and Cu Nanoparticles in Nanocrystals of Antibiotics Tatyana I. Shabatina a, Olga I. Vernaya a, Anastassia V. Nuzhdina a, Vladimir.P. Shabatin a, Alexander M. Semenov b, Michail Ya. Melnikov a a Departments of Chemistry and b Biology, M.V. Lomonosov Moscow State University, Leninskie Gory 1-3 Moscow , Russia. tatyanashabatina@yandex.ru Wide and not always reasonable use of antibiotics and other antimicrobial agents in medicine has led to the emergence of many resistant strains of microorganisms. In our days, this problem is solved by the synthesis of new antibiotics and simultaneous use of antibiotics and metals nanoparticles. Cryochemical modification is a powerful method of reducing the size of drug substances particles, changing their form and crystal structure in order to improve their pharmaceutical properties. A possible application of this method is to obtain hybrid nano-compositions of metal particles and drugs. Antibacterial compositions were produced by low temperature freeze drying technique of water solution containing compositions including Ag or Cu nanoparticles and dioxidine or gentamicin. TEM, electron microdiffraction, UV absorption spectroscopy, X-ray diffraction, differential thermal analysis (DTA), Fourier transformation infrared spectroscopy (FTIR) showed the presence in the compositions of Cu/Ag nanoparticles of 5-70 nm in diameter and nanoparticles of antibiotic of nm in diameter (Fig.1). New cryoformed hybrid nanosized compositions of metal particles and antibiotic demonstrates higher antibacterial activity against Escherichia coli 52 compared to the original drug and metal nanoparticles. The work was financially supported by Russian Scientific Foundation (grant RSN ). Keywords: hybrid nanosystems, antibiotics, metal nanoparticles April, 2017

51 O-26 Evolution of Photoredox Catalysis: Out of the Solvent and into the Solid State Vjekoslav Štrukil a a Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička cesta 54, Zagreb, Croatia. vstrukil@irb.hr Recent years have witnessed a tremendous progress in the field of visible light photoredox catalysis (VLPRC). Utilizing metal complexes or organic dyes as photocatalysts in single-electron transfer processes enables visible light to be converted to chemical energy required to activate small organic molecules. Various types of reactions, e.g. amine functionalizations, alcohol deoxygenation, thiol-ene additions, trifluoromethylations etc. have been catalyzed under visible light irradiation. Particularly interesting approach is the combination of photocatalysis with organo- or metal-catalysis. This methodology extends further to large-scale processing by the development of flow reactors suitable for VLPRC, used in the production of pharmaceutically relevant compounds. [1] While all of the published material dealing with VLPRC is focused on solution chemistry, the alternative approach of transferring these reactions to the solid state has not yet been addressed. Bearing in mind the positive environmental impact of solvent-free organic reactions, VLPRC could greatly benefit from reduction or complete elimination of solvents from synthesis steps. [2] In that respect, aging [3] and mechanochemical ball-milling [4] are attractive solid state synthetic techniques that have come to the forefront of clean and efficient green synthesis of chemicals. A photoredox-catalyzed oxidation of alkynes [5] has been selected as a model reaction to demonstrate the effectiveness of solid state approach in VLPRC. Different photocatalysts, solid auxiliaries/supports and light sources have been screened. The intrinsically motionless aging methodology, together with the dynamic conditions of ball-milling, have been compared to photocatalysis in solution. Whereas light is the principal driving force in all VLPRC reactions, in this case ball-milling has proved as an efficient means to increase mass transfer and therefore facilitate the photocatalysis in the solid state. Keywords: photoredox catalysis, solid state, aging, ball-milling [1] M. H. Shaw, J. Twilton and D. W. C. MacMillan, J. Org. Chem., 2016, 81, [2] K. Tanaka and F. Toda, Chem. Rev., 2000, 100, [3] M. J. Cliffe, C. Mottillo, R. S. Stein, D.-K. Bučar and T. Friščić, Chem. Sci., 2012, 3, [4] D. Margetić and V. Štrukil, Mechanochemical Organic Synthesis, Elsevier, [5] X. Liu, T. Cong, P. Liu and P. Sun, J. Org. Chem., 2016, 81, April,

52 O-27 Substituent Influence on Self-Assembly of Pharmaceutical Drug Compounds Katharina Edkins a a School of Medicine, Pharmacy and Health, Durham University Queen s Campus, University Boulevard, Stockton-on-Tees, TS17 6BH, United Kingdom. Katharina.Fucke@durham.ac.uk Small organic molecules, especially in the pharmaceutical sciences, tend to crystallise in a plethora of different crystal forms, either as pure compounds or with the inclusion of solvent molecules. Due to their different physico-chemical characteristics, such as melting point, compressibility, solubility and thus bioavailability, and physical and chemical stability, different crystal forms can pose a problem to the manufacture of medicines.[1] It is thus crucial to understand the crystallisation behaviour and manufacturability of these compounds in order to avoid problems in the life-time of the medicine and costly recalls comparable to ritonavir[2] or rotigotine.[3] Bioactive molecules and pharmaceuticals typically have multiple functional groups, enabling them to interact with receptors and thus show pharmacological action. In the solid-state, the interactions through these functional groups are the driving forces of molecular recognition and self-assembly. By applying X-ray and neutron diffraction methods as well as thermoanalysis, vapour sorption and spectroscopic analysis in combination with computational techniques, we are probing the strong and weak interactions within the crystal forms and during the crystallisation in order to understand and predict their characteristics. Due to the molecular complexity of pharmaceutical compounds, it is generally difficult to deconvolute the influence of specific substitution on the self-assembly of related compounds. We are thus using model compounds with reduced complexity and tailored interaction capability to systematically gauge the influence of substituents. Examples are presented in a series of tetrahydrocarbazolone derivatives to investigate the destabilising effect of steric bulk on the predominant hydrogen bonding interaction in the solid-state and solution.[4] Using bromination as another simple model for steric bulk, a series of resorcylic acid derivatives are discussed in terms of solvate formation due to changed interaction motifs. Finally, using the model compound class of triphenyl imidazoles, the impact of bio-isosteric replacement in the group of halogens will be presented.[5] Keywords: Pharmaceuticals, inclusion compounds, substituent effect [1] R. Hilfiker, Polymorphism: In the Pharmaceutical Industry, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, [2] S. R. Chemburkar, J. Bauer, K. Deming, H. Spiwek, K. Patel, J. Morris, R. Henry, S. Spanton, W. Dziki, W. Porter, J. Quick, P. Bauer, J. Donaubauer, B. A. Narayanan, M. Soldani, D. Riley and K. McFarland, Org. Process Res. Dev. 2000, 4, 413. [3] I. B. Rietveld and R. Ceolin, J. Pharm. Sci., 2015, 104, [4] R. M. Edkins, E. Hayden, J. W. Steed and K. Fucke, Chem. Commun., 2015, 51, [5] T. Kitchen, C. Melvin, M. N. Mohd Najib, A. S. Batsanov and K. Edkins, Cryst. Growth Des., 2016, 16, April, 2017

53 O-28 Crystalline Materials to Molecules Leonard R. MacGillivray Department of Chemistry, University of Iowa, Iowa City, IA, 52245, USA. The presentation will describe a method being developed in our laboratory that enables noncovalent bonds to be utilized, in a general way, to direct the formation of covalent bonds in crystals. We show how small organic molecules and inorganic complexes can be used to direct photochemically-induced [2+2] cycloaddition reactions in the solid state. We demonstrate how the method enables molecules to be generated stereoselectively, in quantitative yield, and gram amounts. Recent work on our use of halogen bonds to sustain the solid-state reactions is highlighted. The relevance of the approach to organic synthetic chemistry and pharmaceutics will be discussed. Related work in the field of organic semiconductor materials will also be presented. 2 7 April,

54 O-29 Crystal Engineering of Multi-Component Pharmaceutical Materials Michael J. Zaworotko a a Department of Chemical Sciences and Bernal Institute, University of Limerick, Limerick, Republic of Ireland. xtal@ul.ie That composition and structure can so profoundly impact the bulk properties of crystalline solids has provided impetus for exponential growth in the field of crystal engineering [1] over the past 25 years. This lecture will address how crystal engineering has evolved from its early focus upon structure design (form) to its current emphasis about control over bulk properties (function). Strategies for the generation of two classes of multi-component pharmaceutical materials that can serve as drug substances will be presented: Multicomponent pharmaceutical materials, MPMs, such as cocrystals [2] have recently emerged at the preformulation stage of drug development. This results from their modular and designable nature, which in turn facilitates the discovery of new crystal forms of active pharmaceutical ingredients, APIs, with changed (sometimes dramatically changed) physicochemical properties. The concepts of supramolecular heterosynthons and ionic cocrystals will be explained and case studies will be presented that illustrate how cocrystallisation, especially of ionic cocrystals, could represent a low-risk, high-reward route to better medicines. Crystalline hydrates, are another class of multicomponent materials of relevance to pharmaceutical science. However, unlike most cocrystals, there is little in the way of predictability about the structure or composition of molecular hydrates. This prompted us several years ago to question if hydrates are perhaps the nemesis of crystal engineering. [3] We have conducted systematic studies upon crystalline hydrates with emphasis upon molecules that are devoid of hydrogen bond donors. [4] We shall present new results that address hydrate screening, expectation of whether or not hydrates will form and crystal packing patterns. In this talk, we will discuss the relevance of our structural results with the ones obtained from thermal analysis, competition experiments and kinetics. In summary, this lecture will emphasize how crystal engineering could offer a paradigm shift from the more random, high-throughput methods that have traditionally been utilized in pharmaceutical materials discovery and development. In short, crystal engineering can teach us how to custom-design the right crystalline material for the right application. Keywords: crystal engineering, hydrate, cocrystal [1] (a) G.R. Desiraju, Crystal Engineering: The Design of Organic Solids Elsevier, 1989; (b) B. Moulton and M. J. Zaworotko, Chemical Reviews, 2001, 101, [2] N. Duggirala, M. L. Perry, Ö. Almarsson and M. J. Zaworotko, ChemComm, 2016, 52, [3] H. D. Clarke, K. K. Arora, H. Bass, P. Kavuru, T. T. Ong, T. Pujari, L. Wojtas and M. J. Zaworotko, Crystal Growth & Design, 2010, 10, [4] A. Bajpai, H. S. Scott, T. Pham, K. J. Chen, B. Space, M. Lusi, M. L. Perry and M. J. Zaworotko, IUCrJ, 2016, in press April, 2017

55 O-30 Surface Effects in Polymorphism. When Do They Matter? Aurora J. Cruz-Cabeza, a A. M. Belenguer, b G. I. Lampronti, c C. A. Hunter b and J. K. M. Sanders b a School of Chemical Engineering and Analytical Science, The University of Manchester, UK.. b Department of Chemistry, University of Cambridge, UK. c Department of Earth Sciences, University of Cambridge, UK. aurora.cruzcabeza@manchester.ac.uk In the organic solid state, polymorphism is a common phenomenon. Polymorphs may differ in crystal conformations, symmetries or the interactions governing their crystal structures. Beyond the crystal lattice, polymorphs may also differ in the structures and properties of their surfaces. Whilst the role of crystal surfaces in the kinetics of nucleation and growth of polymorphs is well acknowledged, it is often ignored when it comes to thermodynamics. Crystals obtained by classic crystallization techniques are large enough (μm to cm) so that only a small proportion of their molecules sit at the surface. At those length scales, surface effects are so insignificant that they can be safely ignored. However, crystals produced by alternative experimental techniques to crystallisation may be much smaller in size. If the crystallites reach the nano-meter length scales, their thermodynamics can be considerably altered because of surface effects. In this context, we have studied the polymorphism of an aromatic compound with mechanochemistry [1]. Two polymorphs (forms A and B) were discovered and were consistently obtained through variations of the ball-mill grinding conditions. Our investigations show that our milling experiments always lead to the thermodynamically stable form. However, the thermodynamically stable form switches from B to A as the size of the crystallites becomes smaller. Molecular modeling confirms that the relative stability of these polymorphs is dependent on crystal size. Equilibrium sizes at the end of the milling experiments vary with the milling conditions. We also investigate the effect of solvent concentration and nature on the polymorphic outcome of the ball-mill grinding experiments. Keywords: polymorphism, ball-mill grinding, molecular modelling [1] A. M. Belenguer, G. I. Lampronti, A. J. Cruz-Cabeza, C. A. Hunter, and J. K. M. Sanders, Chemical Science, 2016, 7, April,

56 O-31 From Crystallographic Structure to the Surface Properties of Pharmaceutical Materials Kevin J Roberts Centre for the Digital Design of Drug Products, School of Chemical and Process Engineering, University of Leeds, Leeds, LS2 9JT, UK. There is a growing interest in the prediction of the surface properties of active pharmaceutical ingredients in relation to their formulation downstream into practical dosage forms. In particular, it is well known [1] that surface properties can impact on the physical and chemical properties of crystalline particulate solids, and hence upon the critical quality attributes that impact on product performance, for both drug substance and drug product. This talk will overview the use of synthonic modelling techniques [2] using inter-molecular energy calculations and the atom-atom method. It will highlight how synthonic analysis can be applied to reveal the balance of intermolecular interaction between those of an intrinsic nature which stabilise the bulk structure and those of an extrinsic nature which, being surface-terminated, contribute to the surface energetic properties of the material. The utility of these techniques will be illustrated in terms of their use in predicting the: Crystal morphology and surface chemistry of para amino benzoic acid (paba); Whole crystal surface energies for urea and biuret habit-modified urea and its interrelationship with data derived from IGC analysis; API crystal/excipient compatability in formulating ketoprofen; API/API inter-crystal cohesivity of fine powders of fluticasone propionate and budesonide; Use of synthon surface saturation in predicting the aggregation of salmeterol xinafoate; Cross-correlation of predicted surface chemistry benzyl and paba with experimental studies using NEXAFS spectroscopy. The potential extension of these techniques to the design of drug products and the processes needed to manufacture them will be overviewed and discussed. Keywords: nanostructured calcite, lipids adsorption, supported lipid layers [1] Material science: solid form design and crystallisation process development, K J Roberts, R Docherty and S Taylor in Pharmaceutical Process Development: Current Chemical and Engineering Challenges, RSC Drug Discovery Series No. 9 ( ISBN ), (Edited by J Blacker and M T Williams), The Royal Society of Chemistry, Cambridge, 2011, [2] Synthonic engineering: from molecular and crystallographic structure to the rational design of pharmaceutical solid dosage forms, K J Roberts, R B Hammond, V Ramachandran and R Docherty, Chapter 7 in Computational Approaches in Pharmaceutical Solid State Chemistry (Edited by Y.A. Abramov), 2015 Wiley, Inc April, 2017

57 O-32 Tuning Hydrate Properties Through Doping Jennifer A. Swift, Elizabeth Koch and Kelly McKenna Department of Chemistry, Georgetown University, Washington, DC 20057, U.S.A. Transformations between anhydrous and hydrated molecular crystal forms are an important class of solid state reactions. Thymine, one of the four DNA nucleobases, crystallizes from aqueous solution in either a hydrate (TH) or an anhydrous (T) phase. Herein we examine both low and high temperature phase transitions in TH single crystals, and show how these processes are affected by the inclusion of low concentrations of dopants. Keywords: Nucleic acid, hydrate, phase change 2 7 April,

58 O-33 Structural Chemistry, Fuzzy Logic and the Law Joel Bernstein a Department of Chemistry, Ben-Gurion University of the Negev, P.O. Box 653, Beer Sheva, Israel yoel@bgu.ac.il. Faculty of Science, New York University Shanghai, Pudong New Area, Shanghai , China. jb3678@nyu.edu While chemistry is considered to be one of the exact sciences, much of the reasoning in the practice of chemistry is not based on absolutes always and never but rather on general rules and exceptions to those rules. This means that in the practice of their discipline, chemists necessarily resort to what is often called fuzzy logic. Some of those chemists are recruited to serve as consultants and expert witnesses in patent litigations that necessarily involve technological and scientific issues often including chemistry. As a result of the fuzzy nature of much of chemical logic, accomplished well established chemists can find themselves on opposite sides of a courtroom, each representing what he or she honestly believes is correct science, even though in terms of the legal question to be addressed, they are diametrically opposed. In this talk I will provide examples of each of these aspects of the relationship between the fuzzy logic of chemistry and the role of expert witnesses in patent litigation. Keywords: fuzzy logic, expert witness, patents April, 2017

59 O-34 Additive Effects on the Appearance and Kinetics of Polymorphs of p-aminobenzoic acid (PABA) James F. B. Black a, Roger J. Davey a and Robert D. Willacy b a School of Chemical Engineering and Analytical Science, The Mill (D37), The University of Manchester, United Kingdom, M13 9PL; b GSK Medicines Research Centre, Gunnels Wood Road, Stevenage, Hertfordshire, United Kingdom, SG1 2NY. james.black@manchester.ac.uk The importance of control over crystallisation in polymorphic systems as it relates to processing, patenting and regulatory control in industry is well known. Despite this there remains a lack of fundamental understanding concerning the processes of nucleation and crystal growth surrounding the competitive appearance of different crystal forms. In this contribution we report studies of the enantiotropic system, p-aminobenzoic acid [1] (PABA) which has two known forms, α stable above 13.8 o C and β stable below this transition temperature.[2] The two forms are easily distinguished by optical microscopy and PXRD. Crystallisation from IPA both above and below the transition temperature yields the kinetically preferred α form (left image). In this work we show how tailor-made additives may be selected in order to switch the preferred polymorph from α to β (right image) both above and below the transition temperature. In addition to this we present quantitative evidence on how these additives affect the nucleation and growth kinetics of both forms. These data show, for the first time, the connection between the kinetic effects imparted by the additives and their ability to control the polymorph appearance of PABA. Keywords: tailor-made additives, p-aminobenzoic acid, polymorphism, enantiotropic, nucleation kinetics, growth kinetics [1] S. Gracin and Å. C. Rasmuson, Crystal Growth & Design, 2004, 4, [2] H. Hao, M. Barrett, Y. Hu, W. Su, S. Ferguson, B. Wood and B. Glennon, Organic Process Research & Development, 2012, 16, April,

60 O-35 Aspects of Cocrystal Solid State Chemistry Bill Jones Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, UK The concept of cocrystallization (the incorporation of two or more molecules in the same crystal in a defined stoichiometric ratio) is not new. In recent times, however, an increased awareness of them has resulted in an explosion of interest from both academia and industry. From an academic viewpoint they provide an interesting approach to studying competing supramolecular synthons between different functional groups (without the need for complex synthetic chemistry), the challenge of relating crystal structure to physical property (e.g. the relationship between melting points of the constituents and the individual molecules; possible stability to moisture), the likelihood of polymorphism and/or propensity to hydrate/solvate formation and in particular the tantalizing question of which molecules will pair up and which will not. Associated with this has been the issue of how best to screen for possible cocrystal formation given the fact that different cocrystals of the same two molecules may have different stoichiometric compositions. From an industrial perspective the main interest at present would seem to be the advantage that cocrystallization can bring to impart advantageous solid state properties on an otherwise challenging drug candidate e.g. solubility/bioavailability and stability of crystal form. My lecture will summarise some of the key aspects of cocrystal chemistry including approaches to screening for formation, questions of bulk and surface stability vis a vis dissociation to the individual components. It will also touch upon some of our recent work on photochemical and photophysical properties and how they may be used to examine certain mechanisms for photo-degradation and fluorescence. Keywords: calix[4]arenes, nanosized structures and materials April, 2017

61 O-36 The Use of Halogen Bonding and Hydrogen Bonding in Versatile Supramolecular Synthetic Strategies Christer B. Aakeröy, a Christine L. Spartz, a Tharanga K. Wijethunga a a Department of Chemistry, Kansas State University, Manhattan, KS, 66503, USA. aakeroy@ksu.edu As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. Since hydrogen- and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. It has been shown that readily accessible calculated molecular electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in co-crystals as long as the potential differences are weighted appropriately [1-3]. The use of reliable co-crystals synthesis in practical applications is also explored including the use of halogen-bond interactions for transforming liquid iodoperfluoroalkanes into crystalline materials with low-vapor pressure, considerable thermal stability, and moisture resistance [4]. In addition, we have been able to extract desired molecular tautomers into the solid state using supramolecular selectivity driven by both hydrogen- and halogen-bond based interactions [5] and hydrogen bonds have been employed in order to stabilize energetic materials [6]. Keywords: halogen bonding, hydrogen bonding, supramolecular synthesis [1] C.B. Aakeröy, C.L. Spartz, S. Dembowski, S. Dwyre, J. Desper, IUCrJ, 2015, 2, [2] C.B. Aakeröy, T.K. Wijethunga, M. Đaković, J. Desper, Cryst. Growth Des., 2016, 16, [3] C.B. Aakeröy, Acta Crystallogr. Sect. B, 2015, 71, [4] C.B. Aakeröy, T.K. Wijethunga, J. Benton, J. Desper, ChemCommun., 2015, 51, [5] K. Epa, C.B. Aakeröy, J. Desper, S. Rayat, K. Chandra, A.J. Cruz-Cabeza, ChemComm., 2013, 49, [6].C.B. Aakeröy, T.K. Wijethunga, J. Desper, Chem. Eur. J. 2015, 21, April,

62 O-37 Supramolecular Design of Topochemical Solid-State Reactions Demetrius C. Levendis, Sanaz Khorasani, Delbert Botes and Manuel A. Fernandes Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, PO WITS 2050, South Africa The topochemical criteria first outlined by Schmidt and coworkers has provided a useful guideline as to whether or not a reaction will occur in the solid state. Potentially reacting molecules should typically be less than 4.2 Å apart and suitably oriented for dimerization. In our recent work on the [2+2] photodimerization of o-ethoxy-cinnamic acid [1] we have shown some exceptions to this rule. In reactions involving a thermal [4+2] dimerization, electron donor/acceptor (EDA) interactions influence the way in which pairs of dithiin (acceptor) and anthracene (donor) molecules assemble, forming heteromolecular crystals of charge-transfer (CT) complexes that can potentially react in the solid state. In these CT complexes it is therefore desirable to not only form a CT pair, but for this pair to crystallize in stacks of alternating donor and acceptor molecules that conform to the topochemical criterion. Typically the crystal structures consist of stacks of alternating electron donor and acceptor molecules in a 1:1 ratio. These crystals can then undergo a thermally induced solid-state (SS) Diels Alder reactions in a singlecrystal-to-single-crystal (SCSC) fashion, with the dithiin molecules as the dienophiles and anthracenes as the diene. Reactions are anticipated to take place at temperatures well below their melting points. The nature of the R-groups on the dithiin (short alkanes, cycloalkanes, aromatic groups or chiral molecules) and X-groups on the anthracene (H, Me, Br, allyl) critically affects the packing of the molecules and hence their reactivity. In some cases no CTs are formed, while in others where CTs do form there is no reaction in the solid- state at reasonably low temperatures (<100 o C), even though donor and acceptor molecules fall well within the topochemical limits [2-3]. These crystals can however react at higher temperatures, but involve phase transformation and crystal degradation. In this paper we discuss the effect of the dithiin substituents, R 1 and R 2, and of the anthracene substituents, X, on the formation of CT complexes and on their reactivity. Keywords: topochemical principle, solid-state reaction, Diels-Alder, charge-transfer complex [1] M. A. Fernandes and D. C. Levendis, CrystEngComm, 2016, 18, [2] S. Khorasani, M.A. Fernandes, Cryst. Growth Des., 2013, 13, [3] S. Khorasani, D. S. Botes, M. A. Fernandes and D. C. Levendis, CrystEngComm, 2015, 17, April, 2017

63 O-38 Polymorphism and Solvatomorphism of some Bis-hydrazone Compounds Dinabandhu Das a School of Physical Sciences, Jawaharlal Nehru University, New Delhi , India. jnu.dinu@gmail.com Polymorphism [1] and solvatomorphism [2], two important phenomena, are widely studied in solid-state chemistry especially in the field of organic compounds. Although polymorphism implies the observation of at least two 'different' crystal structures of a same chemical entity, recently there are few reports, which demonstrate the observations of two or more polymorphs of one compound which are isostructural. [3] This type of polymorphism is named as isostructural polymorphism.[4] In this presentation, polymorphism of some bis-hydrazone compounds will be described, highlighting a case of reversible isostructural polymorphism. Preferential inclusion of particular guest molecules over the others by a host has tremendous importance in purification and separation processes. [5] Selective inclusion properties of some bis-hydrazone host compounds will be discussed in this presentation. Keywords: Polymorphism, solvatomorphism, isostructurality, selective inclusion [1] A. J. Cruz-Cabeza, S. M. Reutzel-Edens and J. Bernstein, Chem. Soc. Rev., 2015, 44, [2] H. G. Brittain, J. Pharm. Sci., 2012, 101, 464. [3] K. K. Jha, S. Dutta, V. Kumar and P. Munshi, CrystEngComm, 2016, 18, [4] S. J. Coles, T. Threlfall and G. Tizzard, Cryst. Growth Des., 2014, 14, [5] V. Jayant, D. Das, Cryst. Growth Des. 2016, 16, 4183 and references therein. 2 7 April,

64 O-39 Smart Calixarene Crystals Valery V. Gorbatchuk, Marat A. Ziganshin, Karina V. Gataullina, Askar K. Gatiatulin Institute of Chemistry, Kazan Federal University, Kremlevskaya 18, Kazan, Russia. Smart properties of crystalline calixarenes and other hosts were observed boosting their selectivity and clathrate stability. Absolute selectivity of host response to guest inclusion and release was found, which goes far beyond the capability of ordinary key-to-lock mechanism. While current concept of molecular recognition is based on the preferential binding of complementary species, the present work uses specific cooperative properties of host crystals such as their memory of previously bound guest, pseudopolymorphism of host-guest clathrates with more than one step of guest inclusion, favorable hydration effect on binding of hydrophobic guests by hydrophilic hosts, and effect of clathrate preparation history on guest inclusion capacity and clathrate stability. Thus, small guest molecules having no more than one functional group capable of H-bonding or donor-acceptor interactions can be discriminated even from their close homologues. A true recognition was found in a two-step formation of benzene clathrate with tert-butylthiacalix[4]arene derivative both on vapor sorption isotherm and in kinetic response of mass-sensitive sensor [1]. This experiment is extremely selective being capable to detect benzene qualitatively and quantitatively in mixtures with any other compounds. Inclusion cooperativity of glassy calixarenes makes possible also a visual detection of organic vapors in mixtures giving a response to a very small step in guest concentration [2]. An observed ability of several calixarenes to remember evolved guests does not have any precedents by selectivity. This memory can be read in simultaneous TG/DSC experiment as an exothermic effect of host collapse from loose to dense phase without mass change. The memory parameters (enthalpy and temperature of polymorphic transition) strongly depend on the guest structure. This smart property persists also for guest mixtures [3]. In some cases, such memory effect can be found only after a solid-phase guest exchange in calixarene clathrates [4]. The procedure of clathrate preparation by guest exchange is rather selective itself and gives a surge in guest inclusion capacity and clathrate stability both for calixarenes and beta-cyclodextrin [5]. This may produce clathrates that cannot be formed by host-guest interaction in binary systems. The highest clathrate stability was found for calixarene capable of special anti-sieve effect, so that larger guests can be bound, while smaller ones are excluded [6]. Keywords: molecular recognition, host memory, thermal stability [1] G. D.Safina, L. R.Validova, M. A.Ziganshin, I. I.Stoikov, I. S.Antipin and Gorbatchuk, V. V. Sensors and Actuators B., 2010, 148, 264, [2] K.V. Gataullina, M.A. Ziganshin, I.I. Stoikov, A.T. Gubaidullin and V.V. Gorbatchuk, Phys. Chem. Chem. Phys., 2015, 17, 15887, [3] G.D. Safina, M.A. Ziganshin, A.T. Gubaidullin and V.V. Gorbatchuk, Org. Biomol. Chem., 2013, 11, 1318, [4] S.F. Galyaltdinov, M.A. Ziganshin, A.B. Drapailo and V.V. Gorbatchuk, J. Phys. Chem. B, 2012, 116, 11379, [5] V. V. Gorbatchuk, A. K. Gatiatulin, M. A. Ziganshin, A.T.Gubaidullin and L.S.Yakimova, J. Phys. Chem. B, 2013, 117, 14544, [6] S. F. Galyaltdinov, M. A. Ziganshin, A. T. Gubaidullin, S. G. Vyshnevsky, O. I. Kalchenko and V. V. Gorbatchuk, CrystEngComm, 2014, April, 2017

65 O-40 Solid State Features of Calixarenes Kinga Suwinska, Faculty of Mathematics and Natural Sciences, Cardinal Stefan Wyszynski University in Warsaw, K. Wóycickiego 1/3, PL Warszawa, Poland. Solid state studies of calixarenes and calix-type host molecules and their inclusion complexes are a source of information about geometry and interactions for both individual molecules and supramolecular complexes. X-ray diffraction studies of crystalline samples provide direct information about molecular structure (atoms types and distribution, geometrical parameters, i.e. bond lengths, bond angles and torsion angles, molecular conformation and absolute configuration) and crystal structure (crystal composition, i.e. molecular ratio for complex crystals and/or presence of solvent(s) molecules, intermolecular interactions, especially determination of the networks of hydrogen bonds and short intermolecular contacts). Solid state investigations are of great importance in particular in case of studying calixarene and calix-type compounds due to their great ability to form molecular inclusion complexes, co-crystals and supramolecular assemblies. In CSD (Cambridge Structural Database ) over 6000 structures of calix-type compounds are deposited so far. Approximately 1/3 of the entries are organometallic compounds and 2/3 are classified as organic compounds. The analysis of over 4000 entries classified as organic compounds reveals that calixarene structures are in great majority (approx entries). Among them about 2270 entries refers to calix[4]arenes. In this presentation solid state features of calixarenes and their complexes will be described. The very first published crystal structure of calix-type compound: (left) molecular formula; (right) molecular structure [1] Keywords: calixarenes, molecular inclusion complexes, inclusion compounds, molecular crystals, host-guest complexes, co-crystals, X-ray crystal structure, solid state [1] Nilsson, B.; Acta Chem. Scand. 1968, 22, April,

66 O-41 Cross-Photodimerization Reactions Utilizing Polyfluorophenyl- Phenyl Interactions Ryan H. Groeneman a, Michael A. Sinnwell b, and Leonard R. MacGillivray b a Department of Biological Sciences, Webster University, St. Louis Missouri, 63119, USA; b Department of Chemistry, University of Iowa, Iowa City Iowa, 52242, USA. ryangroeneman19@webster.edu In recent years, the ability to align olefins in the solid state that undergo [2+2] cycloaddition reactions has continued to be an active area of research. To properly position reactant molecules in solids, a template approach has proven to be very successful in the formation of numerous target molecules. In nearly all examples, the photoreactions have involved two identical reactants. A second possible and less investigated outcome is a cross photoproduct where two different reactant molecules undergo the light induced [2+2] cycloaddition reaction. While the ability of perfluorophenyl-phenyl interactions as a driving force to align different olefin-containing molecules has been reported, currently there is no systematic study on a series of cross photoproducts produced in this manner. To this end, we will report on a series of cross photoproducts based on a symmetrical octafluoro stilbene trans-1,2-bis(2,3,5,6-tetrafluorophenyl)ethylene as well as an unsymmetrical stilbene trans-1-(2,3,5,6-tetrafluorophenyl)-2-(2,3,4,5,6-pentafluorophenyl)ethylene. Crystal structures before and after photoreactions will be presented as well as the non-covalent interactions observed in each co-crystal. In addition, we will discuss the limited types of cross photoproducts and the synthetic approach required for each class of products. Keywords: [2+2] cycloaddition reactions, polyfluorophenyl-phenyl interactions, cross photoproduct April, 2017

67 O-42 Molecular Rotors in Porous Supramolecular Architectures Angiolina Comotti, Silvia Bracco, Fabio Castiglioni, Mattia Negroni and Piero Sozzani Department of Materials Science, University of Milano Bicocca, Via R. Cozzi 55, Milan, Italy. A challenging issue is the dynamics of porous solids and the insertion of molecular rotors in their building blocks, promising access to the control of rotary motion by chemical stimuli. The combination of porosity with ultra-fast rotor dynamics was discovered in molecular crystals and covalent frameworks, by 2 H spinecho NMR spectroscopy and T 1 relaxation times.[1-3] The rotors, as fast as 10 7 Hz at 200 K, are exposed to the crystalline channels, which absorb CO 2 and I 2 vapors even at low pressure. Interestingly, the rotor dynamics can be switched on and off by vapor absorption/desorption, showing a remarkable change of material dynamics. Novel mesoporous organosiloxane frameworks allowed to realize periodic architectures of fast molecular rotors containing dynamic C-F dipoles in their structure.[4] The dipolar rotors showed not only the rapid dynamics of the aromatic rings (ca Hz at 325 K), as detected by solid-state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Crystals with permanent porosity were exploited in an unusual way to decorate crystal surfaces with regular arrays of dipolar rotors. The inserted molecules carry alkyl chains which are included as guests into the channel-ends.[5] The rotors stay at the surface due to a bulky molecular stopper which prevents the rotors from entering the channels. The host-guest relationships were established by 2D solid-state NMR and GIAO HF ab initio calculations. Flexible molecular crystals were fabricated by a series of shape-persistent azobenzene tetramers that form porous molecular crystals in their trans configuration. The efficient trans cis photoisomerization of the azobenzene units converts the crystals into a non-porous phase but crystallinity and porosity are restored upon Z E isomerization promoted by visible light irradiation or heating. We demonstrated that the photoisomerization enables reversible on/off switching of optical properties as well as the capture of CO 2 from the gas phase.[6] Control of molecular rotor dynamics by I 2 molecule absorbed in the channels of a porous molecular crystal shown below: Keywords: Porous Materials, Molecular Rotors, Solid State NMR [1] A. Comotti, S. Bracco, P. Sozzani Acc. Chem. Res. 2016, 49, [2] A. Comotti, S. Bracco, A. Yamamoto, M. Beretta, N. Tohnai, M. Miyata, P. Sozzani J. Am. Chem. Soc. 2014, 136, 618. [3] A. Comotti, S. Bracco, T. Ben, S. Qiu, P. Sozzani Angew. Chem. Int. Ed. 2014, 53, [4] S. Bracco, M. Beretta, A. Comotti, A. Falqui, K. Zhao, C. Rogers, P. Sozzani Angew Chem. Int Ed. 2015, 54, [5] L. Kobr, K. Zhao, A. Comotti, S. Bracco, P. Sozzani, J.C. Price, C.T. Rogers, J. Michl J. Am. Chem. Soc. 2012, 134, [6] M. Baroncini et al. Nature Chem. 2015, 7, April,

68 O-43 Is the Crystallisation of Pharmaceuticals Controlled by Thermodynamics or Kinetics? Sarah (Sally) L. Price a a Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom. s.l.price@ucl.ac.uk Crystal Structure Prediction (CSP) methods were developed on the assumption that an organic molecule would crystallize in its most stable crystal structure. Even implementing this approach is a challenge to computational chemistry methods, as shown by the Cambridge Crystallographic Data Centre s blind tests.[1] Polymorphism adds additional challenges, as this is usually a kinetic phenomenon with metastable polymorphs being unable to transform to the more stable structure in the solid state. CSP is being developed as an aid to polymorph screening[2, 3] through calculating the crystal energy landscape, the set of crystal structures that are thermodynamically plausible as polymorphs. However, the crystal energy landscape usually includes more crystal structures than known polymorphs, raising the question as to why more polymorphs are not found.[4] This can be due to the approximations in the calculations, particularly the neglect of thermal effects but also the lack of consideration of kinetics. Sometimes the prediction of a putative polymorph can allow the design of a specific experiment to find it, for example by using an isomorphous crystal of another molecule as a template.[5] More commonly, the crystal energy landscape can rationalize observations of complex crystallization behavior, such as the occurrence of disorder,[6] or multiple solvate formation. The crystal energy landscapes of some pharmaceuticals raise questions as to whether the conformations in observed polymorphs are determined by solvent effects. Even for simple model molecules, such as 3-chloromandelic acid, the crystallization of enantiopure and racemic structures is difficult to predict.[7] Whilst the crystallization behavior of some molecules is easily predicted, many pharmaceuticals and chiral compounds really challenge our understanding of crystallization. Keywords: Crystal Structure Prediction, Pharmaceutical development, Computational Thermodynamics [1] A. M. Reilly et al. [2] S. L. Price and S. M. Reutzel-Edens, Drug Discovery Today, 2016, 21, [3] S. L. Price, D. E. Braun and S. M. Reutzel-Edens, Chem. Commun., 2016, 52, [4] S. L. Price, Acta Cryst. B, 2013, 69, [5] V. K. Srirambhatla, R. Guo, S. L. Price and A. J. Florence, Chem. Commun., 2016, 52, [6] L. S. Price, J. A. McMahon, S. R. Lingireddy, S. F. Lau, B. A. Diseroad, S. L. Price and S. M. Reutzel-Edens, J. Molec. Struct., 2014, 1078, [7] R. K. Hylton, G. J. Tizzard, T. L. Threlfall, A. L. Ellis, S. J. Coles, C. C. Seaton, E. Schulze, H. Lorenz, A. Seidel-Morgenstern, M. Stein and S. L. Price, J.Amer. Chem. Soc., 2015, 137, April, 2017

69 O-44 Absorptive Organic and Hybrid Materials for Gases and Polymers Piero Sozzani, Jacopo Perego, Daniele Piga, Donata Asnaghi, Irene Bassanetti, and Silvia Bracco Department of Materials Science, University of Milano Bicocca, Via R. Cozzi 55, Milan, Italy. The fabrication of porous architectures for the confinement of gases and polymer chains to pores is a challenging research area. The matrices range from fully-organic and metal-organic frameworks to porous molecular crystals of synthetic and biological origin, such as dipeptides.[1] We were mostly intrigued in comparing the matrices depending on the nature of the interactions, pore shape, surface area and pore capacity. Like gases, flexible polymer chains can diffuse inside the galleries undergoing severe steric requirements which tune their conformations, dynamics and properties. Fast- 1 H, 19 F and 2D hetero-correlated MAS NMR spectroscopies played a key role in determining the hostguest interactions at the interfaces and the relationships between the components. A few case studies will be highlighted. A peculiar kind of porous crystalline solid derives from the use of hard and soft interactions in a hierarchical construction. Primary supramolecular toroidal structures are formed by robust metal-organic bonds: they can self-assemble four-by-four into the shape of Platonic solids, held together by van der Waals and coulombic interactions.[2] Anions play a major role in modulating the architectures. The 3D crystalline structures are permanently porous and able to entrap reversibly vapors and gases. In a further example, 1,3-butadiene vapors could be separated from other C4 hydrocarbon by a MOF matrix [3], which provides structural flexibility and unique guest-responsive accommodation. Regarding the relevant issue of manipulating and transforming polymer chains in a confined environment, we varied the conducting properties of polyacrylonitrile chains by thermal transformation into graphitized nanofibers.[4] Moreover, isolation of single polysilane chains increased the rate of carrier mobility in comparison with that in the bulk state due to the elimination of the slow interchain hole-hopping.[5] The main chain conformation of polysilane could be controlled by changing the nanochannel cross-section, as evidenced by Raman spectroscopy and solid-state NMR: Ligand (left), supramolecular toroidal structure (center) and its arrangement into a porous material (right). Keywords: Polymer Inclusion, Gas Detection, Solid State NMR [1] V.N. Yadav, A. Comotti, S. Bracco, P. Sozzani, T.Hansen, M. Hennum, C.H. Gorbitz Angew. Chem. Int. Ed. 2015, 54, [2] I. Bassanetti, A. Comotti, P. Sozzani, S. Bracco, G. Calestani, F. Mezzadri, L. Marchio J. Am. Chem. Soc. 2014, 136, [3] T. Uemura, S. Kitagawa, P. Sozzani, A. Comotti, S. Bracco, et al. J. Am. Chem. Soc., 2015, 137, [4] A. Comotti, S. Bracco, M. Beretta, J. Perego, M. Gemmi, P. Sozzani Chem. Eur. J. 2015, 21, [5] T. Kitao, S. Bracco, A. Comotti, P. Sozzani, M. Naito, S. Seki, T. Uemura, S. Kitagawa J. Am. Chem. Soc. 2015, 137, April,

70 O-45 Organics in SC-XRD: from Alpha to (almost) Omega Holger Ott, a Tobias Stuerzer a and Michael Ruf b a Bruker AXS GmbH, Oestliche Rheinbrueckenstr. 49, Karlsruhe, Germany; b Bruker AXS Inc., 5465 E. Cheryl Parkway, Madison, WI 53711, USA. holger.ott@bruker.com Absolute configuration (Alpha α) plays a central role in the functions and properties of many organic and metalorganic compounds, such as natural products, catalysts, and pharmaceuticals. For example, with a simple change of handedness at one single stereo-center the scent of Carvone changes from spearmint to caraway. Similarly, in chiral pharmaceuticals one isomer can exhibit a healthful physiologic activity, while the second stereo isomer is inactive, or might even be toxic. X-ray crystallography is the definitive method to determine the absolute configuration with the least experimental effort. Even better, recent developments, such as large active-area CPAD detectors, ever brighter microfocus sealed-tube and liquid-metal X-ray sources, and continuous scanning modes have significantly lowered the experimental threshold. Modern equipment opens the possibility to measure extremely small anomalous differences in Bijvoet pairs. Today, even for light-atom molecules, consisting of period 2 elements only, an accurate determination of the absolute configuration is often a question of minutes only. The interest in pharmaceutical research to analyze organic samples under non-ambient pressure (Pi π) has immensely increased. Typically, the main focus is on the identification of different polymorphs. However, the method is also suitable to elucidate reaction mechanisms or even to identify metastable modifications which sometimes exhibit a higher pharmaceutical activity. Limits associated with the usage of a Diamond-Anvil Cell (DAC), such as a diminished accessibility of the reciprocal space, were substantially overcome with recent improvements in hardware and software. Experimental setup, data acquisition, and data processing quality are now at a level which enables an ever larger user group to successfully master high-pressure measurements. Focusing on high-pressure und absolute structure determination experiments, this presentation gives a deeper insight in two most exciting fields in crystallography for organics. The analysis of various chiral compounds and samples under high-pressure will be presented to demonstrate the ease-of-use of modern methods and tools. Keywords: absolute structure, high pressure, CPAD detector April, 2017

71 O-46 A Plethora of 0D Porous Molecular Solids K. Travis Holman Department of Chemistry, Georgetown University, Washington, DC, USA. travis.holman@georgetown.edu There is much contemporary interest in the development of new materials for gas capture/sequestration, separation, sensing, etc. Efforts in this regard have mainly been directed toward molecule-derived materials that exhibit permanent open pores (e.g., metal-organic frameworks (MOFs), covalent organic frameworks (COFs), polymers of intrinsic microporosity (PIMs), and intrinsically porous molecular solids (PMSs). Much less is understood, however, about the properties of zero dimensional (0D) porous solids, which, in a static view of their structures, do formally possess interconnected pores, but nonetheless exhibit exploitable voids/cavities of appreciable volume (> 25 Å 3 ). As will be discussed, members of this historically unusual, but growingly ubiquitous family of molecular solids can offer several advantages. They are solution processable. They are often intrinsically incollapsible. They can be alloyed (i.e., solid solutions). They can be cheap. By offering pores that completely encapsulate putative sorbates, they have the potential to optimize thermodynamic selectivity with respect to gas/guest capture. Moreover, the kinetics of gas uptake and/or release can vary enormously with rates spanning several orders of magnitude and are largely dependent upon molecular and crystalline structure, features which can be engineered and exploited. This presentation will highlight studies in our laboratory concerning the design and properties of 0D porous molecular solids derived from shape persistent macrocycles. It will be argued that such materials are in fact ubiquitous, but have gone relatively unrecognized because of massive biases in the CSD that arise from experimental biases in the means by which crystals are grown and the means by which structures are determined [1]. The intrinsic 0D pores of these materials have been exploited for the capture, sorption, kinetic separation, and/or extreme kinetic confinement of commodity gases and other small molecules. Some simple 0D porous solids exhibit highly selective (e.g., C 2 > C 3 or C 3 > C 4 hydrocarbons) and tunable gas enclathration behavior [2]. Others are capable of confining gases in the solid state at temperatures as high as 400 C above the normal boiling point of the gas [3]. Perhaps counterintuitively, others allow gas exchange on a timescale that is reminiscent of open pore materials. Keywords: porosity, clathrates, gas sorption, porous molecular solids, cavitands, 0D porous solids [1] C. M. Kane, O. Ugono, L. J. Barbour, K. T. Holman, Chem. Mater. 2015, 27, [2] C. M. Kane, A. Banisafar, T. Dougherty, L. J. Barbour, K. T. Holman, J. Am. Chem. Soc. 2016, 138, [3] A. I. Joseph, S. H. Lapidus, C. M. Kane, K. T. Holman, Angew. Chem. Int. Ed. 2015, 54, April,

72 O-47 Solid State Conformational Flexibility in Cyclic Peptoids Consiglia Tedesco, a Eleonora Macedi, a Alessandra Meli, a Francesco De Riccardis, a Irene Izzo, a Michela Brunelli, b Gavin B. M. Vaughan, b Andrew N. Fitch, b Vincent J. Smith, c Leonard J. Barbour c a Dipartimento di Chimica e Biologia "A. Zambelli", Università di Salerno, via Giovanni Paolo II 132, Fisciano, Italy. b European Synchrotron Radiation Facility, CS40220, Grenoble CEDEX 9, France; c Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. ctedesco@unisa.it Biological processes rely on control of the dynamic behaviour of biomolecules, the intrinsic flexibility of proteins enables accurate guest recognition and specific substrate conversion. The design and synthesis of artificial systems able to mimic biological functions is the aim of inexhaustible research activity in the field of molecular nanotechnology. Cyclic peptoids for their biostability and potential diversity seem to be the ideal candidates to evoke biological activities and novel chemical properties [1,2]. Peptoids differ from peptides in the backbone position of the side chains, which are attached to the nitrogen atoms. Due to the lack of the amide proton, CH OC hydrogen bonds and CH- interactions, play a key role in the solid-state assembly of cyclic -peptoids: face to face or side by side arrangement of the macrocycles mimick -sheet secondary structure in proteins [3]. In particular, side chains may act as pillars, extending vertically with respect to the macrocycle plane, inducing the columnar arrangement of the peptoid macrocycles [3,4]. Recently we reported on a cyclic peptoid compound, strategically decorated with propargyl and methoxyethyl side chains, which undergoes a reversible single-crystal-to-single-crystal transformation upon guest release/uptake (see figure). The transfomation is connected to the formation of an unprecedented CH zipper, which can reversibly open and close, allowing for guest sensing [5]. Thus, the peculiar conformational flexibility of cyclic peptoids is the key to their solid state dynamic behaviour. Keywords: conformational flexibility, peptoids, solid state assembly, guest recognition [1] N. Maulucci, I. Izzo, G. Bifulco, A. Aliberti, C. De Cola, D. Comegna, C. Gaeta, A. Napolitano, C. Pizza, C. Tedesco, D. Flot and F. De Riccardis, Chem. Commun., 2008, [2] I. Izzo, G. Ianniello, C. De Cola, B. Nardone, L. Erra, G. Vaughan, C. Tedesco and F. De Riccardis, Org. Lett., 2013, 15, 598. [3] C. Tedesco, L. Erra, I. Izzo and F. De Riccardis, CrystEngComm 2014, 16, [4] C. Tedesco, A. Meli, E. Macedi, V. Iuliano, A. G. Ricciardulli, F. De Riccardis, G. B. M. Vaughan, V. J. Smith, L. J. Barbour and I. Izzo, CrystEngComm, 2016, DOI: /C6CE01800A. [5] A. Meli, E. Macedi, F. De Riccardis, V. J. Smith, L. J. Barbour, I. Izzo and C. Tedesco, Angew. Chem. Int. Ed. Engl. 2016, 55, April, 2017

73 O-48 Stopping Crystal Growth in its Tracks: Preventing Pathological Crystallization Michael D. Ward Department of Chemistry and the Molecular Design Institute, New York University, 100 Washington Square East, New York, NY The crystal growth of conventional materials like silicon has been refined for decades and has led to textbook crystal growth models. Confidence in these models quickly evaporates when considering complex inorganic solids and molecular crystals, however, despite the importance of these materials to technology, biology, and human health. In particular, many crystalline materials are associated with diseases, from malaria to kidney stones.[1] This presentation will illustrate the beauty and complexity of crystal growth, through mechanisms often hidden and deceptive, of pathological molecular crystals, including kidney stones as well as xenostones that form as a consequence of active pharmaceutical ingredients that form crystals in renal spaces. Observation at multiple length scales, using techniques ranging from atomic force microscopy (AFM) to optical microscopy, reveal the consequences of the complexity of dissymmetric surfaces of organic crystals,[2,3] which stems from their inherent low molecular and crystal symmetry.[4,5,6] Armed with an understanding of crystal physics and crystal surface structure at the molecular level, crystal growth inhibitors can be designed that bind to specific crystal sites and prevent the formation of pathological crystals, suggesting a pathway to therapies for crystalbased diseases in general. Moroever, real-time in situ AFM permits permits kinetic analyses of crystal growth at the nanoscale that reveals the mode of action of crystal growth inhibitors in knockout mouse models.[7,8] Keywords: Crystal growth, dislocations, atomic force microscopy [1] L. N. Poloni and M. D. Ward, Chem. Mater., 2014, 26, 477. [2] L. N. Poloni, A. P. Ford and M. D. Ward, Cryst. Growth. Des. 2016, 16, [3] W. J. P van Enckevort and P. Bennema, Acta Crystallogr A, 2004, 60, 532. [4] J. D. Rimer, Z. An, Z. Zhu, M. H. Lee, D. S. Goldfarb, J. A. Wesson and M. D. Ward, Science, 2010, 330, 337. [5] A. G. Shtukenberg, Z. Zhu, Z. An, M. Bhandari, P. Song, B. Kahr and M. D. Ward, Proc. Natl. Acad. Sci., 2013, 110, [6] A. G. Shtukenberg, L. N. Poloni, Z. Zhu, Z. An, M. Bhandari, P. Song, A. L. Rohl, B. Kahr and M. D. Ward, Cryst. Growth Des., 2015, 15, 921. [7] A. Sahota, J. S. P., K. M. Capaccione, M.Yang, K. Noll, D. Gordon, D. Reimer, I. Yang, B. T. Buckley, Marianne Polunas, Kenneth R. Reuhl, M. R. Lewis, M. D. Ward, D. S. Goldfarb and J. A. Tischfield, Urology, 2014, 84, 1249.e9. [8] L. Hu, Y. Yang, H. Aloysius, H. Albanyan, M. Yang; J.-J. Liang, A. Yu, A. Shtukenberg, L. Poloni, V. Kholodovych, J. Tischfield, D. S. Goldfarb, M. D. Ward and A.Sahota, J. Med. Chem., 2016, 59, April,

74 O-49 Energy-Structure-Function Maps and the Discovery of Porous Molecular Crystals Graeme M. Day a a School of Chemistry, University of Southampton, Southampton, SO17 1BJ, United Kingdom. G.M.Day@soton.ac.uk The design of molecular crystals with targeted properties is the goal of crystal engineering. However, our predictive understanding of how a crystal s properties relate to its structure, and how crystal structure in turn relates to molecular structure, are not yet sufficiently reliable to confidently design functional materials. One reason for this is that the crystal structure adopted by a molecule is rarely determined by a single, predictable structure-directing interaction, but typically results from a balance of many relatively weak intermolecular interactions. It is, therefore, common for a molecule to have many nearly equi-energetic possible crystal structures, with the best structure (the global lattice energy minimum) favoured by only a few kj mol -1 or less over alternative structures that might have very different physical properties. This existence of competing low energy crystal structures is related to the prevalence of polymorphism in molecular crystals, as well as the observation that small changes to chemical structure can lead to dramatic changes in crystal packing. Computational methods for crystal structure prediction (CSP) have been developed to help anticipate the crystal structure that a molecule will form. These methods are based on a global search of the lattice energy surface and a ranking of local energy minima according to their calculated relative stabilities [1]. Each of the crystal structures in the resulting ensemble encodes a set of properties, many of which are calculable using computer simulations. This talk will discuss how the set of predicted structures, their calculated energies and simulated properties, which we present as an energy-structure-function (ESF) map, can be used to guide the discovery of functional molecular crystals, as well as the optimisation of properties within a family of molecules [2]. The ESF mapping approach will be illustrated with its use in the discovery of porous molecular crystals with large methane storage capacities and high guest selectivities [3]. Keywords: crystal structure prediction, porous materials, gas storage [1] D. H. Case, J. E. Campbell, P. J. Bygrave and G. M. Day, J. Chem. Theory Comput., 2016, 12, 910. [2] A. G. Slater et al, in preparation. [3] A. Pulido et al, Nature, 2017, accepted for publication April, 2017

75 O-50 The Solid-State Properties of Gels Formed with Phenylalanine and its Derivatives Gareth O. Lloyd a a Institute of Chemical Sciences, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh, Scotland, United Kingdom, EH14 4AS. g.o.lloyd@hw.ac.uk Gelation by small molecules represents a characterisation nightmare for solid-state chemists. This is mostly due to the inherent dynamics and instability of the solid component of the two phases present in the gel, the other phase being liquid, in most cases. In this presentation we highlight our attempts to characterise the solid state of the gels formed by phenylalanine and its derivatives (Phe) [1,2]. To accomplish this we utilise electron microscopy, X-ray diffraction and NMR to develop a more complete picture of the structure and dynamics of the fibrous materials that make up the solid network of the gels (see Figure below for examples of two types. DMSO gel on the left, and hydrogel on the right). Crystallography of periodic structures allows for the atomic detail of the crystalline fibres of the Phe hydrogels (gels made with water). NMR crystallography on the hydrated gels is accomplished allowing for confirmation of the structures without physical manipulation of the gels, i.e. drying or solvent removal that often results in phase changes of dynamic small molecule gelators. Dynamics of the fibres can also be determined utilising NMR techniques such as HR-MAS and STD. Aggregation of all these techniques leads us to assign the crystalline phases of the hydrogels as a family of isostructural monohydrate forms. The DMSO gels are non-crystalline but through NMR characterisation the solid-state the Phe molecules appear to have similar conformations to that found in the hydrate forms. Finally, halogenation of the aromatic group provides insights into the interactions resulting in these solid forms and how to manipulate the properties of the solid forms and the resultant gels. Keywords: Supramolecular gel, amino acids, NMR [1] L. Adler-Abramovich, L. Vaks, O. Carny, D. Trudler, A. Magno, A. Caflisch, D. Frenkel and E. Gazit,, Nat. Chem. Biol., 2012, 8, 701. [2] W.-P. Hsu, K.-K. Koo and A. S. Myerson, Chem. Eng. Commun., 2002, 189, April,

76 O-51 The Preparation of Nanoparticles and Nanostructures of Steroid Neurohormones. Yury N. Morozov, Vladimir V. Chernyshev, and Gleb B. Sergeev Department of Chemistry, M.V. Lomonosov Moscow State University Leninskie Gory 1-3 Moscow , Russia, To produce nanoparticles of poorly water-soluble drug substances, we have developed a unique low temperature strategy based on a dynamic combination of high and low temperature, gas and solid state and inert carrier gases. This strategy allows the scaling, it applicable for poorly water soluble drugs without any limitations, obtained nano-powders do not contain residual amounts of solvent. The developed low temperature technology has been used to produce nanoparticles of hormone 5- androstenediol. The obtained crystals had an average size of 220 ± 20 nm. We have also studied the transformation of steroid neuro-hormone dehydroepiandrosterone (DHEA), known to be prone to polymorphism, into new structures depending on experimental conditions. Six known polymorphic structures (denoted by the ordinal Roman numbers) have been previously obtained using various solvents, with FI and FII being the most stable form. Our approach allowed us to obtain new polymorphs of DHEA, which we have called FVII and FVIII. The crystallographic structure of FVII polymorph fully described [1]. The peculiarity of the FVII structure is the presence of quasi-infinite helical chains of DHEA molecules, organized through the system of hydrogen bonds formed by hydroxyl grope only. We found that that under optimal conditions, the content of the FVII and FVIII polymorphs is 85%, and 15% respectively. Formation of these structures occurs when CO 2 used as a carrier gas, the evaporator temperature is 140º C and condenser was cooled by liquid nitrogen. The average size of the crystals is 100±10 nm. We suggest that nucleation, growth and formation of nanoparticles is carried out by homogeneous mechanism in the gas phase as a result of deep supersaturation due to the sharp temperature drop and the strengthening of the role of weak intermolecular interactions. The phase composition of the resulting nano-form DHEA can be controlled by changing experimental conditions. When CO 2 carrier gas is replaced with helium in comparable conditions, the contribution of the various forms changes: a content of known structure FIII - 55%, content of FVII reduced to 30%, content of FVII is not changed. These features are associated with the mechanism of loss of the excess energy of the hot molecules DHEA in a homogeneous inter-molecular interaction with molecules of the carrier gases having different masses, number degrees of freedom ant thermo-physical properties. Removing the carrier gas and carrying out of the process in vacuum, dramatically affects the structure. It was found that in the condensation in the conditions, which exclude collisions of the molecules in the gas phase and the heterogeneous nucleation and growth of particles on a cold surface, the original form FI with 100% yield, is converted into form FII. The average particle size DHEA is in this case 120 nm. The obtained results show that the developed strategy opens up new opportunities for the design and engineering of nanocrystals of various drug compounds. Keywords: nanoparticles of drug substances, steroid neurohormone, 5-androstendiol, dehydroepiandrosterone (DHEA). [1] V.V. Chernyshev, Yu.N. Morozov, G.B. Sergeev, I.S. Bushmarinov, A.A. Makoed, G.B. Sergeev, Cryst. Growth Des., 2016, 16, April, 2017

77 O-52 Towards a Knowledge-Based Crystal Packing Score Neil Feeder The Cambridge Crystallographic Data Centre, Cambridge, CB2 1EZ, UK. feeder@ccdc.cam.ac.uk For nearly 50 years, the ICCOSS community has lead the way in building our understanding of how organic molecules assemble themselves into stable crystalline forms. Such knowledge has great commercial impact, especially in the pharmaceutical industry where structure, form and function of crystalline drugs go hand in hand with the highly regulated development of dosage forms.[1] This has driven significant developments in solid form screening and characterisation techniques[2] allowing the efficient experimental exploration of crystal form landscapes. Alongside this, tremendous advances have been made in computational approaches to predict organic crystal structures[3] that can add a useful perspective to the experiments. Nevertheless both experimental and computational approaches require significant investment of material or time or expertise to confidently make a solid form selection. Even when these elements are in abundance, unexpected outcomes can result as exemplified by Norvir [4] and Neupro [5]. At the CCDC we are developing knowledge-based structural informatics approaches that can provide rapid and accessible insight into organic crystal form landscapes that compliment these experimental and computational methods. The Cambridge Structural Database (CSD)[6] of 850,000+ small molecule crystal structures, represents a vast knowledge base of molecular geometry and intermolecular interaction preferences that we can mine to reveal the underlying rules that control crystal packing. Such methods, integrated within a pharmaceutical solid form selection process, can be used to carry out a simple solid form health check, assessing the likelihood that the stable form has indeed been uncovered.[7] Our latest area of research centers on the development of a consolidated knowledge-based crystal packing score that might quantitatively assess the relative stability of a form. In practice such a method could be run as soon as the crystal structure has been determined to immediately inform the solid state scientist as to the probability of that structure being the stable form. Here we will introduce two approaches 1) based upon the Full Interaction Mapping methodology[8] which seeks to quantify how well the observed packing shell satisfies the likely intermolecular geometry preferences derived from the CSD; 2) a summation of atom atom R F scores (ratio of observed frequency of occurrence in the CSD to the frequency expected at random)[9] for each observed intermolecular contact. The complementarity of the two methods will be explored by application to a range of polymorph pairs of drug-like molecules available in the CSD. Keywords: Crystal Form, Polymorphism, Structure Score, Structural Informatics [1] C. C. Sun, J. Pharm. Sci. 2009, 98, 5, [2] S. R. Byrn et al, J. Pharm. Sci., 2010, 99, 9, [3] A. M. Reilly et al., Acta Cryst. B 2016, 72, 439. [4] J. Bauer, et al, Pharm. Res., 2001, 18, 859. [5] K.R. Chaudhuri, Expert Opin. Drug Deliv., 2008, 5 (11), [6] C. R. Groom et al, Acta Cryst. B 2016, 72, 171. [7] N. Feeder, et al, J. Pharmacy and Pharmacology, 2015, 67, 857. [8] P. A. Wood, et al CrystEngComm, 2013, 15, [9] R. Taylor, CrystEngComm, 2014, 16, April,

78 O-53 Unique Magnetic Properties of All-Organic Radical Liquid Crystals Rui Tamura, a Yusa Takemoto, a Katsuaki Suzuki, a Satoshi Simono a and Yoshiaki Uchida a,b a Graduate School of Human and Environmental Studies, Kyoto University, Kyoto , Japan; b Graduate School of Engineering Science, Osaka University, Osaka , Japan. tamura.rui.8c@kyoto-u.ac.jp Liquid crystals, which are defined as thermal mesophases between crystalline and isotropic phases and can also be regarded as high temperature polymorphs of crystals, are unique soft materials that combine fluidity and anisotropy. From another viewpoint, liquid crystalline (LC) phases are considered to be a sort of complexity system consisting of non-equilibrium dynamic states due to the molecular motion and the coherent collective properties of molecules in the LC state. Accordingly, they are very sensitive to external stimuli, such as heat, light, temperature, pressure, electric or magnetic field, and added chiral dopants, so that LC superstructure can be easily altered. Since 2004, we have reported the preparation and mangetic properties of chiral rod-like all oraganic LC compounds with a stable cyclic nitroxide radical unit in the central core position and a negative dielectric anisotropy (De < 0).[1] Consequently, we could discover a unique magnetic phenomenon, referred to as positive magneto-lc effects, a generation of spin glass-like inhomogeneous ferromagnetic interactions (average spin-spin exchange interaction constant J > 0) induced by low magnetic fields in the various LC phases at high tenperatures ( C ).[2] Here we talk about i) the origin and mechanism of the generation of positive magneto-lc effects,[2,3] ii) the enhancement of positive magneto-lc effects in biradical and diradical LC compounds,[4] iii) the observation of magneto-electric effect in the ferroelectric and ferromagnetic LC phase,[5] and iv) the extension of an LC layer structure to biocompatible magnetic nanoemulsions which can be used as a magnetic resonance imaging (MRI) contrast agent and a magnetic carrier of drug delivery system (DDS) for biomedical application. Keywords: nitroxide radical liquid crystals, positive magneto-lc effects, magneto-electric effect [1] (a) N. Ikuma, et al., Angew. Chem. Int. Ed., 2004, 43, 3677; (b) R. Tamura, Y. Uchida, K. Suzuki, in Handbook of Liquid Crystals 2 nd Edition, Wiley-VCH, Weinhiem, 2014, vol. 8, p 837. [2] Y. Uchida, et al., J. Am. Chem. Soc., 2010, 132, [3] K. Suzuki, et al., J. Mater. Chem., 2012, 22, [4] K. Suzuki, et al., Chem. Commun. 2016, 52, [5] (a) N. Ikuma, et al., Adv. Mater., 2006, 8, 477; (b) K. Suzuki, et al., Soft Matter, 2015, 11, 5563; (c) R. Tamura, Y. Uchida, K. Suzuki, in Advances in Organic Crystal Chemistry: Comprehensive Reviews 2015, Springer, 2015, p April, 2017

79 O-54 Rationalising the Solid State Properties of Dithiadiazolyl Radicals Using a Combined Theoretical and Experimental Approach Bernard Dippenaar a, Catharine Esterhuysen a and Delia Haynes a a Department of Chemistry, University of Stellenbosch, Stellenbosch, South Africa. abdippenaar@sun.ac.za The synthesis of a 1,2,3,5-dithiadiazolyl radical, RCNSSN, was first reported in 1980 [1]. The 1,2,3,5- dithiadiazolyl (DTDA) radicals are a family of heterocyclic sulfur nitrogen-containing neutral radicals (Fig. 1). Studies have shown that the spin density in these radicals is localised on the SN heterocycle [2]. The R- group on the DTDA radicals can be changed without affecting the electronic structure of the radical, allowing manipulation of the solid-state structures, and hence the properties, of these materials. DTDA radicals are also attractive candidates for the development of novel organic materials with magnetic properties. These DTDA radicals do, however, tend to dimerise in the solid state, resulting in diamagnetic materials, and a lot of research has been dedicated to overcoming this dimerisation utilising various intermolecular interactions. In this study, DTDA dimerisation energy was investigated by performing various computational calculations. The interaction energies between pairs of radicals were calculated at the UB3LYP/ G(d,p) level of theory utilising the Gaussian09 and Amsterdam Density Functional (ADF) software packages. Furthermore, the spin-dependent density was analysed with Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) calculations, to shed light on the other intermolecular interactions between the radicals and how these could be manipulated in order to obtain DTDA radicals with improved properties. Results from theoretical studies on known DTDAs have been used in order to predict whether a series of uncharacterised DTDAs will be monomeric in the solid state. A series of radicals known to be monomeric in the solid state, p-o 2N-, pcn- and pbr-c 6F 4CNSSN, were synthesised in order to use a new technique for co-refining X-ray and polarised neutron diffraction data [3]. This will allow for an investigation of the spindependent electron density in these radicals. Figure 1 shows the compound (4-Phenyl-1,2,3,5-dithiadiazolyl) (4-perfluorophenyl-1,2,3,5- dithiadiazolyl) on the left, with the spin density localised on the SN heterocycle on the right. Keywords: DTDA, NBO, AIM, Gaussian, ADF, XRD, PND [1]1. A. Vegas, A. Pérez Salazar, A. J. Banister and R. G. Hey, J. Chem. Soc. Dalton Trans., 1980, [2] See for example P. J. Alonso, G. Antonerra, J. I. Martínez, J. J. Novoa, F. Palacio, J. M. Rawson and J. N. B. Smith, Appl. Mag. Reson., 2001, 20, 231. [3] M. Deutsch, B. Gillon, N. Claiser, Gillet, C. Lecomte and M. Souhassou, IUCrJ, 2014, 1, ; M. Deutsch, N. Claiser, S. Pillet, Y. Chumakov, P.Becker, JM. Gillet, B. Gillon, C. Lecomte and M. Souhassou, Acta Cryst., 2012, A68, April,

80 O-55 Design Strategies for the Prediction of Porous Organic Cage Topologies Valentina Santolini, a Enrico Berardo a and Kim E. Jelfs a a Department of Chemistry, Imperial College London, South Kensington Campus, London, SW7 2AZ, United Kingdom vs13@ic.ac.uk Porous organic materials are a class of materials that are constructed by the intermolecular packing of discrete organic molecules that contain void space in an internal cavity[1], and are typically solution processable. Many experimental and computational studies have been conducted on porous cages, however design and prediction of new molecular structures still represents a great theoretical challenge[2]. In this context, we developed a computational strategy (summarized in the Figure) to generate new porous organic molecules and test their experimental feasibility. This is based on an automatic procedure that assembles building blocks with different numbers of reactive ends into cages with the underlying topology of Platonic and Archimedean solids[3]. Once different topologies are generated from an initial pair of precursors, the software proceeds to a geometric and energetic characterization of each molecule, to understand which structure is the most stable and therefore more experimentally likely to form. All the cages are assembled according to reversible Dynamic Covalent Chemistry reactions[4] that provide the opportunity for thermodynamic control over the product. For this reason, throughout the procedure the cage with the lowest relative energy is considered the most likely experimental outcome. The solvent is only considered when its scaffolding effect plays an important role in keeping the cavity of the cage open[5]. The prediction strategy has been successfully tested on a number of experimentally available structures[3], and is currently being used to predict the formation of a wide range of novel organic cages in the context of a computational-experimental collaboration with the group of A. Cooper (University of Liverpool). A highthroughput screening robot has been used to carry out the synthesis of 78 new cages, starting from a selection of different functional precursors, which have been mixed in a combinatorial way. The computational software is working in parallel at the prediction of the same cages, and results are so far promising. In the future, we are planning to apply the software to the prediction of multi-component systems (where 3 or more different precursors are involved) and to the discovery of promising hypothetical candidates for synthesis. Keywords: porous organic cages, topology, prediction [1] G. Zhang, and M. Mastalerz, Chem. Soc. Rev., 2014, 43, [2] K. E. Jelfs et. al., J. Am. Chem. Soc., 2013, 135, [3] V. Santolini, M. Miklitz, E. Berardo, K.E. Jelfs, Submitted. [4] P. T. Corbett et. al., Chem. Rev, 2006, 106, [5] V. Santolini, G. A. Tribello, K.E. Jelfs, Chem. Commun., 2015, 51, April, 2017

81 O-56 Hydrogen Bonding Motifs in Ammonium Carboxylate Salts Jerry L. Atwood and Donna L. Beauchamp Department of Chemistry, University of Missouri-Columbia, Columbia, MO 65211, USA The world market for pharmaceuticals exceeds 1.5 trillion dollars US annually. Well over 95% of drug sales involve the organic solid state. Of course, the major portion of this market involves new compositions of matter covered by patents. With regard to US patent law, new polymorphs and pseudopolymorphs are new compositions of matter, and they are usually patentable. There are standard methods for discovering new crystal forms, and these methods constitute important endeavours in both industrial and academic laboratories. In this discussion, I will describe new strategies for the isolation of polymorphs and pseudopolymorphs of organic compounds (pharmaceuticals). Indeed, in my opinion our community is just now on the frontier of such discoveries. 2 7 April,

82 P-1 Tuning Thermo-Mechanical Properties of Thermosalient Organic Materials Lukman O. Alimi, a Prem Lama, a Vincent J. Smith a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. lukman@sun.ac.za Tuning thermo-mechanical properties of ordered organic materials for desirable applications remains a monumental challenge in the field of material science despite their great potentials for high performance mechanical actuators, artificial muscles, solar cells, photonics, bioelectronics, explosives and flexible electronics[1]. Here we examine the thermal behaviour of two different thermosalient organic materials namely 4-Aminobenzonitrile (ABN) and 4-(Dimethylamino)benzonitrile (DMABN) by cocrystallization and mechanochemical methods at different mole ratio combinations of ABN and DMABN viz AD_1:1, AD_1:2 and AD_2:1. The materials obtained after thorough grinding were characterized by means of PXRD, differential scanning calorimetry (DSC), IR and hot stage microscopy (HSM). Surprisingly, only AD_1:2 shows no thermosalient effect but exhibits thermal behaviour that is completely different from that of the starting materials. Hence, AD_1:2 was crystallized in acetone and the crystals obtained was characterized using SCXRD to give unit cell parameters different from the individual components and shows a similar thermal behaviour as observed for the mechanochemical materials. Further analysis of the crystal structure reveals the presence of both weak hydrogen bonding and C-H interactions, which could be responsible for the positive thermal expansion behaviour exhibited by AD_1:2 when compared with the thermosalient behaviour shown by the individual starting materials (ABN and DMABN) where either of these interactions exists in their respective packing arrangements. Keywords: Thermosalient effect, tuning, thermo-mechanical, cocrystallization and mechanochemical methods [1] Ghosh, S.; Reddy, C. M. Angew. Chem., Int. Ed. 2012, 51, April, 2017

83 P-2 Halogen and Hydrogen Bonding in Host Guest Compounds Francoise M. Amombo Noa, a Susan A. Bourne a and Luigi R. Nassimbeni a a Department of Chemistry, University of Cape Town, Private Bag, Rondebosch 7701, South Africa. ammfra002@myuct.ac.za The host compounds tetrakis (4-bromophenyl) ethylene and its iodo-analogue form inclusion complexes with halogenated organic guests. All the host-guest structures have been elucidated followed by the analysis and classification of their nonbonded halogen halogen contacts. Kinetics of desolvation haven been studied and the concomitant activation energies have been established. The velocity of the enclathration for the solid hostmethyl iodide (MeI) vapor reactions and associated rate law have been studied. [1] Series of exchange experiments were performed on the structures having 1, 2-dichloroethane (DCE) as guests by exposing their crystals to the vapors of MeI. Their kinetics of exchange was monitored by NMR spectroscopy, and the reactions were interrupted and the structures of the inclusion compounds containing both the incoming and outgoing guests were solved. One of the intermediate structures yielded a unit cell which has quadrupled in volume and shows both DCE and MeI in distinct and separate crystallographic sites. [2] Similar host compounds with fluorenyl moiety were utilized in the study of hydrogen bonding versus halogen bonding with 3-bromopyridine and its chloro-analogue as guest. The hydrogen bonding motif (Host) O-H O (Host)-H N (Guest) was prominent while the halogen halogen interactions are of secondary importance in the packing of the structures. [3] (a) Kinetics of desolvation, (b) Guest exchange mechanism in the structures and (c) Hydrogen and halogen bonding in selected diol host compounds. Keywords: Halogen halogen interactions, Guest exchange, Kinetics, Hydrogen bonding versus halogen bonding. [1] FMA. Noa, SA. Bourne and LR. Nassimbeni, Cryst. Growth Des., 2015, 15, [2] FMA. Noa, SA. Bourne, H. Su and LR. Nassimbeni, Cryst. Growth Des., 2016, 16, [3] FMA. Noa, SA. Bourne, H. Su, E. Weber and LR. Nassimbeni, Cryst. Growth Des., 2016, 16, April,

84 P-3 Multi-Component Solid Solutions Composed of Theophylline and Structural Isomers of Fluorobenzoic Acids Mihails Arhangelskis, a Mérina K. Corpinot, b Dejan-Krešimir Bučar b and William Jones c a Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal H3A 0B8, Canada; b Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK; c Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1RL, UK. mihails.arhangelskis@mcgill.ca In our recent publication [1] we have investigated the structural landscape of cocrystals composed of theophylline (thp) and fluorobenzoic acids (FBAs). Our study revealed that the thp cocrystals exhibit unpredictable structures featuring various types of supramolecular interactions, thus highlighting the difficulties in predicting supramolecular interactions in molecules that involve numerous hydrogen-bonding functional groups. In this contribution we will discuss the peculiar structural features of four cocrystals that were discovered in our initial studies, namely thp:2,3,5-trifba, thp:2,3,6-trifba, 2,3,5,6-tetraFBA and thp:3,5-difba. The first three cocrystals are isomorphous and based on the type A supramolecular interaction (Figure on the left). The thp:3,5-difba cocrystal, on the other hand, displays a unit cell that is nearly identical to the unit cells of the first three cocrystals. The positions and arrangement of the thp molecules in this cocrystal is also identical to one seen in the first three cocrystals. The cocrystal components are, however, sustained by type C supramolecular interactions. The thp:3,5-difba cocrystal is therefore pseudo-isomorphic to the structures of thp:2,3,5-trifba, thp:2,3,6-trifba and 2,3,6-triFBA (Figure on the right). The structural similarity of the four cocrystals prompted us to investigate whether a polymorph of thp:3,5- difba cocrystal containing type A supramolecular interaction could be produced via heteronuclear seeding. Whilst a pure cocrystal product had not been obtained, these experiments resulted in the discovery of a series of three- to six-component solid solutions of varying complexity. Structural investigations revealed that that 3,5-diFBA engages in hydrogen bonding with thp via interaction of the type A. The materials have been extensively characterized using powder X-ray diffraction, solid-state NMR and thermal methods. Strong correlations between the compositions of the solid solutions, their lattice parameters and dissociation temperatures were observed. Theoretical calculations were used to rationalize the observed synthon hierarchies and quantify the energies of individual intermolecular interactions. Attempts were also made to incorporate other FBA molecules into solid solutions, yet they were unsuccessful. It was observed that thp cocrystal involving 3,5-diDBA, 2,3,5-triFBA, 2,3,6-triFBA and 2,3,5,6- tetrafba exhibit structural features that are not present in thp cocrystals involving other FBA isomers. Our investigations suggest that (contrary to Kitaigorodskii s proposition) molecular volume relationships are not the only decisive factor that governs the formation of solid solutions. Keywords: solid solution, supramolecular synthon, theophylline. [1] M. K. Corpinot, S. A. Stratford, M. Arhangelskis, J. Anka-Lufford, I. Halasz, N. Judaš, W. Jones, D.-K. Bučar, CrystEngComm 2016, 18, April, 2017

85 P-4 The Investigation of the Interactions Between CO2 and p-tertbutylcalix[4]arene in the Solid State Jeanice L. Basson, a Prem Lama a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. jlbasson@sun.ac.za The high density and low density polymorphs of the non-porous organic host, p-tert-butylcalix[4]arene (TBC4), have shown interesting interactions with CO 2 in the solid state. The guest-free low density polymorph of TBC4 (space group P2 1/n) is a well-known CO 2 absorber and is able to undergo a structural change to accommodate CO 2 molecules in intermolecular cavities [1]. At a low CO 2 pressure the guest molecules occupy the intrinsic voids of the macrocycle. However, under high CO 2 pressure the host structure converts to a tetragonal form (space group P4/n) that contains additional extrinsic spaces filled by one guest molecule each. This porous phase becomes metastable upon CO 2 removal to give rise to a tetragonal apohost phase that persists at ambient conditions. In contrast, the high density polymorph of TBC4 (space group P2 1/c) is unable to absorb CO 2 and remains in a close-packed structure up to 35 bar of CO 2. However, increased interaction between CO 2 and the host at high pressure results in a gas-induced transformation [2] to the tetragonal low density polymorph. Keywords: CO2 capture, p-tert-butylcalix[4]arene, sorption analysis [1] K. Udachin, I. Moudrakovski, G. Enright, C. Ratcliffe and J. Ripmeester, Phys. Chem. Chem. Phys., 2008, 10, [2] P. Thallapally, B. McGrail, S. Dalgarno, H. Schaef, J. Tian and J. Atwood, Nature Mater., 2006, 7, April,

86 P-5 Enantiomeric Conversion in Two 3D Copper-Glutarate based MOFs. Charl X. Bezuidenhout, Vincent J. Smith, Catharine Esterhuysen and Leonard J. Barbour. Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. Two 3D Cu(II)-glutarate-based MOFs with flexible linkers, [Cu 2(glu) 2(bpa)] and [Cu 2(glu) 2(bpp)],[1] undergo spontaneous phase changes upon solvent loss at room temperature. These MOFs are an extension of the isoreticular series, containing rigid linkers, previously reported.[2] Using single crystal X-ray diffraction (SCXRD), we show that the phase changes result in new narrow-channel phases, with a large reduction in solvent-accessible volume as compared with the original wide-channel phases. Moreover, the [Cu 2(glu) 2(bpa)] MOF displays a stepped sorption isotherm upon CO 2 sorption at RT. This is indicative of the framework reverting to the wide-channel phase. The positions of the CO 2 molecules in the channels of the frameworks were determined using SCXRD analysis of crystals exposed to supercritical CO 2. Finally, a scan of the potential energy surface using molecular mechanics was conducted to elucidate the mechanism by which the phase change occurs. This appears to be a direct enantiomeric conversion of the glutarate ligands as a result of structural constraints. Keywords: phase-change, carbon dioxide, potential energy scan [1] I. H. Hwang, J. M. Bae, W.-S. Kim, Y. D. Jo, C. Kim, Y. Kim, S.-J. Kim, S. Huh, Dalton Trans. 2012, 41, [2] C. X. Bezuidenhout, V. J. Smith, P. M. Bhatt, C. Esterhuysen, L. J. Barbour, Angew. Chem. Int. Ed. 2015, 54, April, 2017

87 P-6 Inhibition of [2+4] Diels-Alder Reactions in Charge-Transfer Crystals Delbert S. Botes, a Sanaz Khorasani, a Welni Duminy, a Demetrius C. Levendis a and Manuel A. Fernandes a a Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, Johannesburg 2050, South Africa @students.wits.ac.za Solid-state reactions, besides being environmentally friendly, provide a means of obtaining unique molecules and new crystalline forms. The crystal lattice controls the reaction outcome resulting in both regio- and stereoselectivity in the obtained products. However, difficulties in co-crystallising applicable reactants together in a crystal lattice have limited work in this field. By exploiting electron donor interactions, it is possible to cocrystallise molecules together to form heteromolecular charge-transfer crystals where the reactants are correctly orientated to potentially undergo reaction.[1] Charge-transfer crystals made using 1,4-dithiintetracarboxylic type compounds and anthracene derivatives consist of stacks of electron donor and acceptor molecules in a 1:1 ratio and are potentially able to undergo thermally induced [2+4] Diels-Alder reactions where the former act as the diene and the latter the dienophile. Examples of these types of reactions have been studied through single crystal X-ray crystallography and have illustrated that the reactions occur with low temperature heating (30-50 C) and proceed in a single-crystal-tosingle-crystal (SCSC) manner whereby the product Diels-Alder adduct forms within the reactant crystal. Schmidt s topochemical principle and Kaupp s model involving phase rebuilding and transformation followed by crystal degradation are current models which have been used to explain how these reactions occur.[2-3] Here we present examples involving bis(n-benzylimino)-1,4-dithiin as the electron acceptor with anthracene and several derivatives as electron donors [anthracene (ant), 9-vinylant, 9-bromoant, 9-cyanoant, 9- formylant and 2-methylant] where the cycloaddition reaction does not occur in a SCSC manner and is inhibited at low temperatures. Analysis through single crystal X-ray diffraction as well as differential scanning calorimetry show that the reactions proceed at far higher temperatures in the solid state compared to others studied. The benzyl substituents inhibit the Diels-Alder reaction from occurring at lower temperatures with their arrangement in the crystal lattice preventing the molecules from being able to move favorably for the reaction to be achievable. This shows that although distance as well as the positioning of molecules are important in the reactivity of molecules in the solid-state, the nature of the groups involved in a reaction also contribute greatly to the reaction outcome and the ability for a solid state reaction to occur without loss of crystallinity. Crystallisation <100 C X Crystal Keywords: solid-state reaction, Diels-Alder, charge-transfer complex 1] J. H. Kim, S. V. Lindeman and J. K. Kochi, J. Am. Chem. Soc., 2001, 123, [2] S. Khorasani, D. S. Botes, M. A. Fernandes and D. C. Levendis, CrystEngComm, 2015, 17, [3] M. A. Fernandes and D. C. Levendis, CrystEngComm, 2016, 18, April,

88 P-7 Multicomponent Dithiadiazolyl Crystals as a Route to Novel Magnetic Materials Thalia Carstens, Delia A. Haynes Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7602, South Africa. tc2@sun.ac.za Over the past few years, dithiadiazolyl radicals (DTDAs) have been of interest due to their potential as building blocks for magnetic materials, with increased interest arising with the discovery of weak ferromagnetic ordering in the β phase of 4'-4'-NCC 6F 4CN 2S 2 [1]. DTDAs dimerise readily in the solid state, resulting in spin pairing, and rendering them diamagnetic. It has been shown that variation in the R-group has no significant influence on the electronics of the DTDA ring [2]. It has also been shown that co-crystals of DTDAs can be made, which contain two different radicals (co-formers) in a heterodimer [3]. In an attempt to rationalise the formation of these DTDA co-crystals, a theoretical investigation has been undertaken. Density Functional Theory calculations were performed on the molecules making up the three known DTDA co-crystals, as well as their co-former homodimers, at the UB3LYP/6-311G++(d,p) level of theory to determine the energies of the heterodimers as well as homodimers. This was done to probe the stability of the co-crystal in comparison to its co-formers. Spin-unrestricted periodic calculations were also done on the known co-crystals and co-formers to further investigate thermodynamic properties such as lattice energies, in order to gain an understanding of the driving force behind co-crystal stability. Additionally, an experimental study is underway, whereby chosen DTDAs will be co-crystallised with one another in order to generate novel co-crystals. The results of this study will be compared to the computational results. Keywords: co-crystal, radical, dimerisation, DFT [1] A. J. Banister, N. Bricklebank, W. Clegg, M. R. J. Elsegood, C. I. Gregory, I. Lavender, J. M. Rawson, and B. K. Tanner, Chem. Comm., 1995, [2] D. A. Haynes, CrystEngComm., 2011, 13, [3] C. Allen, D. A. Haynes, C. M. Pask, and J. M. Rawson, CrystEngComm., 2009, 11(10), April, 2017

89 P-8 Multi-Component Photochromic MOFs Dominic Castell, a Varvara I. Nikolayenko a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. castell@sun.ac.za Photochromism is derived from the Greek words phos meaning light and chroma meaning colour. It is described as the reversible transformation of two chemical species that have different absorption spectra in the visible region and is induced by absorption of electromagnetic radiation. [1] Although photochromic compounds such as spirobenzopyrans,[2] azobenzenes (ABs)[3-4] - and fulgides[5-6] - have been studied extensively, few exhibit photochromism in the solid state. Bis-3-thienylcyclopentenes are a unique group of photochromic compounds that can undergo photocyclisation in the solid state to yield thermally stable ring-closed isomers. Subsequent exposure to visible light induces cycloreversion to the ring-open form and these compounds have shown impressive solid-state fatigue resistance (>100 cycles), with relatively high thermal stability of both isomers.[5] Although BTCPs can exist in two conformations (parallel and antiparallel), photocyclisation only appears to occur for the antiparallel isomer. Due to the wide range of potential applications, including ophthalmic lenses (corrective lenses), molecular switches, biomedical research and information technology (data storage), the use of molecular engineering to fine tune - photochromic compounds is a rapidly growing field.[7-8] Recent work conducted in the Barbour group has shown that the inclusion of bis-3-thienylcyclopentene ligands into metal-organic frameworks (MOFs) enables light modulated control of porosity. The study concluded that the observed ring-closure relied upon the flexible nature of the secondary linker. This work expands upon this observation. λ Keywords: Diarylethene, MOF, Photochromism, single-crystal to single-crystal [1] N. K. Nath, M. K. Panda, S. C. Sahoo and P. Naumov, CrystEngComm., 2014, 16, [2] M. Kamenjicki, I. K. Lednev, S. A. Asher, Adv. Funct. Mater, 2005, 15, [3] E. Merino, Chem. Soc. Rev, 2011, 40, [4] O. S. Bushuyev, A. Tomberg, T. Friščić, C. J. Barrett, J. Am. Chem. Soc, 2013, 135, [5] A. Santiago, R. S. Becker, J. Am. Chem. Soc, 1968, 90, [6] Y. Yokoyama, Chem. Soc. Rev, 2000, 100, [7] a) C. B. McArdle, Blackie, Applied Photochromic Polymer Systems, ed. Glasgow, 1992; b) M. Irie, Photo-Reactive Materials for Ultrahigh Density Optical Memory, Elsevier, Amsterdam, [8] M. Irie, Chem. Rev., 2000, 100, 5, April,

90 P-9 Soft Photolithography in Halogen-Bonded Azobenzene Cocrystals Jan-Constantin Christopherson, a Oleksandr S. Bushuyev, a Igor Huskić, a Davin Tan, a Christopher J. Barrett a and Tomislav Friščić a a Department of Chemistry, McGill University, 801 Sherbrooke Street W, Montreal, QC, H3A 0B8, Canada. janconstantin.christopherson@mail.mcgill.ca Our group is investigating the solid-state photochemistry of a series of fluorinated azobenzene (azo) molecules exhibiting unusually long cis-halflives. Specifically, we are using these molecules to develop new crystal engineering strategies for generating photo-sensitive crystalline solids, for example through halogen bond-driven cocrystal formation.[1,2] In that context, we have recently demonstrated a new type of irreversible photo-mechanical behavior, that allows shaping of organic crystals and co-crystals through a crystal-to-crystal cis trans photoisomerization induced by visible light.[3] We now demonstrate that using oxygen-based acceptors as components of azo-based halogen-bonded cocrystals enables the synthesis and even design of novel materials that are both highly dichroic,[4] and can be readily punctured, carved or sliced through visible laser irradiation. In this presentation will outline the discovery and current understanding of this exciting new 'soft photolithographic' effect and, at the same time, highlight a potential new use of cocrystallization as a means to generate organic solids amenable to visible light photolithography. Keywords: azobenzene, halogen bonding, cocrystallisation, dichroism, soft lithography [1] Bushuyev, O. S.; Corkery, T.C.; Barrett, C.J; Friščić, T., Chem. Sci., 2014, 5, 3158; [2] Bushuyev, O.S., Tomberg, A., Vinden, J.R., Moitessier, N., Barrett, C.J., Friščić, T. Chem. Commun., 2016, 52, 2103; [3] Bushuyev, O. S.; Tomberg, A.; Friščić, T., J. Am. Chem. Soc. 2013, 135, 12556; [4] Bushuyev, O.S., Friščić, T., Barrett, C.J., Cryst. Growth Des. 2016, 16, April, 2017

91 P-10 Post-Synthetic Photochemical [2+2] Cycloaddition in Cadmium MOFs Isabella E. Claassens, a Leonard J. Barbour a and Delia A. Haynes a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. iec@sun.ac.za Photochemical cycloaddition can readily occur in the solid state with minimal atomic and molecular motion if potentially reactive double bonds have a parallel alignment to one another and are separated by no more than 4.2 Å.[1] The structural rigidity of metal-organic frameworks (MOFs) can be used to correctly align double bonds in order to undergo [2+2] cycloaddition in the solid state. Post-synthetic modification in this way could ultimately yield a stimulus responsive MOF where photo-induced cycloaddition results in a change in the porosity.[2] In order to investigate this possibility, we prepared single crystals of a photoactive cadmium-based MOF with. The as-synthesised DMA solvate of the MOF, [Cd(bpeb)(obc)] DMA, was irradiated with 365 nm UV light for 15 minutes, after which a 70% yield of cycloaddition was observed. Sorption studies pre- and postcycloaddition will be reported. Preliminary results on solvent-exchanged crystals suggest that isomerisation of the ligand may result in a change in the selectivity of the framework in this MOF. Keywords: photochemical [2+2] cycloaddition, post-synthetic modification, stimulus responsive MOF [1] G. M. J. Schmidt, Apure Appl. Chem., 1971, 27, [2] S. Castellanos, F. Kapteijn and J. Gascon, CrystEngComm, 2016, 18, April,

92 P-11 Structures and Properties of Aminoquinoline Salts Monica Clements, a Margaret Blackie a and Tanya le Roex a a Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. monicac@sun.ac.za It is well-known that the physical properties of a crystalline drug system stem from the packing and association of the molecules in the solid state and that altering these intermolecular interactions could have a profound effect on the physicochemical properties of the drug molecule. [1 3] Exploitation of this concept has become popular in recent years as it allows for an improvement of some undesirable properties without compromising the structure, and thus the efficacy, of the drug. [1] This has prompted researchers to pursue the formation of salts and cocrystals of a number of drug molecules to determine the effect that it has on the physicochemical properties of a drug molecule, such as solubility, thermal stability, bioavailability and, ultimately, the pharmacokinetic profile. Despite these results, the use of this method in the attempt to improve some of the properties of antimalarial compounds has received little attention, despite the urgent need for effective drugs to combat the widespread tropical disease. [4] Given how long it takes to conceptualize, synthesize and test novel compounds, the formation of multicomponent forms of drug molecules could provide added value for already known compounds that have been previously discarded due to poor pharmacokinetic profiles. The work described here explores the formation of multicomponent forms of a small series of compounds comprising three 4-amino-7-chloroquinoline analogues, each with a 1,2,3-triazole moiety linking the 7- chloroquinoline core scaffold and the amino side chain. Each aminoquinoline was cocrystallised together with salicylic acid or pamoic acid, and all structures obtained are reported. The effect that cocrystallisation and salt formation has on selected physicochemical properties is also studied. Keywords: physicochemical, multicomponent, antimalarial, aminoquinolines l [1] N. Schultheiss and A. Newman, Cryst. Growth Des. Des.,2009, 9, [2] J. Steed, Trends Pharmacol. Sci., 2013, 34,185. [3] I. Miroshnyk, S. Mirza, and N. Sandler, Expert Opin. Drug Deliv., 2009, 6, 333. [4] M. Clements, T le Roex and M. Blackie, ChemMedChem., 2015, 10, April, 2017

93 P-12 Additional Guidelines for the Design of Isostructural Molecular Crystals Mérina Corpinot, a Rui Guo, a Samuel A. Stratford, b Mihails Arhangelskis, b Jodie Anka-Lufford, a Antonios Ninos, a Ai Ahirara, a Ivan Halasz, c William Jones, b Sarah L. Price a and Dejan-Krešimir Bučar a a Department of Chemistry, University College London, UK, Department of Chemistry; b University of Cambridge; UK, Department of chemistry; c Division of Physical Chemistry, Ruđer Bošković Institute, Zagreb, Croatia. merina.corpinot.13@ucl.ac.uk New guidelines for the design of structurally equivalent molecular crystals were derived from a structural analysis of new cocrystals and polymorphs of saccharin and thiosaccharin, aided by a computational study. The study shows that isostructural crystals may be obtained through an exchange of >C=O with >C=S in the molecular components of the solids, but only if the exchanged atom is not involved in hydrogen bonding. [1] These results imposed the question of whether other hydrogen- and halogen-bonding functional groups can be exchanged under the same conditions to prepare isostructural cocrystals. With this in mind, we studied the exchange of hydrogen atoms with fluorine atoms in cocrystals of theophylline, [2] the exchange of amide with thioamide functional groups in cocrystals of benzamide, the interchange of phenyl with thiophenyl groups in cocrystals of benzoic acid, as well as the exchange of halogen-bond donors (iodo/bromo) and acceptors (oxygen/sulfur) in cocrystals of benzamide derivatives and 1,4-diiodobenzene. [3] The crystallographic investigations involved more than eighty cocrystals and their outcomes will be discussed in details, while other new guidelines for the design of molecular cocrystals will be proposed. Keywords: cocrystals, isostructurality [1] M. K. Corpinot, R. Guo, D. A. Tocher, A. B. M. Buanz, S. Gaisford, S. L. Price, D.-K. Bučar, submitted for publication. [2] M. K. Corpinot, S. A. Stratford, M. Arhangelskis, J. Anka-Lufford, W. Jones and D.-K. Bučar, CrystEngComm, 2016, 18, [3] Kevin S. Eccles, Robin E. Morrison, Abhijeet S. Sinha, Anita R. Maguire, and Simon E. Lawrence, Cryst. Growth Des., 2015, 15, April,

94 P-13 Gas-Solid Interactions and Sorption in a Porous Hydrogen- Bonded Organic Framework Jan Costandius a and Vincent J. Smith a,b a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa; b Department of Chemistry, Rhodes Univeristy, Grahamstown, 6139, South Africa @sun.ac.za The high-pressure isotherms and gas-solid interactions of the hydrogen bonded molecular organic framework (HOF) of 4,4,4 -nitrilotribenzoic acid (HOF-1) and CO 2 are investigated herein. Hydrogen-bonded molecular organic frameworks or HOFs are organic crystalline structures linked by strong hydrogen-bonding interactions. For the purposes of gas sequestration, HOFs are generally required to be rigid, porous and able to absorb large amounts of a target gas.[1] These properties are investigated in a previously-synthesised HOF, first published by Nandi et al.[2] Standard and high-pressure single-crystal X-Ray diffraction illustrates the porosity and rigidity, and thermal analysis showed the structural robustness of HOF-1 (-40 C < T < 200 C), thereby asserting that HOF-1 meets the criteria of a successful HOF. HOF-1 shows a notably higher uptake for CO 2 over N 2 of 2.75:1 at 50 bar, despite CO 2 and N 2 having comparable kinetic diameters.[3] Computational analysis of the interactions between HOF-1 and CO 2 shows that it is of an electrostatic nature. Keywords: HOF, CO2, Isotherms, Interactions [1] H. Wang, B. Li, H. Wu, T. L. Hu, Z. Yao, W. Zhou, S. Xiang and B. Chen, J. Am. Chem. Soc., 2015, 137, [2] S. Nandi, D. Chakraborty and R. Vaidhyanathan, Chem. Commun., 2016, 52, [3] N. Mehio, S. Dai and D. E. Jiang, J. Phys. Chem. A, 2014, 118, April, 2017

95 P-14 Steric Interactions Revealed by Atoms In Molecules and EDA Sunel de Kock, a Catharine Esterhuysen a and Jan L.M. Dillen a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. sdekock@sun.ac.za Within the framework of Atoms In Molecules, a bond path and associated bond critical point are considered to be sufficient evidence for the existence of a stabilising bonding interaction.[1] However, the presence of such apparent bonding interactions between congested atoms, where the interatomic distances separating them is longer than the sum of their van der Waals radii, has been the source of much controversy in the literature. [2] In this work a series of Au(I) N-heterocyclic carbene (NHC) complexes bearing different substituents at the NHC nitrogen atoms is considered. The molecular graphs exhibit numerous ligand-ligand as well as ligand-metal intramolecular bonding interactions. Although the presence of a bond path implies a stabilising interaction between the atoms in question, it does not offer insight into whether this interaction is stabilising the molecule in its entirety. To gain insight into the energetic effect of these interactions, we compared these complexes in terms of their structures and the Au-ligand bond dissociation energies, and performed Energy Decomposition Analysis [3] to determine the relative contributions of electrostatics, Pauli repulsion, the orbital interaction, and dispersion to the Au-ligand interaction energy. Our results indicate that bond paths between congested atoms can be diagnostic of steric effects, and should not be assumed to be stabilising a molecule as a whole, especially when other, strong interactions may be bringing atoms into close proximity. Keywords: Salicylic acid, 5-sulfosalicylic acid, benzimidazole, adenine, cytosine, fluorocytosine, proton transfer compound, two- and three-point synthons. [1] E. J. C. de Vries, S. Kantengwa, A. Ayamine, and N. B. Báthori, CrystEngComm., 2016, 18, April,

96 P-15 Salts of Salicylic and Sulfosalicylic Acid with Nucleobases and Derivatives Elise J. C. de Vries, Sylvia Kantengwa, Alban Ayamine and Nikoletta B. Báthori Department of Chemistry, Faculty of Applied Sciences, Cape Peninsula University of Technology, P.O. Box 652, Cape Town, 8000, South Africa. In this study synthon engineering concepts were tested by using nucleobases and derivatives, namely adenine, cytosine, benzimidazole and fluorocytosine and crystallising them with salicylic acid and 5- sulfosalicylic acid. These bases were selected to investigate how the hydrogen bond donor and acceptor groups would influence the crystal structure. Salicylic acid was selected to investigate N H O hydrogen bonding and synthon formation, while its derivative, 5-sulfosalicylic acid, was selected to see how the sulfonate group would enhance or disrupt these features. Each of the seven complexes obtained was characterised by single crystal X-ray diffraction, which showed that acid base pairing favoured salt formation. All the salicylic acid complexes adopt similar hetero supramolecular synthons, while 5- sulfosalicylic acid forms more complex structures with more than one type of synthon present. Crystal formation using cytosine or fluorocytosine did not result in the predicted synthon formation. This unexpected outcome highlights the current limitations of synthon engineering. [1] Keywords: Salicylic acid, 5-sulfosalicylic acid, benzimidazole, adenine, cytosine, fluorocytosine, proton transfer compound, two- and three-point synthons. [1] E. J. C. de Vries, S. Kantengwa, A. Ayamine, and N. B. Báthori, CrystEngComm., 2016, 18, April, 2017

97 P-16 A Metallocyclic Host Shows Selectivity Towards para-xylene Marike du Plessis a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. mdp@sun.ac.za Xylenes are extracted during the industrial refinement of crude oil and then used as chemical intermediates towards the manufacture of a variety of products. Separation and purification of the ortho, meta, and para isomers is carried out prior to functionalisation of the methyl substituents in order to exploit their applications in the production of plasticisers, paints, etc. Due to their similar boiling points, the industrial separation of xylene isomers by distillation is expensive and inefficient. Much research has been devoted to finding host compounds that will selectively absorb a specific isomer of xylene in order to fine-tune the properties of the currently most used host-guest systems for this application, namely zeolites [1]. We are studying metallocycles for their ability to discriminate between small guest molecules such as xylenes. In this regard, we have obtained promising results with a metallocycle previously reported by our group [2]. The activated host is capable of selectively absorbing p-xylene from binary and ternary mixtures of xylene isomers in equal ratios in the liquid phase. When exposed to a mixture of ortho- and meta xylene in a 1:1 ratio, it selectively absorbs the meta isomer. Guest exchange at the solid liquid interface frequently occurs as a single-crystal transformation for this specific host. Single-crystal X-ray diffraction analysis revealed the position of p-xylene in the channels of the host and attempts to obtain the ortho and meta solvates for comparison are still under way. Significant conformational changes are observed in the imidazole moieties of the host, which twist in order to accommodate the guest molecules, transforming the empty pockets of the apohost into a continuous solvent filled channel. The selectivity of this apohost for p- xylene is supported by PXRD and GC results which indicate that the apohost will even adsorb a significant amount of p-xylene from 99% commercially pure o-xylene containing only trace amounts of the para isomer. Furthermore the apohost shows a subtle but notable solvochromic response to p-xylene, which is supported by UV/vis experiments. Keywords: xylene separation, metallocycle, host-guest chemistry [1] K. A. O. Santos, A. A. Dantas Neto, M. C. P. A. Moura and T. N. Castro Dantas, Braz. J. Petrol. Gas., 2011, 5, 25. [2] L. Dobrzańska, G. O. Lloyd, H. G. Raubenheimer and L. J. Barbour, J. Am. Chem. Soc., 2006, 128, April,

98 P-17 Activation-Dependent Breathing in a Flexible Metal-Organic Framework Emile R. Engel, a Abdelaziz Jouaiti, b Charl X. Bezuidenhout, a Mir Wais Hosseini, b and Leonard J. Barbour a a Department of Chemistry & Polymer Science, University of Stellenbosch, Matieland 7602, Stellenbosch, South Africa; b Laboratoire de Chimie de Coordination Organique, Université de Strasbourg, F-67000, Strasbourg, France. ere@sun.ac.za Metal-organic framework (MOF) crystals often maintain their single-crystal character during solvent exchange,[1] i.e. when the MOF is submerged in a new guest solvent, allowing for guest exchange by diffusion. Employing a relatively volatile solvent for exchange potentially lowers the activation temperature, thereby increasing the probability of obtaining high-quality single crystals of an activated phase. Similarly, activation methods such as supercritical drying[2] and freeze-drying[3] have been shown to affect MOF properties by improving surface areas and pore performance. In general, however, detailed structural investigations of the effect of solvent-mediated activation are limited. A non-interpenetrated MOF with a paddle-wheel secondary building unit has been activated by direct thermal evacuation, guest exchange with a volatile solvent, and supercritical CO 2 drying. Conventional thermal activation yields a mixture of crystalline phases and some amorphous content. Exchange with a volatile solvent prior to vacuum activation produces a pure breathing phase[4] with high sorption capacity, selectivity for CO 2 over N 2 and CH 4, and substantial hysteresis. Supercritical drying can be used to access a guest-free open phase. Pressure-resolved differential scanning calorimetry was used to confirm and investigate a systematic loss of sorption capacity by the breathing phase as a function of successive cycles of sorption and desorption. A corresponding loss of sample integrity was not detectable by powder X-ray diffraction analysis. This may be an important factor to consider in cases where flexible MOFs have been earmarked for industrial applications. Keywords: metal-organic framework breathing, solvent exchange, hysteresis [1] (a) H. Li, M. Eddaoudi, M. O Keeffe, O. M. Yaghi, Nature 1999, 402, 276. (b) R. Medishetty, D. Jung, X. Song, D. Kim, S.S. Lee, M. S. Lah, J. J. Vittal, Inorg. Chem. 2013, 52, [2] (a) A. P. Nelson, O. K. Farha, K. L. Mulfort, J. T. Hupp, J. Am. Chem. Soc. 2009, 131, 458. (b) K. Gedrich, I. Senkovska, N. Klein, U. Stoeck, A. Henschel, M. R. Lohe, I. A. Baburin, U. Mueller, S. Kaskel, Angew. Chem. Int. Ed. 2010, 49, [3] M. R. Lohe, M. Rose, S. Kaskel, Chem. Commun., 2009, [4] (a) P. L. Llewellyn, S. Bourrelly, C. Serre, Y. Filinchuk, G. Férey, Angew. Chem. Int. Ed. 2006, 45, (b) G. Wang, K. Leus, S. Couck, P. Tack, H. Depauw, Y.-Y. Liu, L. Vincze, J. F. M. Denayer, P. Van Der Voort, Dalton Trans. 2016, 45, (c) F. Salles, G. Maurin, C. Serre, P. L. Llewellyn, C. Kno fel, H. J. Choi, Y. Filinchuk, L. Oliviero, A. Vimont, J. R. Long, G. Fe rey, J. Am. Chem. Soc. 2010, 132, April, 2017

99 P-18 Effect of Aliphatic Chain Length on Gas Sorption in Coordination Polymers Wesley K. Feldmann, a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. wkf@sun.ac.za Coordination polymers (CPs) are a class of inorganic-organic hybrid materials which are analogous to metalorganic frameworks (MOFs) and range from being 1D chains to 2D sheets to 3D frameworks. CPs have found application in a number of different fields, which include gas sorption, catalysis, sensors and as magnetic materials. Accordingly, the level of research interest in these and similar types of materials over the past two decades has increased dramatically [1]. The aim of the study was to investigate a series of 1D CPs, which are assembled from aliphatic dicarboxylic chains, for their application in gas sorption. A previous study [2] has shown that a 1D CP that incorporates an aliphatic dicarboxylic acid exhibited stepped gas sorption at certain pressures. An example of a structure of a CP targeted for this study is given in the image below. Copper is coordinated to both a chelating ligand, bipyridine and two aliphatic dicarboxylic acids which, in turn, coordinate to another copper center, thus creating the repeating structure of the CP. The 1D chains are able to pack next to one another through π-π stacking and it is proposed that, at certain pressures, the π-π stacking may weaken and the flexible nature of the aliphatic chains may allow gas molecules such as CO 2 to enter into the structure. A number of CPs incorporating a variety of aliphatic dicarboxylic acids have been synthesised and investigated. The acids include: Succinic (4C), Glutaric (5C), Adipic (6C), Pimellic (7C), Suberic (8C), Azelaic (9C) and Sebacic (10C) acid, as increasing the chain length can potentially lead to changes in the strength of the π-π stacking and the conformation that the aliphatic chains may assume. Sorption studies have been carried out on the range of CPs, using both gravimetric and volumetric methods. Keywords: Coordination Polymer, 1 Dimensional, Sorption [1] O. M. Yaghi and J. L Roswell, Micropor. Mesopor., Mat., 2012, 112, 673. [2] L. Li, J. Yang, Q. Zhao and J. Li, Cryst-Eng- Comm-, 2013, 15, April,

100 P-19 Solid-State Nucleophilic Addition in a Highly Flexible MOF Luzia S. Germann a, Arianna Lanza b, Martin Fisch b, Nicola Casati c and Piero Macchi b a Current address: Max Planck Institute for Solid State Research, Stuttgart, Germany. b Department of Chemistry and Biochemistry, University of Bern, Bern, Switzerland c Swiss Light Source, Paul Scherrer Institute, CH-5232 Villigen, Switzerland l.germann@fkf.mpg.de Porous Metal Organic Frameworks (MOFs) with unsaturated and stereochemically accessible metal centers are promising candidates for catalysis or absorbents. Porosity offers the possibility to incorporate and store various guest molecules. Additionally, flexibility of the framework (i.e. breathing) is a desirable property as it can assist the insertion of new ligands in the metal coordination sphere. Highly flexible and porous MOFs based on M(II)-hydroxyl nodes {Co and Mn} and benzotriazolide-5- carboxylato linkers[1] (M-btca) were found to selectively absorb guest molecules, which are trapped in the channels during crystallization or upon solvent exchange processes. Stimulated by the crystal shrinking, occurring at high pressure (P) or at low temperature (T), Co-btca undergoes a reversible nucleophilic addition reaction, where part of the guests react with the previously unsaturated Co(II) ion. Depending on the solvent either a partial (DMF) or a complete (MeOH) saturation of Co(II) occurs. These series of single crystal-to-single crystal transformations were studied in detail by non-ambient XRD.[2] We have observed the first example of temperature or high pressure induced functionalization of MOF nodes.[2] Keywords: Diarylethene, MOF, Photochromism, single-crystal to single-crystal [1] X.-M. Zhang, Z.-M. Hao, W.-X. Zhang X.-M. Chen, Angew. Chemie, 2007, 46, [2] A. Lanza, L. S. Germann, M. Fisch, N. Casati, P. Macchi, J. Am. Chem. Soc., 2015, 137(40), April, 2017

101 P-20 A Systematic in Situ and Real-Time Investigation of Mechanochemical Formation of Pharmaceutical Cocrystals Luzia S. Germann a, Leigh Loots b, Cristina Mottillo b, Joseph Marrett b, Jean-Louis Do b, Nicola Casati c, Robert E. Dinnebier a and Tomislav Friščić b a Max-Planck-Institute for Solid State Research, Stuttgart, Germany. b McGill University,Montreal, Qc, Canada. c Swiss Light Source, Paul Scherrer Institute, CH-5232 Villigen, Switzerland l.germann@fkf.mpg.de The synthesis of cocrystals composed of active pharmaceutical ingredients (APIs) is a rapidly growing research field, and one of the central topics of modern pharmaceutical materials science.[1] A number of different approaches have been developed to screen for and synthesize such pharmaceutical cocrystals, including solution cocrystallization (reaction cocrystallization),[2] vapor-assisted aging (vapor digestion),[3] and mechanochemistry.[4] The latter has been proven not only to be an extremely efficient route for cocrystal discovery, but is also a powerful method for the bulk synthesis of solid phases that are metastable or even impossible to make through other means.[5] In addition, an important hallmark of mechanochemistry the ability to generate new and known pharmaceutical forms regardless of the solubility of individual components.[6] However, the mechanisms of mechanochemical cocrystal formation still remain poorly understood. Very recently, our group has introduced the first technique for real-time and in situ monitoring of ball milling mechanochemistry, and applied it for the evaluation of reaction mechanisms in mechanochemical formation of microporous frameworks.[5] Here, we provide the first systematic study of mechanisms of mechanochemical cocrystal formation involving a library of systematically chosen cocrystal formers. Importantly, by using a novel, high resolution in situ monitoring setup at the X04SA beamline (SLS, Villigen), we are now able to provide a detailed analysis of the appearance of metastable polymorphs and stoichiometric variations in a series of homologous cocrystals. Keywords: cocrystals, mechanochemistry, in situ X-ray powder diffraction [1] D. Tan, L. Loots and T. Friščić, Chem. Commun., 2016, 52, 7760; [2] N. Rodríguez-Hornedo, S. J. Nehm, K. F. Seefeldt, Y. Pagán-Torres and C. J. Falkiewicz, Molecular Pharmaceutics, 3(3), 362; [3] I. Huskić, J.-C. Christopherson, K. Užarević and T. Friščić, Chem. Commun., 2016, 52, 5120; [4] T. Friščić and W. Jones Cryst. Growth Des., 2009, 9, 1621; [5] A. D. Katsenis et al., Nature Commun., 2015, 6:6662; 2 7 April,

102 P-21 Multicomponent Crystals Based on Hydroxamic acids Hayley R. Green, a and Gareth O. Lloyd a a Institute of Chemical Science, Heriot-Watt University, Edinburgh Campus, Riccarton, EH14 4AS, United Kingdom; hrg3@hw.ac.uk Hydroxamic acids are of major biological importance [1,2] due to their ability to sequest iron. They are also of use in metallocrowns [3] and iron coordination chemistry. However little is known about their supramolecular synthons[4] and coordination [2,5,6]. Within the literature there are examples of hydroxamic acid co-crystals [7] and cages [5,6] which are an important foundation for understanding hydroxamic acid interactions. By exploring multicomponent species, including co-crystals and porous molecular materials based around the Hydroxamic acid moiety. This poster shall discuss the supramolecular synthons and interactions displayed by Hydroxamic acids in the solid state. The image below shows two of the supramolecular synthons we wish to study, the hetero hydroxamic acid synthon and the amide-amide tape. By understanding the hydroxamic acid synthons we can better understand the similarities between the hydroxamic acid, amide and carboxylic acid synthons. Keywords: Multicomponent, Synthons, Hydroxamic acid. [1] A. L. Crumbliss, Coord. Chem. Rev., 1990, 105, [2] R. Codd, Coord. Chem. Rev., 2008, 252, [3] E. Gumienna-Kontecka, I. A. Golenya, N. M. Dudarenko, A. Dobosz, M. Haukka, I. O. Fritsky and J. Swiatek-Kozlowska, New J. Chem., 2007, 31, [4] G. R. Desiraju, The crystal as a supramolecular entity, Wiley, [5] Y. Bai, D. Guo, C. Y. Duan, D. Bin Dang, K. L. Pang and Q. J. Meng, Chem. Commun., 2004, 186. [6] T. Beissel, R. E. Powers, T. N. Parac and K. N. Raymond, J. Am. Chem. Soc., 1999, 121, [7] Ö. Almarsson, M. B. Hickey, M. Peterson, M. Zaworotko, B. Moulton and N. Rodriguez- Hornedo, USF Patents, April, 2017

103 P-22 Selectivity of a Pamoate-Based Organic Host Delia A. Haynes, Jean Lombard, Francis Prins, Helene Wahl and Tanya le Roex Department of Chemistry & Polymer Science, Stellenbosch University, Private Bag X1, Stellenbosch 7600, South Africa. dhaynes@sun.ac.za The pamoate salt of 1,10-phenanthroline crystallises as a series of isostructural solvates with dimethylformamide (DMF) [1], tetrahydrofuran (THF), dimethylacetamide (DMA) and dimethylsulfoxide (DMSO). The solvates include the solvent molecules in discrete pockets in the crystal structure. Despite no strong hydrogen bonding between the host and the guest in any of the structures, the host system is selective for DMA over the other solvents - DMA is preferentially included when the host is crystallised from mixed solutions of most mole ratios. All four isostructural solvates can also be made mechanochemically. We have shown that the host is also selective for DMA when synthesised mechanochemically. Attempts to rationalize the selectivity shown by this ionic host will also be presented. Keywords: host-guest, mechanochemistry, selectivity [1] T.-M. Shang, Q.-F.Zhou and J.-H. Sun, Acta Crystallogr., 2007, E63, o506-o April,

104 P-23 In Situ Crystallographic Visualization of CO2 Binding within a Porous Framework Arpan Hazra a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. hazra@sun.ac.za An understanding of solid-state crystal dynamics or flexibility in 3D frameworks showing multiple structural changes is highly demanding for the design of materials with potential applications in sensing and recognition. However, entangled frameworks showing such flexible behaviour pose a great challenge in terms of extracting information on their dynamics because of their poor single-crystallinity. In general, flexible frameworks showing structural transformations in the presence of external stimuli, and having relatively stable intermediate phases, are useful for the selective trapping/capture of different guest molecules, either kinetically or thermodynamically. In the current study, a dynamic MnII-3D framework {(Mn(BDC)(BPNO) 2DMF} n ; BDC = 1,4-benzenedicarboxylate and BPNO = 4,4 -bipyridine-n,n - dioxide) has been shown to exhibit extreme breathing behaviour under CO 2 gas pressure. In-situ singlecrystal diffraction analysis was carried out under CO 2 gas pressure at room temperature using an environmental gas cell in order to obtain a direct visualization of the interaction between CO 2 and the host framework. We have tried to support our results by pressure-gradient differential scanning calorimetry (P- DSC) and variable-pressure powder X-ray analysis. Current study is under going to use the framework as a material to be used in separating CO 2 from the flue gas at ambient temperature. Keywords: 3D porous framework, CO2 loading, X-ray analysis [1] G. Xu, X. Zhang, P. Guo, C. Pan, H. Zhang and C. Wang, J. Am. Chem. Soc., 2010, 132, April, 2017

105 P-24 Thermodynamic Properties from X-ray Diffraction Data of Model Polymorphic Systems Anna A. Hoser a, Ioana Sovago b, Marcin Sztylko a and Anders Ø. Madsen b a Department of Chemistry, University of Warsaw, Pasteura Warsaw; b Department of Chemistry, University of Copenhagen, Copenhagen, Denmark. annahoser@chem.uw.edu.pl Finding the relative stability of polymorphs of molecular crystals is currently one of the most important topics in crystallography, computational chemistry and physics. Beside the lattice/cohesive energy, vibrational entropy has an important contribution to polymorphs stability at room temperature. Due to high computational costs and low accuracy, entropy is very often neglected when relative stability of polymorphs is discussed. Recently, we introduced a new approach normal mode refinement (NoMoRe), which enables the refinement of frequencies of normal modes obtained from ab-initio periodic computations, against single crystal diffraction data [1]. Frequencies obtained from NoMoRe can be used to estimate thermodynamic properties heat capacity and vibrational entropy. The heat capacity calculated after normal mode refinement for naphthalene is in reasonable agreement with the heat capacity obtained from calorimetric measurements (to less than 1 cal mol -1 K -1 below 300 K) [2]. In this contribution I will present results which we obtained for aspirin, gallic acid monohydrate and 4- hydroxyacetophenon polymorphs. Keywords: polymorphs, vibrational entropy, normal mode refinement [1] A. A. Hoser, A. Ø. Madsen, Acta Crystallogr. Section A 2016, 72, [2] A. A. Hoser, A. Ø. Madsen, Acta Crystallogr. Section A 2017, 73, doi: /s April,

106 time / hours ICCOSS XXIII, Stellenbosch, South Africa P-25 In situ Monitoring of Vapour-Induced Reactivity of Metal-Organic Frameworks Using a Benchtop Powder X-ray Diffractometer Igor Huskić, a Joseph Marrett, a Cristina Mottillo, a Dayaker Gandrath, a Ken Harris, b Tomislav Friščić a a Department of Chemistry, Faculty of Science, McGill University, Sherbrooke St. West H3A 0B8, Montreal, Quebec, Canada, b School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, Wales, United Kingdom, igor.huskic@mail.mcgill.ca Zeolitic imidazolate frameworks (ZIFs) are a class of metal-organic frameworks (MOFs), topologically isomorphous to zeolites.[1] A ZIF is made up of transitional metal ions such as Co(II) or Zn, tetrahedrally coordinated with four imidazolate groups. Like most MOFs, ZIFs are often highly porous with large guestaccessible surface areas. In past, ZIFs have been praised for thermal and chemical stability, being able to withstand temperatures >500 ºC, and retaining porosity in boiling aqueous bases and organic solvents.[2] Because of their low toxicity, stability and facile preparation, ZIFs have been hailed as some of main candidates for gas separation, capture and storage, particularly for CO 2 scrubbing from flue gas. Using a simple benchtop powder x-ray diffractometer (PXRD) setup,[3] we have investigated the stability of several zinc-based ZIFs in simulated flue gas atmospheres. Most ZIFs appear stable in the presence of water vapour only, but in the presence of CO 2 they convert to novel non-porous carbonate phases within days or weeks. Such degradation is greatly exacerbated in the presence of ammonia, with full decomposition taking place in a matter of hours Keywords: in situ PXRD studies, MOFs, stability, solid state reactions [1] M. Sturm, F. Brandl, D. Engel, W. Hoppe, Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 1975, 31, [2] K. S. Park, Z. Ni, A. P. Côté, J. Y. Choi, R. Huang, F. J. Uribe-Romo, H. K. Chae, M. O'Keeffe, O. M. Yaghi, Proc. Natl. Acad. Sci. U. S. A. 2006, 103, [3]I. Huskić, J.-C. Christopherson, K. Užarević, T. Friščić, Chem. Commun. 2016, 52, April, 2017

107 P-26 Novel Cocrystals of the Anti-HIV Drug Efavirenz Maryam A. Jordaan, a and Michael M. Shapi a a Faculty of Natural Science, Department of Chemistry and Physics, Mangosuthu University of Technology, 511 Mangosuthu Highway, Durban, 4000, South Africa; jordaan.maryam@mut.ac.za The onset of HIV/AIDS has led to a despairing situation of disease progression affecting millions of people globally with Africa as its most vulnerable target. Efavirenz (Figure 1), commercially known as Sustiva or Stocrin, is a first-line antiretroviral treatment for HIV/AIDS. Efavirenz is categorized as a class 2 compound on the biopharmaceutical classification system (BCS) (i.e. low aqueous solubility but high lipophility and permeability). The low water solubility reduces oral bioavailability, which subsequently leads to decreased efficacy [1]. Pharmaceutical co-crystal formation represents a straightforward way to directly influence the solid-state properties of a drug substance, particularly its solubility and hence bioavailability. Cocrystals (CCs) used in the pharmaceutical industry are defined as complex crystals formed by reaction between an API and a cocrystal former (CCF); unlike salts, CCs do not show proton transfer [2]. Co-crystal (CC) formation is an alternative approach which can be used to improve the bioavailability of efavirenz. We sought to design a novel cocrystal of efavirenz with potential amide and pyridine coformers. Cl F 3 C O N H O Keywords: Efavirenz, cocrystals, bioavailability [1] M. A. Jordaan, P. Singh, B. S. Martincigh, Spectrochim. Acta Mol. Biomol. Spectrosc., 2016, 157, [2] S. R. Lahamage, A. B. Darekar, R. B. Saudagar, Asian J. Res. Pharm. Sci. 2016; 6: 1, April,

108 P-27 Characterization and Supramolecular Modification of a Novel Antimalarial Agent Laurelle M. Joseph, Kelly Chibale and Mino R. Caira Department of Chemistry, University of Cape Town, Rondebosch 7701, South Africa. jsplau002@myuct.ac.za A novel series of imidazopyridazine-based antimalarials has been discovered by the UCT Department of Chemistry. The compound 6-(3-(cyclopropylsulfonyl)phenyl)-3-(4-(methylsufinyl)-phenyl)imidazo[1,2- b]pyridazine (henceforth IMP) was identified as a frontrunner lead compound. IMP was able to completely cure mice infected with the Plasmodium berghei strain of the malaria parasite following the oral administration of 4 50 mg/kg doses [1-2]. Although IMP showed potent antiplasmodial activity, its poor aqueous solubility (< 5 M at ph 6.5) is a factor that could present problems for its further development. One way in which the solubility of IMP could be enhanced is through supramolecular modification. This strategy has been proven to pharmacological activity, but also improved physicochemical properties such as aqueous solubility [3-8]. The aim of this project is to use supramolecular methodology to prepare new solid-state forms of IMP, specifically co-crystals, salts, solvates and cyclodextrin inclusion complexes. Objectives include the isolation of new solid-state forms of the imidazopyridazine, their full characterization using X-ray, thermal and spectroscopic techniques and assessment of their utility in drug delivery. After completing a full solid-state characterization of the starting material, a polymorphic screen was conducted and initial experiments produced a hydrate of IMP. Further studies are currently being conducted to isolate more polymorphs of IMP. Co-crystal screening experiments using the liquid-assisted grinding (LAG) method revealed three hits from attempted reactions between IMP and the co-formers oxalic acid, adipic acid and succinic acid. Novel co-crystals between IMP and succinic acid and between IMP and adipic acid were prepared by co-precipitation and their X-ray crystal structures were solved using single crystal X- ray diffraction. The co-crystals and the hydrate of IMP were further characterized using HSM, TGA, DSC, 1 H NMR and IR spectroscopy. Keywords: antimalarial, supramolecular modification, physicochemical characterization [1] C. Le Manach, T. Paquet, D. G. Cabrera, Y. Younis, D. Taylor, L. Weisner, N. Lawrence, S. Schwager, D. Waterson, M. J. Witty, S. Wittlin, L. J. Street and K. Chibale, J. Med. Chem., 2014, 57, [2] C. Le Manach, D. G. Cabrera, F. Douelle, A. Nchinda, Y. Younis, D. Taylor, L. Weisner, K. L. White, E. Ryan, C. March, S. Duffy, V. M. Avery, D. Watterson, M. J. Witty, S. A. Charman, L. J. Street and K. Chibale, J. Med. Chem. 2014, 57, [3] G. R. Desiraju, J. Am. Chem. Soc., 2013, 135, [4] G. R. Desiraju, J. Chem. Sci., 2010, 122, 667. [5] N. Shan and M. J. Zaworotko, Drug Discov. Today, 2008, 13, 440. [6] G. R. Desiraju, Angew. Chem. Int. Ed. Engl., 1995, 34, [7] T. Loftsson and D. Duchêne, Int. J. Pharm., 2007, 329, 1. [8] T. Loftsson, M. E. Brewster and M. Másson, Am. J. Drug Deliv., 2004, 2, April, 2017

109 P-28 Crystallization of Host-Guest Complexes with a Chiral Hemicucurbit[8]uril Sandra Kaabel, a Filip Topić, b Riina Aav a and Kari Rissanen b a Department of Chemistry, Tallinn University of Technology, Akadeemia tee 15, Tallinn, Estonia; b University of Jyväskylä, Department of Chemistry, Nanoscience Center, P.O. Box. 35, FI Jyväskylä, Finland. sandra.kaabel@ttu.ee The importance of molecular recognition as the basis of most biological systems is well established and has brought about a wide-spread interest in the development of synthetic receptors for e.g. sensors, pharmaceuticals, separation systems and catalysis.[1] Hemicucurbit[n]urils (HC[n]) have emerged as the subbranch of the cucurbituril family, notable for their capability of binding anionic guests.[2] Our group has focused on chiral cyclohexanohemicucurbit[n]urils (cychc[n]) by synthesizing and characterizing (all-r)- or (all-s)-cychc[6] and (all-r)-cychc[8].[3,4] So far, we have shown that the barrel-shaped cychc[8] encapsulates anions as large as hexafluoroantimonate within its cavity, with size and shape selectivity.[5] More recently, we have tried to establish the scope of neutral guests that form host-guest complexes with cychc[8]. Inspired by the report on catalytic activity of HC[6] in the aerobic oxidation of furane and thiophene,[6] we set out to investigate the binding of small organic molecules within cychc[8] to subsequently explore its potential as a chiral catalyst. As a result, a number of 1:1 host-guest complexes with neutral organic molecules have been successfully characterized by single crystal X-ray diffraction analysis. The crystal structure of the host-guest complex of 1,3-dithiolane and cychc[8] (Figure) illustrates the tight encapsulation of the heterocyclic guest within the host cavity. As 1,3-dithiolane is one of the degradation products of sulfur mustard, the most abundant chemical warfare agent dumped in the Baltic Sea [7], application of cychc[8] for leak-monitoring could be envisaged. The complexation of neutral guests was also studied by NMR spectroscopy in solution. Keywords: host-guest chemistry, hemicucurbituril, anion binding, neutral guest binding [1] E. M Peck, B. D. Smith, in Synthetic Receptors for Biomolecules: Design Principles and Applications; ed B. D. Smith, Royal Society of Chemistry, Cambridge, 2015; ch. 1, pp [2] Y. Miyahara, K. Goto, M. Oka, T. Inazu, Angew. Chem. Int. Ed., 2004, 43, [3] R. Aav, E. Shmatova, I. Reile, M. Borissova, F. Topić, K. Rissanen, Org. Lett., 2013, 15, [4] E. Prigorchenko, M. Öeren, S. Kaabel, M. Fomitšenko, I. Reile, I. Järving, T. Tamm, F. Topić, K. Rissanen, R. Aav, Chem. Commun., 2015, 51, [5] S. Kaabel, J.Adamson, F. Topić, A. Kiesilä, E. Kalenius, M. Öeren, M. Reimund, E. Prigorchenko, A. Lõokene, H. J. Reich, K. Rissanen and R. Aav, Chem. Sci, submitted [6] H. Cong, T. Yamato, Z. Tao, J. Mol. Catal. A: Chem. 2013, 379, 287. [7] R. Magnusson, T. Nordlander, A. Östin, J. Chromatogr. A 2016, 1429, April,

110 P-29 Modifying Opto-Electronic Properties of CT Crystals by Solid- State Reaction Sanaz Khorasani, Manuel A. Fernandes and Demetrius C. Levendis Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, 2050 Johannesburg. Charge-transfer materials have found application in electronic materials such as organic metals and field-effect transistors (OFETs). The properties of such materials depend strongly on the electronic structure of the material which in turn depends on the intermolecular interactions. Crystal engineering techniques are usually used to create desired crystalline materials by exploiting the directional properties of weak interactions between molecules. A recent paper by Yokokura et al. (2015) has shown that phase transitions in TCNQ-Anthracene alter the electronic properties of the material from n-type, to ambipolar, to p-type due to temperature driven phase changes in which the orientation of the two components in the material are altered.[1] However, phase changes are an unpredictable inherent property of a material. As an alternative to these techniques, we have been studying single-crystal-to-single-crystal (SCSC) solid-state reactions as a post-crystallization method for modifying such materials. Solid-state chemistry usually involves the manipulation of molecules and materials through photochemical, thermal, or mechanical reaction methods. In solid-state reactions, the crystal lattice provides both sterio- and regioselective control of the reaction products obtained and their resulting crystal structures. While studies into polymorphs and co-crystals can be used to create interesting materials by crystal engineering, solid-state reactions provide another path towards creating new materials which cannot be made by other methods. As an example of the work we have carried out, we report here on reactions in chargetransfer complexes of substituted anthracenes and 1,4-dithiine-tetracarboxylic N,N -dimides which usually undergo topochemical thermal SCSC [4 + 2] Diels-Alder reaction in the solid state.[2] These CT crystals are usually reacted around 40 C and can be trapped at a desired degree of conversion by cooling back room temperature. This allows their structures to be determined by X-ray diffraction at various degrees of conversion, and examined using Hirshfeld surfaces and lattice energy calculations to find evidence of reaction cooperativity and feedback mechanisms. Such studies lead to an understanding of the behaviour of molecules within crystals in response to the solid-state reaction, possibly allowing solid-state reactions to be used as a crystal engineering tool in the future. Keywords: charge-transfer complexes, crystal engineering, solid-state reaction [1] S. Yokokura et al., Chem. Mater., 2015, 27, [2] S. Khorasani, M.A. Fernandes, Cryst. Growth Des., 2013, 13, April, 2017

111 P-30 In-Situ Crystallographic Analysis to Understand the Host-Guest Interaction in a Soft Porous Material Prem Lama a and Leonard J. Barbour, a a Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa; lamaprem1983@gmail.com A variety of rigid porous materials have been synthesized which have shown potential application in terms of catalysis and gas separations due to high porosity and pore volumes.[1] As compared to rigid porous coordination polymers, due to the tunability of size, shape and pores by using desired metal ions and the organic linkers, a number of flexible co-ordination polymers have been reported.[2] As a result of this flexibility, porous co-ordination polymers can undergo expansion or contraction of the pores in the presence or absence of the guest molecules to produce structural change.[3] The flexible porous co-ordination polymers also knows as soft porous materials have better affinity to offer variety of pores on adsorption of different molecules which can be stabilized by non covalent interactions such as H-bonding, π π inetraction or van der Waals interations etc. One of such soft porous system have been synthesized and characterized by in-situ single-crystal X-ray diffraction using an environmental gas cell.[4] Keywords: porous materials, flexible coordination polymers [1] (a) McDonald, T. M.; Lee, W. R.; Mason, J. A.; Wiers, B. M.; Hong, C. S.; Long, J. R. J. Am. Chem. Soc. 2012, 134, (b) Lama, P.; Aijaz, A.; Neogi, S.; Barbour, L. J.; Bharadwaj, P. K. Cryst. Growth Des. 2010, 10, (c) Eddaoudi, M.; Li, H.; Yaghi, O. M. J. Am. Chem. Soc. 2000, 122, (d) Zhang, Z.; Zaworotko, M. J. Chem. Soc. Rev. 2014, 43, (e) Aggarwal, H.; Bhatt, P. M.; Bezuidenhout, C. X.; Barbour, L. J. J. Am. Chem. Soc. 2014, 136, [2] (a) Henke, S.; Schneemann, A.; Fischer, R. A. Adv. Funct. Mater. 2013, 23, [3] (a) Nijem, N.; Wu, H.; Canepa, P.; Marti, A.; Balkus, Jr. K. J.; Thonhauser, T.; Li, J.; Chabal, Y. J. J. Am. Chem. Soc. 2012, 134, (b) Coudert, F.-X.; Mellot- Draznieks, C.; Fuchs, A. H.; Boutin, A. J. Am. Chem. Soc. 2009, 131, (c) Alhamami, M.; Doan, H.; Cheng, C.-H. Materials, 2014, 7, [4] (a) Lama, P.; Aggarwal, H.; Bezuidenhout, C. X.; Barbour, L. J. Angew. Chem., Int. Ed. 2016, 55, Jacobs, T.; Lloyd, G. O.; Gertenbach, J.-A.; Müller-Nedebock, K. K.; Esterhuysen, C.; Barbour, L. J. Angew. Chem., Int. Ed. 2012, 51, April,

112 P-31 Solid-State Supramolecular Chemistry of a Series of Organic Zwitterions Jean Lombard, Delia A. Haynes and Tanya le Roex Department of Chemistry and Polymer Science, University of Stellenbosch, P. Bag X1, Matieland, 7602, Republic of South Africa. jeanl@sun.ac.za Zwitterions are molecules containing both a positive and a negative charge so that as a whole they are neutral. In general, zwitterions are usually difficult to isolate due to their high reactivity [1,2], however a recently reported series of zwitterions have been found to be quite stable [3]. These zwitterions have an unusual shape, as well as hydrogen-bonding capability, which led us to further investigate the possibility of these zwitterions forming solvates, polymorphs, and co-crystals. It has long been known that reactions between electrophilic π systems and aprotic bases (nucleophiles) lead to dipolar species, and this series of zwitterions is formed by reaction of acetylenedicarboxylic acid with pyridine and other pyridine derivatives. This simple one-pot synthesis and subsequent crystallisation of the zwitterion was attempted in various solvents and solvent mixtures, as well as at different temperatures, in order to determine which solid-state forms each zwitterion can adopt. In most cases the product was crystalline and thus could be identified using X-ray diffraction techniques, followed by further investigation using thermal analysis. Mechanochemical synthesis was also attempted (neat- as well as liquid-assisted grinding). Furthermore, we attempted to form co-crystals by combining each zwitterion (in solution as well as mechanochemically) with numerous other organic molecules chosen based on known intermolecular interactions. Five zwitterions have successfully been synthesised, and in four of these cases a related salt was also obtained from the same starting materials, which seems to be the kinetic product of the reaction. Although similar zwitterions have been known to form solvates, these zwitterions seem to close-pack in all cases. A few exist as hydrates, but no inclusion of other guests was observed. Zwitterions 1 and 4 were found to be polymorphic and the relationship between polymorphs and the conditions under which each is formed were investigated. Zwitterions 2 and 3 were found to form a co-crystal with melamine and the structures of these cocrystals have been determined. The existence of further co-crystals with these two zwitterions are strongly suspected based on NMR data. Keywords: zwitterion, polymorph, co-crystal [1] A. Dieckmann, M. Breugst and K. J. Houk, J. Am. Chem. Soc., 2013, 135, [2] V. Nair, R. S. Menon, A. R. Sreekanth, N. Abhilash and A. T. Biju, Acc. Chem. Res. 2016, 39, [3] L. Loots, D. A. Haynes and T. Le Roex, New J. Chem., 2014, 38, April, 2017

113 P-32 New Routes to Biopolymer Breakdown using Solid-State Reactivity Leigh Loots, a Fabien Hammerer, b Jean-Louis Do, b Christopher W. Nickels, b Tomislav Friščić b and Karine Auclair b a Department of Chemistry and Polymer Science, Stellenbosch University, Private Bag X1, Stellenbosch, 7600, South Africa; b Department of Chemistry, McGill University, Montreal, Quebec, H3A 0B8, Canada. leigh.loots@gmail.com Solid-state, solvent-free reactivity is rapidly becoming a mainstream approach for clean, versatile synthesis, including the making of pharmaceutical materials and molecules,[1] catalysis[2] as well as for large-scale production of advanced materials such as metal-organic frameworks (MOFs).[3] In that context mechanochemistry,[4] or chemical reactivity induced by milling or grinding, has been particularly successful, and was recently joined by accelerated aging,[5] a novel synthetic methodology that enables the assembly of molecules and materials under mild conditions, without bulk solvent and with minimal input of energy. Both mechanochemistry and accelerated aging provide a unique opportunity to conduct high-yielding transformations independent of reactant solubility. As a result, both techniques have found application for the conversion of traditionally poorly soluble, inert feedstocks, such as metal oxides, into value-added materials, such as MOFs.[4,5] In principle, such benefits of mechanochemistry and accelerated aging are also applicable to poorly soluble organic feedstocks, notable biological polymers constituting bio-waste. This presentation will outline our recent advances in developing new, clean and low-energy routes for the breakdown of cellulose and related biopolymers through solvent-free techniques. In particular, we will demonstrate a novel, clean and efficient route for the production of glucose, the principal precursor for the production of bioethanol. Keywords: Mechanochemistry, Accelerated Aging, Green Chemistry; Solid-state; Biomass [1] D. Tan, L. Loots, T. Friščić, Chem. Commun,. 2016, 52, 7760; [2] J. G. Hernández, T. Friščić, Tet. Letters, 2015, 56, 4253; [3] M. J. Cliffe, C. Mottillo, R. S. Stein, D.-K, Bučar, T. Friščić, Chem. Sci., 3, 2495; [4] S. James, C. J. Adams, C. Bolm, D. Braga, P. Collier, T. Friščić, F. Grepioni, K. D. Harris, G. Hyett, W. Jones, A. Krebs, J. Mack, L. Maini, A. G. Orpen, I. P. Parkin, W. C. Shearouse, J. W. Steed, D. C. Waddell, Chem. Soc. Rev., 2012, 41, 413; [5] C. Mottillo, Y. Lu, M.-H. Pham, M. J. Cliffe, T.-O. Do, T. Friščić, Green Chemistry, 2013, 15, April,

114 P-33 High Performance Metal-Organic Materials (MOMs) for Advanced CO2 Separation Processes David G. Madden, a Hayley S. Scott, a Amrit Kumar, a Kai-Jie Chen, a John J. Perry a and Michael J. Zaworotko a * a Bernal Institute, Department of Chemical Sciences, University of Limerick, Plassey House, Castletroy, Limerick, Republic of Ireland. xtal@ul.ie Sequestration of CO 2, either from gas mixtures or directly from air (Direct Air Capture, DAC), is a technological goal important to large-scale industrial processes such as gas purification and the mitigation of carbon emissions. Traditional energy intensive processes employ chemisorbent materials for CO 2 capture. The use of physisorbent materials represents a fundamentally different approach to carbon capture since it relies upon the physical properties of CO 2. In principle, advanced physisorbents that selectively capture CO 2 from gas mixtures offer significant upside potential for a revolution in carbon capture technology since they would require much less energy for recycling, can exhibit high working capacity and can be designed to have their sorption performance unaffected by moisture. A new generation of physisorbents, known as HUMs, have emerged thanks to a crystal engineering approach. HUMs combine <0.7 nm pores with strong electrostatics and exhibit new benchmarks for the strength of sorbent-sorbate interactions. HUMs are highly selective and can target even the most difficult separations such as removal of trace impurities of CO 2 from gas mixtures and CO 2 capture from complex wet gas mixtures. The incorporation of strong electrostatics from inorganic moieties combined with ultramicropores can offer improved CO 2 capture performance from even the most challenging gas separation processes.[1,2] Keywords: Metal-Organic Materials, CO2 Sorption, Separation [1] Madden, D. G.; Scott, H. S.; Chen, K. J.; Kumar, A.; Sanii, R.; Bajpai, A.; Lusi, M.; Curtin, T.; Perry, J. J.; Zaworotko, M. J.. Phil. Trans. A, 2016, (DOI: [2] Kumar, A.; Madden, D. G.; Lusi, M.; Chen, K.-J.; Daniels, E. A.; Curtin, T.; Perry, J. J.; Zaworotko, M. J. Angew. Chem. Int. Ed., 2015, 54 (48), April, 2017

115 P-34 Docking, Ranking and Scoring Power of Electrostatic Interaction Energy Maura Malinska a a Faculty of Chemistry, University of Warsaw, Pasteura 1, Warsaw, Poland. mmalinska@chem.uw.edu.pl Molecular recognition is a fundamental step in essentially any biological process. Enzyme catalysis, cellular signaling, protein-protein association, protein crowding, reactant transport, and the noncovalent binding of a receptor with a ligand molecule, to name only a few, involve the recognition between two or more molecular binding partners, leading either to their association or to their rejection. Molecular docking predicts the binding pose of a ligand and also estimates the ligand-receptor binding free energy by evaluating critical phenomena involved in the intermolecular recognition process. However, accurately predicting relative binding affinities and biological potencies for ligands that interact with proteins remains a significant challenge for computational chemists. In the present study, based on an extensive dataset of 240 protein ligand complexes from the PDBbind refined database[1] (version 2015), the performance of electrostatic interaction energy (Ees) obtained from reconstructed charge density of protein-ligand complexes with the aid of UBDB[2] was systematically evaluated by examining the accuracies of binding pose prediction (docking power) and binding affinity estimation (ranking and scoring power). The combination of the aspherical atom databank approach and the Exact Potential Multipole Method[3] enables the calculation of pure electrostatic interaction energies. Four docking programs, including two commercial programs (GOLD and Surflex-Dock) and two academic programs (AutoDock and UCSF DOCK) were used to generate set of different poses. Overall, the ligand binding poses and rank of the ligand could be identified in most cases by the Ees but the score of the binding affinities for the entire dataset could not be well predicted. However, for some types of protein families, relatively high linear correlations between Ees and experimental binding affinities could be achieved. MM thanks the Polish National Science Centre for financial support within Sonata grant UMO- 2016/11/D/ST4/03745 Keywords: binding free energy, charge density, pseudoatom databank [1] Cheng, T., Li, X., Li, Y., Liu, Z. & Wang, R J. Chem. Inf. Model. 49, [2] Jarzembska, K. N. & Dominiak, P. M Acta Crystallogr. Sect. A 68, 139. [3] Volkov, A., Koritsanszky, T. & Coppens, P Chem. Phys. Lett. 391, April,

116 P-35 Physico-Chemical and Pharmacological Properties of New Nanostructures of Phenazepam Yury N. Morozov a, Dmitry V. Chistykov b, Vladimir P. Shabatin a, Vladimir V. Chernyshev a, Tatiana A. Voronina c, and Gleb B. Sergeev a a Departments of Chemistry b Bioengineering and Bioinformatics, M.V. Lomonosov Moscow State University, Leninskie Gory 1-3 Moscow , Russia, c Research Zakusov Institute of Pharmacology, Baltijscaya 8, Moscow , Russia. yunmor@mail.ru We have developed an original strategy for production of organic nanoparticles, based on a dynamic combination of high and low temperature, gas and solid phases, and inert carrier gases with various thermo-physical properties. It has proved to be useful for synthesis of nanoscale particles of pharmaceuticals. In this approach, crystals of initial drug substances are sublimated in a stream of heated nitrogen. A mixed flow of molecules is then directed to the cold surface, where they undergo a quick cooling accompanied by a deep supersaturation, homogeneous gas phase nucleation, followed by formation and growth of nanoparticles, which are then stabilized on a cold surface. The developed technology allowed us to obtain nanoparticles of a number of organic drug substances, in particular, to synthesize nanocrystalline powders of a known tranquilizer phenazepam with a new polymorphic structure. Crystallographic description of this new polymorph has been reported earlier [1]. The process does not affect the molecular structure of the compound, as confirmed by NMR and thin layer chromatography. To identify the structure of nanophenazepam we also used IR-Fourier spectroscopy and differential scanning calorimetry (DSC). According to transmission electron microscopy (TEM), BET adsorption technique and X-ray diffraction, the average size of the crystals of nanophenazepam is 50±12 nm. The nanosized compound has 1.3 times greater water solubility and 3.9 times higher dissolution rate than the pristine phenazepam powder. When working with nanoparticles of drugs, much attention has to be paid to their toxicity. The relative toxicity of nanophenazepam was tested by its effect on glial cells C6 of rats. It was found that nanophenazepam suppresses the proliferation of cells to the less extent compared to the original one. Pharmacological properties of nanophenazepam studied by intragastric administration to rats. We have found that nanopowders have increased anxiolytic and reduced sedative activity. Besides, the muscle relaxation activity of nanosized substance was a lot less than the one of the original phenazepam. Thus, nanophenazepam has a much higher therapeutic index. Experimental results show that the new nanosized polymorph of phenazepam exhibit potentially advantageous physical chemical properties. Further studies are needed to identify the differential therapeutic effect of size of nanoparticles and structural changes. Both of these factors can lead to the phenomenon of synergy and affect the therapeutic efficacy of drugs. Keywords: nanoparticles of drug substances, polymorphism of drugs, pharmacological properties, phenazepam, [1] G.B. Sergeev, B.M. Sergeev, Yu.N. Morozov and V.V. Chernyshev, Acta Crystallography 2010, E66, o April, 2017

117 Intensity ICCOSS XXIII, Stellenbosch, South Africa P-36 The Hydrochromic Behavior of a Porous, Organic Material is Explained by TD-DFT Dirkie C. Myburgh, a Catharine Esterhuysen, a Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa; dcm@sun.ac.za A macrocyclic ligand [1] containing a conjugated Schiff-base [2] like moiety undergoes a photo-isomerization in the solid state upon absorption of gaseous H 2O. Upon crystallization, 18 Å wide channels are formed throughout the crystal structure allowing the absorption of and interaction with a gaseous compound. A range of conformations within the Schiff-base-like moiety were proposed and tested at the DFT level of theory to see if they will result in the visible material properties. The Gaussian09 package along with various DFT functionals were used to perform quantum chemical calculations and predict various physical and chemical properties. This includes predicting UV/Vis spectra and transition states, calculating MO topologies and total energies and performing system optimizations. The yellow-to-red color conversion was attributed to the formation of the amine from the alcohol. Initially the equilibrium lies toward the alcohol however upon coordination with H 2O the alcohol-state becomes less favorable and the system gets locked in the amine form. The HOMO-LUMO electronic transition gave rise to an initial peak at 405 nm causing a complementary and initial yellow color but after coordination to water a portion of the peak shifts to 514 nm resulting in the final red color of the crystal nm 514 nm Wavelength (nm) Keywords: time dependent density functional theory (TD-DFT), photoisomerism, hydrochromism, electronic transition, highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) [1] S. Srimurugan and B. Viswanathan, Tetrahedron Letters, 2005, 46, [2] E. Hadjoudis and I. M. Mavridis, Chem. Soc. Rev., 2004, 33, April,

118 P-37 Ball Milling Mechanochemistry Under Non-Conventional Conditions Christopher W. Nickels, and Tomislav Friščić a Department of Chemistry, McGill University, 801 Sherbrooke St. W., Montreal QC H3A 0B8, Canada christopher.nickels@mail.mcgill.ca As mechanochemistry continues to become more widely accepted across academia and industry alike, [1] so to do the techniques and equipment evolve to reflect this increased interest. This presentation will outline our recent studies of mechanochemical reactions under non-conventional conditions, including reactions under elevated pressures, and reactions under ultraviolet (UV) irradiation. In particular, we will describe milling reactions under pressures of selected inert (e.g. nitrogen, argon, etc.) or reactive (e.g. hydrogen, oxygen, etc.) gases. We will also describe a dedicated instrument for simultaneous ball milling and UV irradiation, enabling the coupling of a wide range of photoreactions with mechanochemical transformations. Keywords: Mechanochemistry, Ball Milling, Photochemistry, Gas Pressure [1] S.L. James et al., Chem. Soc. Rev., 2012, 41, April, 2017

119 P-38 Copper Box: From Discrete Voids to Channels Varvara I. Nikolayenko a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. vin@sun.ac.za In order to maximize attractive intermolecular contacts, molecules in crystals tend to pack as close to one another as possible. As a result, the engineering of porosity (empty space) in crystalline solids remains a highly topical area of focus, with many materials finding applications in gas storage, sensing and separation as well as molecular recognition.[1] The literature contains many examples of metal-organic frameworks (MOFs)[2], covalent organic frameworks (COFs)[3] and hydrogen-bonded organic frameworks (HOFs)[4] for conventional porosity studies. However, it is only recently that the permeability of transiently porous materials has come into focus. Transient porosity refers to materials that have a seemingly nonporous solid-state structure but are highly permeable - such materials have interstitial lattice voids that are not linked to one another or to the crystal surface. Flexible and dynamic metal-organic solids that can expand or shrink (i.e. breathe) as a result of external stimuli such as temperature,[5] pressure,[6] light,[7] electric or magnetic field and guest inclusion.[8] Herein we present the previously described discrete (0D) dinuclear metallocycle [Cu 2(L1) 2Cl 4] 2CH 3OH 1, (where L1 is the ligand 1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene) which undergoes activation as well as a series of guest exchanges in a single-crystal to single-crystal (SC-SC) fashion. Furthermore, each exchange is accompanied by cooperative motion of the host imidazole rings, inducing a highly guest specific change in the solvent-accessible space available, and thus breathing in what was previously described as a rigid material. Keywords: Metallocycle, Guest-exchange, single-crystal to single-crystal [1] a) A. Dhakshinamoorthy, M. Alvaro and H. Garcia, Chem. Commun., 2012, 48, ; b) M. E. Medina, A. E. Platero- Prats, N. Snejko, A. Rojas, A. Monge, F. Gandara, E. Gutiérrez-Puebla and M. A. Camblor, Adv. Mater., 2011, 23, ; c) H.-L. Jiang and Q. Xu, Chem. Commun., 2011, 47, ; d) S. Ma, Pure Appl. Chem., 2009, 81, [2] H.-C. Zhoua and S. Kitagawa, Chem. Soc. Rev., 2014, 43, [3] S. S. Han, H. Furukawa, O. M. Yaghi, and W. A. Goddard III, J. Am. Chem. Soc. 2008, 130, [4] P. Li, Y. He, H. D. Arman, R. Krishna, H. Wang, L. Weng and B. Chen, Chem. Commun., 2014, 50, [5] H. Kim, D. G. Samsonenko, M. Yoon, J. W. Yoon, Y. K. Hwang, J.-S. Chang, K. Kim, Chem. Commun. 2008, [6] A. H. Fuchs, A. Boutin, M. A. Springuel-Huet, A. Nossov, A. Gedeon, T. Loiseau, C. Volkringer, G. Ferey, F. X. Coudert, Angew Chem., 2009, 48, [7] N. Yanai, T. Uemura, M. Inoue, R. Matsuda, T.Fukushima, M. Tsujimoto, S. Isoda, S. Kitagawa, J. Am. Chem. Soc. 2012, 134, [8] R. Matsuda, R. Kitaura, S. Kitagawa, Y. Kubota, T. C. Kobayashi, S. Horike, M. Takata, J. Am. Chem. Soc. 2004, 126, April,

120 P-39 Multicomponent Crystals of Baclofen Kudzanai Nyamayaro a and Nikoletta B. Báthori a a Department of Chemistry, Cape Peninsula University of Technology, P. O. Box 652, Cape Town 8000, South Africa. bathorin@cput.ac.za The formation of multicomponent crystals, such as solvates, salts or cocrystals of drug substances is a popular way of creating a new patentable solid form of the selected active pharmaceutical ingredient. The practical prospects of using cocrystals in pharmaceutical formulations were highlighted [1] and the progress in their application in the last ten years were summarized recently by Almarsson and Zaworotko. [2] Baclofen (BAC, (RS)-4-amino-3-(4-chlorophenyl)butanoic acid), a -amino acids is a GABA B receptor agonist which is recently used in the treatment of addictive behaviours, such as opiate addiction or early stage of alcoholism. We have previously used BAC to form multicomponent crystals with a series of organic acids and concluded that -amino acids, such as BAC, are promising crystal engineering tools because of their structural flexibility and hydrogen bonding properties. [3] In this contribution, six multicomponent crystals of BAC were formed with nitric acid and a series of nitroand bromo-substituted carboxylic acids (3-nitrobenzoic acid, 3NBA, 4-nitrobenzoic acid, 4NBA, 3,5- dinitrobenzoic acid, DNBA, 3,5-dinitrosalicylic acid, DNSA, and 3,5-dibromosalicylic acid, DBSA, Scheme). The aim was to investigate the influence of the systematic variation of functional groups of the coformer on the crystal packing and on the physical-chemical properties of the newly formed crystalline materials. The crystal structure, thermal analysis and powder X-ray analysis of the multicomponent crystals are presented and conformation and protonation properties of the baclofen moiety are discussed. Keywords: pharmaceutics, multicomponent crystals, synthon, [1] O. Almarsson and M. J. Zaworotko, Chem. Commun. 2004, [2] N. K. Duggirala, M. L. Perry, O. Almarsson and M. J. Zaworotko, Chem. Commun. 2016, 52, [3] N. B. Báthori and O. E. Y. Kilinkissa, CrystEngComm 2015, 17, April, 2017

121 P-40 Inclusion of (±)-α-lipoamide in Native and Methylated Cyclodextrins Terence J. Noonan, Susan A. Bourne and Mino R. Caira a Centre for Supramolecular Chemistry Research, Department of Chemistry, University of Cape Town, Private Bag, Rondebosch 7701, South Africa. NNNTER002@myuct.ac.za (±)-α-lipoamide is a bioactive compound and is converted to unbound lipoic acid within the body. This compound is of interest for its use as nutritional supplement and as therapeutic agent. It is an antioxidant with a wide range of potential uses, including administration as an antiretroviral agent and is currently used in the clinical treatment of diabetic neuropathy. The utility of this compound is drastically hindered by its poor solubility profile and thermal and metabolic stabilities [1-3]. The aim was to make use of supramolecular methods to alter the physicochemical properties of this compound without modifying its biological activity. Cyclodextrin (CD) inclusion complexation was the method of choice as it has many proven examples of improving stability and/or solubility of the included guest molecules. Successful complexation was accomplished with the native cyclodextrins α-, β- and γ-cd as well as the methylated cyclodextrins DIMEB, TRIMEB and TRIMEA. The complexes were characterized by applicable thermal methods including hot stage microscopy, differential scanning calorimetry and thermal gravimetric analysis. Stoichiometry was determined by proton NMR spectroscopy and complexation was confirmed by powder X-ray diffraction and in cases where it was possible the crystal structures were determined by means of single crystal X-ray diffraction. Phase solubility studies with a range of CDs are intended to be carried out in the near future with the title compound as substrate to establish the extent of its solubility enhancement and to estimate complex association constants in aqueous solution. Keywords: (±)-α-lipoamide, cyclodextrin complexation, solubility [1] A. Baur, T. Harrer, M. Peukert, G. Jahn, J. Kalden and B. Fleckenstein, Klin. Wochenschr., 1991, 69, [2] N. Ikuta, H. Sugiyama, H. Shimosegawa, R. Nakane, Y. Ishida, Y. Uekaji, D. Nakata, K. Pallauf, G. Rimbach and K. Terao, Int. J. Mol. Sci., 2013, 14, [3] M. Koufaki, Expert Opin. Ther. Pat., 2014, 24, April,

122 P-41 Large Supramolecular Assemblies of a Bowl-Shaped Host Clive L. Oliver, a Nikoletta B. Báthori, b Graham E. Jackson, a David Kuter, a Dyanne L. Cruickshank a and Richard Payne a a Department of Chemistry, University of Cape Town, Rondebosch, 7701, South Africa, b Crystal Engineering Unit, Department of Chemistry, Faculty of Applied Sciences, Cape Town, 8000, South Africa. clive.oliver@uct.ac.za. Nature is able to produce large, supramolecular assemblies of macromolecules with intricate complexities such as found in viruses and cellular membranes. These complicated structures are held together by non-covalent interactions which are ultimately crucial in the functioning of these complex biological systems. Smallmolecule supramolecular chemists are inspired by these complex supramolecular systems in nature, however, large, synthetic, multi-component (n > 3) supramolecular assemblies which enclose chemical space are still relatively rare phenomena in the field of small-molecule, supramolecular chemistry. Atwood and MacGillivray reported the first example of such an assembly by showing that the bowl-shaped host molecule C- methylcalix[4]resorcinarene 1 can spontaneously assemble in a nitrobenzene solution to form a large, chiral, supramolecular assembly consisting of 6 molecules of 1 and 8 water molecules.[1] Despite the approximately 125 structures reported since this discovery containing 1 co-crystallised with various guest and/or solvent molecules, only one similar hexameric assembly of 1 was reported by Holman et al. where 6 of the 8 water molecules were replaced by 2-ethylhexanol molecules.[2] Here we present a crystallisation of 1 from 1-butanol, which yielded two different types of hexameric assemblies within the same crystal structure.[3] Furthermore, the two unique assemblies are linked part of the time into a heterodimer of hexameric assemblies which we entitle a supra-heterodimer, a 38-component assembly consisting of 129 hydrogen bonds. To the best of our knowledge, the isolation of two different large, supramolecular assemblies (n > 3) within the same crystal structure has not been observed before and neither has identical large supramolecular assemblies been shown to link into discrete units. In addition, we report a hexameric assembly of 1-propanol with 1 which increases the interior cavity size by simultaneous insertion of water and 1-propanol as the 'stitching molecules, indicating a possible means of engineering the size of these cavities. Keywords: supramolecular, supra-heterodimer, 38-component [1] MacGillivray, L. R., Atwood, J. L., Nature, 1997, 389, [2] Ugono, O., Holman, K. T., Chem.Commun., 2006, [3] Oliver, C. L, Báthori, N. B., Jackson, G. E., Kuter, D., Cruickshank, D. L., 2016, CrystEngComm, 18, April, 2017

123 P-42 Hydrates and Solvates as Precursors on the Design of Pharmaceutical Materials Gabriela S. Rauber a,b, Raimundo Ho c, Nandkishor K. Nere c ; Shailendra Bordawekar c ; Ahmad Y. Sheikh c ; William Jones b a CAPES, Ministry of Education of Brazil, Brasilia , BRA; b Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK; c AbbVie Inc., 1 North Waukegan Road, North Chicago, IL, USA. gs487@cam.ac.uk The design of crystalline materials with improved physicochemical properties is a key aspect in drug development. Among the strategies used to produce the appropriate API, we highlight the use of solvates and hydrates as intermediates towards the formation of specific anhydrous/non-solvated forms for molecules that exhibit very high level of crystal form complexity. One aim is to address the question as to whether the outcome of these stress-induced transformations during the drying can be predicted or rationalised. Carbamazepine dihydrate (CBZ:2H 2O), which exhibits needle-like morphology, was selected for drying experiments. CBZ:2H 2O has been extensively studied previously and has been shown to dehydrate to a variety of different polymorphic forms in different studies in the literature. Samples, obtained from ethanol/water mixtures of different composition, with two dominant crystal surfaces were investigated. CBZ:2H 2O face (0k0) showed steps of approximately 13 Å height perpendicular to the main crystallographic axis, while sample containing (h00) main face presented steps of approximately 7.5 Å height parallel to the main growth axis. The experiments showed that under dehydration conditions (0% RH/40 o C), the crystals developed micrometric cracks and domains, nanosized voids and whiskers on both surfaces, although the (h00) face was more susceptible to crack formation. Dehydration leads to CBZ polymorph I in both samples. The results show that the crystal lattice changes only after removal of a considerable amount of water and the materials formed after dehydration present low crystallinity. The oriented texture observed by AFM could be correlated to crystallographic features and suggests lattice continuity along the c axis of CBZ:2H 2O. This characteristic agrees with the packing similarity observed between the dihydrate and CBZ form I. The results of surface and bulk analyses could be correlated to the mechanism of dehydration and can be compared with other CBZ materials and previous studies in the literature.[1,2] It is suggested that dehydration occurs via the release of water following a cooperative route. If the domains formed upon dehydration are, however, very small the anhydrous material appears to have only short range order, with no prominent structural relationship between the parent and daughter phases.[3] Inconsistencies observed in the CBZ dihydrate literature concerning the polymorphic outcome can potentially be explained by how dehydration conditions influence resulting domain sizes, the creation of crystal defects and the nucleation process. These aspects may hinder the prediction of stress-induced transformations. As previously discussed, polymorphic prediction on the basis of molecular structure remains challenging.[4,5] It is likely to remain a challenge if additional solid state aspects along with use of a variety of experimental probes are not considered. Keywords: carbamazepine, dehydration/desolvation, AFM. Acknowledgements: G. Schneider Rauber thanks CAPES-Brazil and COT-UK for her scholarship (CsF BEX 9530/13-4). The authors acknowledge AbbVie Inc. for collaboration and funding. [1] K.Kachrimanis and U.J.Griesser, Pharm.Res., 2012, 29, [2] J.Y.Khoo et.al., PowderTechnol., 2013, 236, [3] S.Petit and G.Coquerel, Chem. Mater., 1996, 8, [4] A.J.Cruz-Cabeza, S.M.Reutzel-Edens, and J.Bernstein, Chem. Soc. Rev., 2015, 44, [5] V. S. Minkov et. al., Cryst. Growth Des., 2014, 14, April,

124 P-43 Crystal Morphology and Interfacial Stability of RS-Ibuprofen in Relation to its Molecular and Synthonic Structure T.T.H Nguyen a, I. Rosbottom a, I. Marziano b, R.B. Hammond a, K.J. Roberts a a Centre for the Digital Design of Drug Products, School of Chemical and Process Engineering, University of Leeds, Leeds, UK, LS2 9JT; b Pfizer Worldwide Research and Development, Sandwich, CT13 9NJ, UK. k.j.roberts@leeds.ac.uk The key intermolecular (synthonic) interactions, crystal morphology and surface interfacial stability of the anti-inflammatory drug RS-ibuprofen are examined in relation to its bulk crystal and surface chemistry, and to rationalise its growth behaviour as a function of crystallisation environment. The OH O H-bonding dimers between adjacent carboxylic acid groups are calculated to be the strongest bulk (intrinsic) synthons, with other important synthons arising due to interactions between the less-polar phenyl ring and aliphatic chain. Morphological prediction, using the attachment energy model predicts a prismatic facetted shape, in good agreement with the shape of the experimentally grown crystals from the vapour phase. Crystals grown from solution are found to have higher aspect ratios, with those prepared in polar protic solvents (EtOH) producing less needle-like crystals, than those prepared in less polar and aprotic solvents (toluene, acetonitrile and ethyl acetate). Examination of the surface chemistry reveals that the most important extrinsic (surface-terminated) synthons on the capping {011} surface involve H-bonding interactions, whilst those on the side {002} surfaces mostly involve van der Waal s (vdw) interactions. This suggests that a polar, protic solvent is more likely to bind to the capping {011} surface and inhibit growth of the long axis of the needle, compared to apolar and/or aprotic solvents. A previously unreported re-entrant face is found to appear in the external crystal morphology at higher supersaturations, not due to twinning, which is provisionally identified as either the {112} or {012} form. Analysis of the calculated surface entropy α-factors suggest that the capping faces would be expected to be least smooth on the molecular level, with a higher degree of unsaturated extrinsic synthons, in comparison to the {002} and {100} faces. This is consistent with growth mechanism data previously published 1, and with the observed re-entrant morphological instability at the capping surfaces. Keywords: Crystal Morphology, Morphological Instability, Surface Chemistry [1] Nguyen, T. T. H.; Hammond, R. B.; Roberts, K. J.; Marziano, I.; Nichols, G., CrystEngComm 2014, 16, April, 2017

125 P-44 Influence of Solvent Composition on the Crystal Morphology and Structure of p-aminobenzoic Acid Crystallised from Mixed Ethanol and Nitromethane Solutions I. Rosbottom a, C.Y. Ma a, T.D. Turner a, R.A. O Connell a, G. Sadiq c, J. Loughrey b, R.J. Davey c and K.J. Roberts a a Centre for the Digital Design of Drug Products, School of Chemical and Process Engineering, University of Leeds, Leeds, UK, LS2 9JT; b School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK; c School of Chemical Engineering and Analytical Science, University of Manchester, Oxford Road, Manchester, UK, M13 9PL. k.j.roberts@leeds.ac.uk The demand for active pharmaceutical ingredients (API) to be crystallised with high purity and tailored physical properties for downstream processing has resulted in enhanced scrutiny on the solvent selection for API crystallisation. Here the crystalline form and morphology of a model pharmaceutical-like material para aminobenzoic acid (paba) produced from mixed solutions of ethanol (EtOH) and nitromethane (NMe) are examined, and the behavior is discussed with respect to rationalization using molecular modelling tools. Crystallisation from solutions with between 10% and 60% NMe content yield a mixture of α-paba and a previously unreported NMe solvate structure whose hydrogen bonding structure and chemistry has some similarities to α-paba. Solutions with between 70% and 90% NMe content yielded only α-paba. Molecular modelling calculates that NMe has a greater propensity to interact with the NH 2 and phenyl ring of paba than EtOH, and the position of the NMe molecule within the solvate is in close proximity to the NH 2 of paba. The lattice energy and intermolecular interactions are calculated to be weaker in the solvate structure than α-paba, along with a decrease in crystal packing density. The crystal morphology produced from solutions with increasing NMe content becomes progressively less needle-like. The π-π stacking interactions in the solvate structure are increased in intermolecular distance and more offset when compared to α-paba. These stacking interactions dominate the growth along the needle-axis of α-paba[1,2] and molecular modelling of NMe calculates that it has a greater propensity to interact with the phenyl ring than EtOH, and therefore is more likely to disrupt these stacking interactions. This study rationalizes the crystallisation, solvate formation and morphology of paba in mixed EtOH:NMe environments using molecular modelling techniques. This study is relevant to enhancing the technology to use digital design techniques to guide the solvent selection in pharmaceutical crystallisation, hence reducing time and resource consuming experimental solvent screening. Keywords: Solvate/pseudopolymorphism, Crystal Morphology, Solvent Mixtures [1]. R.A. Sullivan, R.J. Davey, CrystEngComm, 2015, 17, [2]. I. Rosbottom, K.J. Roberts, R. Docherty, CrystEngComm, 2015, 17, April,

126 P-45 How Good Is My Solid Form? The CCDC Approach to a Health Check Ghazala Sadiq and Neil Feeder The Cambridge Crystallographic Data Centre, Cambridge, CB2 1EZ, UK. sadiq@ccdc.cam.ac.uk Solid form selection of the Active Pharmaceutical Ingredient (API) is a key stage in the drug product development process. Uncontrolled crystal form polymorphism can have a critical impact on pharmaceutical drug product robustness, exemplified by Norvir [1] and Neupro [2]. The Norvir example illustrates how such polymorphism can be driven by a stronger set of hydrogen bonds in the stable form. The application of informatics-based assessment of new chemical entities complements experimental studies and provides a deeper understanding of the qualities of the structure. The information provided by structural analyses is incorporated into the assessment of risk for the drug candidate. Informatics techniques, which harness the knowledge contained within over 850,000 plus entries in the Cambridge Structural Database (CSD)[3], are quick to apply and are straightforward to use allowing an assessment of progressing drug candidates. Software including such methodologies is being developed under the guidance of the Crystal Form Consortium (CFC); a partnership between the CCDC and global pharmaceutical & agrochemical companies. The basis of a Structural Informatics crystal form assessment Health Check [4] is to analyse the properties of a specific crystal form in comparison to properties observed for similar structures in the CSD and to relate this commonality to thermodynamic stability. Deviation from the norm for the crystal form under investigation could then be taken as an indication that a more stable polymorph might exist for that molecule. The structural features studied typically focus on the crystal packing, intramolecular interactions, intermolecular interactions, propensity and the geometry of interactions observed. Here we will describe what a health-check is, what structural informatics tools included in CSD-Materials are used to carry out a health check and how the potential application of these tools can be used to minimise risk in solid form design. Keywords: Polymorphism, Interaction, Pharmaceutical, Solid Form [1] J. Bauer, et al, Pharm. Res., 2001, 18, 859. [2] K.R. Chaudhuri, Expert Opin. Drug Deliv., 2008, 5 (11), [3] C. R. Groom, I. J. Bruno, M. P. Lightfoot, S. C. Ward, Acta Crystallogr.,Sect. B:Struct. Sci.,Cryst. Eng. and Mat., 2016, 72, 171. [4] N. Feeder, E. Pidcock, A.M. Reilly, G. Sadiq, C.L. Doherty, K.R. Back, P. Meenan and R. Docherty J. Pharmacy and Pharmacology, 2015, 67, April, 2017

127 P-46 Cryochemical Synthesis of New Polymorphic β-modification of Antibacterial Substance 2,3-bis(hydroxymethyl)chynoxaline-n,n'- dioxide Tatyana I. Shabatina, Olga I. Vernaya, Yulia. V. Kuchina, Yurii N.Morosov, Vladimir.P. Shabatin a Departments of 1 Chemistry Lomonosov Moscow State University, Moscow, Russia, tatyanashabatina@yandex.ru Modern drugs are complex organic compounds and they are often poorly soluble in water. Special methods and nanotechnologies were developed to obtain drug nanofoms. Wide and not always reasonable use of antibiotics and other antimicrobial agents in medicine has led to the emergence of many resistant strains of microorganisms. In our days, this problem is solved by the synthesis of new antibiotic substances and their new crystal moifications. Well-dispersed (average diameter 110 nm) new β- modification of 2,3-bis(hydroxymethyl)chynoxaline-N,N'-dioxide (dioxidine) was prepared by means of cryochemical modification using low temperature condensation of drug substance vapor and freeze drying technique of water solutions of α-modification of 2,3-bis(hydroxymethyl)chynoxaline-N,N'-dioxide as the initial reagent. The data of nuclear magnetic resonance and gas chromatography, confirmed the sameness of the chemical nature of the primary and modified substances. The data of X-ray phase analysis, differential thermal analysis (DTA) and Fourier transformation infrared spectroscopy (FTIR) showed the differences in crystal packing and phase state of α- and β- modification of 2,3-bis(hydroxymethyl)chynoxaline-N,N'- dioxide. TEM data showed the formation of nanoparticles of antibiotic of nm in diameter. 2 2 theta New cryoformed nanosized form of antibiotic demonstrates higher antibacterial activity against Escherichia coli 52 compared to the original drug/. Acknowledgements. The work was financially supported by Russian Scientific Foundation (grant RSN Keywords: drug nanoforms, antibiotics, polymorphic modifications 2 7 April,

128 P-47 Salt of Tryptophan with S-Camphor-10-Sulphonic Acid Amina Sayed a and Ayesha Jacobs a a Department of Chemistry, Cape Peninsula University of Technology, PO Box 652, Cape Town 8000, South Africa. amina.sayed17@gmail.com L-tryptophan, (2S)-2-amino-3-(1H-indol-3-yl)propanoic acid, is an essential amino acid and is typically obtained from the diet[1]. Its enantiomer, D-tryptophan, (2R)-2-amino-3-(1H-indol-3-yl)propanoic acid, is less prevalent in nature[2]. L-tryptophan, a precursor of the neurotransmitter serotonin is used as a nutritional supplement to treat insomnia and depression [3]. The interest in obtaining enantiomerically pure compounds has led to increased research in chiral resolution processes. One of the oldest and most employed crystallisation technique to achieve resolution is the formation of diastereomeric salts using an acidic or a basic chiral resolving agent. In this study we have employed S-camphor-10-sulphonic acid as a potential resolving agent of a racemic mixture of tryptophan. Co-crystallisation of DL-tryptophan with S-camphor-10-sulphonic acid resulted in a salt[4]. The amino acid is in the cationic form with the proton transferred from the acidic co-former to the amino acid. S-camphor-10-sulphonic acid was unsuccessful at resolving DL-tryptophan. Dissolution of the respective camphorsulphonic acid and DL-tryptophan in methanol/water gave crystals which contained equimolar amounts of the D- and the L-tryptophan. b 0 c Keywords: tryptophan, camphorsulphonic acid, amino acid, chiral resolution [1] G. Wu, Amino Acids, 2009, 37, 1. [2] P. K. Pallaghy, A. P. Melnikova, E. C. Jimenez, B. M. Olivera and R. S. Norton, Biochemistry, 1999, 38, [3] S. N. Young and M. Leyton, Pharmacol. Biochem. Behav., 2002, 71, 857. [4] A. Sayed and A. Jacobs, J. Chem. Crystallogr., 2016, 46, April, 2017

129 P-48 Temperature-Dependence of Flexible Metal-Organic Framework Co(OBA)(bpmp): Hysteric Sorption of CO2, CH4 and C2H6 and in-situ Crystallographic Observation of Gas Loading Phumile Sikiti, Charl X. Bezuidenhout and Leonard J. Barbour Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. Flexible metal-organic frameworks that undergo structural phase changes upon gas adsorption are promising materials for gas storage and separations, and achieving synthetic control over the temperature at which the stable activated form occurs is crucial to the design of such materials for specific applications. The isoreticular structures of Co(OBA)(bpmp) (OBA = 4,4 -Oxybisbenzoicacid, bpmp = N,N -bis(4- pyrdylmethyl)piperazine) has been obtained MeOH/DMF via solvthermal reaction at different temperatures. The resulting structure of (Co(OBA) 4(bpmp) 2 (DMF) n) (Co-OBA-bpmp@80) paddle wheel and (Co(OBA) 4(bpmp) 2 (DMF) n) (Co-OBA-bpmp@120) distorted paddle wheel SBU depend on the temperature applied during the synthesis, revealing a temperature susceptible isoreticular isomerism. Single-crystal X-ray diffraction analyses suggest that this new compounds are isoreticular but they both display different unique sorption properties towards CO 2, CH 4, and C 2H 6 at high pressure. (Co-OBAbpmp@80) and (Co-OBA-bpmp@120) sorption of CO 2 at 298 K at high pressure shows a three-step isotherm with hysteresis and (Co-OBA-bpmp@80) show an opening at 11bar for C 2H 6 and (Co-OBAbpmp@120) shows a giant hysteresis for C 2H 4 gas at room temperature. Pressures-Powder-Xr-ray diffraction agreed with sorption both compounds and Pressure- Diffraction Scanning Calorimetry for both compounds on CO 2 also supported the sorption. In-situ single-crystal diffraction analysis was carried under CO 2 gas pressure at 298 K using an environmental gas cell in order to observe the interaction between CO 2 for (Co- OBA-bpmp@120) after activation for CO 2 and CH 4. Keywords: Flexible metal organic framework, Sorption, Hysteric [1] M. Taylor, T. Runčevski, J. Oktawiec, M. Gonzalez, R. Siegelman, J. Mason, J. Ye, C. Brown, and J. Long, J. Am. Chem. Soc. 2016, 138, [2] P. Lama, H. Aggarwal, C. Bezuidenhout, and L. Barbour, Angew. Chem. Int. Ed., 2016, 55, [3] P. Kanoo, R. Matsuda, R. Kitaura, S. Kitagawa, and T. Maji, Inorg. Chem. 2012, 51, April,

130 P-49 Molecular Selectivity by Host-Guest Methods Jacky S. Bouanga Boudiombo, Luigi Nassimbeni and Susan A. Bourne Department of Chemistry, University of Cape Town, Private Bag, Rondebosch 7701, South Africa. Molecular selectivity by host-guest procedures is an increasing method to help in the separation of enantiomers. In this study, two similar bile acids, cholic acid (CA) and deoxycholic acid (DCA), were used as hosts to separate the mixtures of several isomer guests. The different compounds prepared were analyzed by single crystal X-Ray diffraction. Our first guest mixtures were the isomers of methylacetophenones (MeAC) whose normal boiling points range from 214 to 226. We prepared equimolar mixtures of the three isomers in pairs and dissolved the CA host in them, such that the total guest to host ratio was 5. The crystals obtained from the 2-MeAC / 4-MeAC yielded the compound (CA 4-MeAC). The inclusion compound crystallized in the space group P21. The separation was therefore completely successful for this mixture of isomers. The 2-MeAC guests are located in channels formed by the host structure. Further analytical measurements carried out by NMR and thermal analysis are in agreement with the structural results. Keywords: Host-guest method, bile acids, enantiomers April, 2017

131 P-50 Selective Enclathration of Methyl- and Dimethyl-Piperidines by Fluorenol Hosts Nicole Sykes, a Hong Su a, Edwin Weber b, Susan A. Bourne a and Luigi R. Nassimbeni a a Department of Chemistry, University of Cape Town, Private Bag, Rondebosch 7701, South Afriac; b Institut für Organishe Chemie, TU Bergakademie Freiberg, Leipziger Strasse 29, D Freiberg/Sachs, Germany. Nicole.Sykes@alumni.uct.ac.za Two similar fluorenyl diol hosts 9,9 -(ethyne-1,2-diyl)-bis(fluoren-9-ol) (H1) and 9,9 -(1,4-phenylene)- bis(fluoren-9-ol) (H2) have been employed to study their selectivity towards methylated piperidines. Crystal structures show strong similarities in the packing of these inclusion compounds, but the interesting result arises from the competition of these hosts for equimolar 2,6- and 3,5-dimethylpiperidine (2,6DMP and 3,5DMP). H1 selects 3,5DMP while H2 selects 2,6DMP. Packing analysis and lattice energy calculations failed to explain this result, but the DSC profiles of the four host-guest compounds are in agreement with the selectivity experiments. Exo Hea t Flo w Wei ght (%) Endo Temperature ( C) Temperature ( C) Keywords: Host-Guest compounds, Hydrogen bonding, Selectivity 2 7 April,

132 P-51 Family of Isostructural Single-Component Crystals Davin Tan, a Athanassios D. Katsenis, a Tomislav Friščić a a Department of Chemistry, McGill University, 801 Sherbrooke St. W., H3A 0B8 Montreal, QC, Canada. davin.tan@mail.mcgill.ca, tomislav.friscic@mcgill.ca Isostructurality in sets of compounds that include more than two members is a rare phenomenon,[1-4] as minor changes in the molecular structure can very often lead to significant differences in the way the molecules pack in the solid state. We now report a highly unusual set of eight isostructural compounds, discovered in a series of N,N -biscyclohexyl-arylsulfonylguanidines that differ in the substitution pattern of the arylsulfonamide moiety. In particular, the eight compounds adopt an almost identical P3 2 crystal structure, which persists despite significant chemical and structural variations of the substituent in ortho-position to the sulfoguanidine group from hydrogen to fluorine, chlorine, bromine, methyl or nitro groups. In addition, the crystal structure is conserved also upon simultaneous exchange of hydrogen atoms in positions 2 and 5, or 2 and 6, for fluorine atoms. In this highly persistent and chiral crystal structure, the molecules of non-chiral compounds assemble through intermolecular S=O... H-N hydrogen bonds to form helical chains that propagate along a three-fold crystallographic screw axis. To the best of our knowledge, this surprisingly large set of isostructural crystals represents the so far largest family of isostructural compounds. Keywords: Isostructural, arylsulfonyl-guanidines. [1] C. M. Reddy, M. T. Kirchner, R. C. Gundakaram, K. A. Padmanabhan, G. R. Desiraju, Chem. Eur. J., 2006, 12, [2] J. Galcera, T. Friščić, K. Hejczyk, L. Fábián, S. M. Clarke, G. M. Day, E. Molins, W. Jones, CrystEngComm, 2012, 14, [3] B. R. Bhogala, S. Basavoju, A. Nangia, Cryst. Growth. Des., 2005, 5, [4] K. B. Landenberger, O. Bolton, A. J. Matzger, Angew. Chem. Int. Ed., 2013, 52, April, 2017

133 P-52 From Serendipity to Design: Thermosalient Crystals Based on Etter-type N,N -bisarylureas Davin Tan, a Gregorio J. Hernández, a Tomislav Friščić a a Department of Chemistry, McGill University, 801 Sherbrooke St. W., H3A 0B8 Montreal, QC, Canada. davin.tan@mail.mcgill.ca, tomislav.friscic@mcgill.ca Thermosalient behavior, i.e. physical motion of crystals upon thermally-induced change in crystal structure, has recently become one of the highly active areas of solid-state organic chemistry.[1] Although such behavior of crystalline organic solids, also known as the jumping crystal effect, has been known since 1980s, systematic studies have begun only recently, inspired by the potential applications of thermosalient materials in harvesting and transduction of thermal energy.[2,3] So far, approximately two dozen jumping crystals have been reported in the literature and, despite a growing number of recent systematic investigations,[4] the development of such materials is still in its infancy, with new materials typically being discovered by trial-anderror. We now present the serendipitous discovery of a class of organic jumping crystals based on "Etter-type" N,N -diphenylureas which provides access to a family of chemically-related materials with notable propensity for thermosalient behavior. Keywords: Thermosalient, jumping crystals. [1] P. Naumov, S. Chizik, M. K. Panda, N. K. Nath, E. Boldyreva, Chem. Rev., 2015, 115, [2] N. K. Nath, M. K. Panda, S. C. Sahoo, P. Naumov, CrystEngComm, 2014, 16, [3] M. K. Panda, T. Runčevski, S. C. Sahoo, A. A. Belik, N. K. Nath, R. E. Dinnebier, P. Naumov, Nature Commun., 2014, 5, [4] Z. Skoko, S. Zamir, P. Naumov, J. Bernstein, J. Am. Chem. Soc., 2010, 132, April,

134 P-53 Directional Locomotion of Chiral Azobenzene Crystals by Phase Transition Takuya Taniguchi, a Haruki Sugiyama, b Hidehiro Uekusa, b Motoo Shiro, c Hideko Koshima, c and Toru Asahi a,c a Department of Advanced Science and Engineering, Waseda University, 2-2 Wakamatsu-cho, Shinjuku-ku, Tokyo, Japan; b Department of Chemistry and Materials Science, Tokyo Institute of Technology, Ookayama , Meguro-ku, Tokyo, Japan; c Research Organization for Nano & Life Innovation, Waseda University, 513 Wasedatsurumaki-cho, Shinjuku-ku, Tokyo, Japan. s @ruri.waseda.jp Mechanical motion of molecular crystals has attracted much attention recently and the future applications to actuators and artificial muscles are anticipated. Recently, we have reported that thin crystals of chiral azobenzene derivative trans-(s)-1 bent with twisting upon UV light irradiation [1]. In the course of experiments, we found that the crystal of trans-(s)-1 occurred single-crystal-to-single-crystal phase transition by heat. Here, we report the characterization of thermal phase transition and the discovery of directional locomotion of crystals of trans-(s)-1 induced by the reversible single-crystal-to-single-crystal phase transition. Single crystal of trans-(s)-1 occurs reversible single-crystal-to-single-crystal phase transition at 145 C. X- ray crystallographic analysis before and after the phase transition revealed that the thickness (a axis) and length (b axis) contracted and the width (c axis) of crystal elongated at high temperature after the phase transition. When heated the crystal on substrate, bending motion was observed during the transformation. This was because phase transition started from substrate side of the crystal and then proceeded to whole of the crystal. We discovered that long needle-like crystal of trans-(s)-1 (1 cm in length) moved slowly like inchworm at the speed of 2 mm/h under the repeating cycles of heating and cooling near the transition temperature. Furthermore, thin plate-like crystal of trans-(s)-1 (2 cm in length and 70 µm in thickness) flipped in 0.1 sec and moved very fast at the speed of 1 cm/s upon heating or cooling near the transition temperature without repeating the cycle of heating and cooling. Temperature distribution on crystal was measured by an infrared thermography and then the mechanism of directional locomotion was proposed. Keywords: locomotion, single-crystal-to-single-crystal phase transition, chiral azobenzene crystal [1] T. Taniguchi, J. Fujisawa, M. Shiro, H. Koshima and T. Asahi, Chem. Eur. J., 2016, 22, April, 2017

135 P-54 Ternary Co-Crystals Using Hydrogen and Halogen Bonds: Identifying the Weak Links Filip Topić a and Kari Rissanen a a Department of Chemistry, Nanoscience Center, University of Jyväskylä, P.O. Box 35, University of Jyväskylä, Finland. filip.topic@gmail.com In the last two decades, co-crystals have emerged as a prominent topic in crystal engineering.[1] One of the main challenges in the study of co-crystals has been their rational and systematic preparation, which would in turn allow for the fine tuning of their structure and properties. This is especially so for the co-crystals consisting of three (ternary) or more components. Recently, we reported a robust strategy for the preparation of ternary co-crystals using hydrogen and halogen bonds, combining thioureas, crown ethers and perfluorinated halogen bond donors.[2] These components form reliable and mutually orthogonal hydrogen (thioureas and crown ethers) and halogen bonds (thioureas with perfluorinated halogen bond donors). Our initial studies demonstrated a high success rate, yielding ternary co-crystals for 15/20 co-former combinations. We then set out to test the generality of our strategy by expanding the co-former set with a number of perfluoroalkyl (di)iodide halogen bond donors, crown ethers and thioureas. In total, crystal structures of over 50 different ternary co-crystals were obtained, allowing us to discuss a number of factors governing their successful formation. In particular, the sterical factors, metrics of the co-former molecules and the packing preferences of the co-formers containing aromatic rings were found to significantly affect the co-crystallization outcome. Keywords: crystal engineering, ternary co-crystals, hydrogen bonding, halogen bonding [1] C. B. Aakeröy, Acta Cryst., 2015, B71, 387. [2] F. Topić and K. Rissanen, J. Am. Chem. Soc., 2016, 138, April,

136 P-55 Fractional Occupancy of Solvent Excluded Volume in the Solid State Dewald P. van Heerden, a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. dpvh@sun.ac.za The larger thermal motion of solvent molecules often impedes their accurate modelling in crystal structures. For the purpose of aiding structure solution, we set out to estimate the fraction of available space that a solvent occupies, on average, in the solid state. The Cambridge Structural Database (CSD), version 5.37[1] was explored and lists of solvated structures without disorder exported to Materials Studio.[2] After determination of the solvent excluded volumes of close to structures, a tentative guide of 45% occupancy is proposed. A number of different topologies have been defined to aid in the delineation and measurement of regions potentially occupied by solvent in crystal structures. The van der Waals surface (VdW) of a molecule is defined as the boundary of the union of hard spheres representing its constituting atoms, while the solventaccessible surface (SAS) is traced out by the centre of a probe sphere representing a solvent molecule as it is rolled over the VdW surface. The solvent-exclusion surface (SES) consists of the convex regions of the VdW surface that are in contact with the probe and the concave re-entrant portions that smooth over cusps in between atoms.[3] A number of Python scripts were written to enable the selection of a specific solvent molecule within the multitude of crystal structures obtained from the CSD. The multiplicity of each atom in the asymmetric unit of a solvent molecule (m, equal to the number of symmetry operators in the space group for atoms located on positions not associated with a symmetry element) is summed and divided by the number of atoms making up the solvent molecule (n) to afford the number of solvent molecules per unit cell, S = (Σm) n. SES volumes employing a probe radius of 1.2 Å were subsequently calculated for structures from which the solvent was deleted to impose virtual porosity.[4] The fraction of the excluded volume occupied by solvent molecules was found to vary between 40% for nonpolar guests such as n-hexane (1244 structures investigated) and benzene (3725) and 50% for polar, coordination-prone solvents such as tetrahydrofuran (7777) and acetonitrile (7892). This tentative guide provides a means of estimating the possible number of disordered solvent molecules within a crystal structure based on available space. Keywords: Solvent accessible volume, Cambridge Structural Database, Solvates [1] C.R. Groom, I.J. Bruno, M.P. Lightfoot, S.C. Ward, Acta Cryst., 2016, B72, 171. [2] Biovia Materials Studio 2016, Dassault Systèmes. [3] B. Lee, F.M. Richards, J. Mol. Biol., 1971, 55, 379; F.M. Richards, Annu. Rev. Biophys. Bioeng., 1977, 6, 151. [4] L.J Barbour, Chem. Commun., 2006, 11, April, 2017

137 P-56 Volatile Solvent Trapping by a Solvatochromic Metallocycle Lisa M. van Wyk, a Varvara I. Nikolayenko a and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa. lmvw@sun.ac.za As numerous volatile organic solvents are used en masse in both research and industry, effective solvent trapping and recycling will lead to a diminished environmental impact and reduction of the health risks associated with repeat exposure. Thus systems involved in the sensing and reversible trapping of these volatile organic solvents would be invaluable. Porous materials are extensively described in the literature. Furthermore, the Barbour group has shown certain metallocycles to be transiently porous.[1,2] Some metallocycles may even exhibit solvatochromic behaviour and could therefore be used as molecular sensors.[3-6] One such metallocycle is [Cu 2Cl 4L 2] 2DMSO, where L is 1,4-bis[(2-methylimidazol-1-yl)methyl]benzene. The acetonitrile (ACN) and acetone analogues of this system, as well as two apohost forms, have already been described in the literature.[6] This metallocycle is essentially non-porous due to the two coordinated dimethyl sulfoxide (DMSO) molecules blocking the aperture. This bond can be cleaved, using solvent exchange (the most successful of which is ACN), to yield new uncoordinated solvates. Various solvates were generated via solvent exchange, the resultant variation in colour indicating the solvatochromic nature of this metallocycle. The diethyl ether solvate was then found, by thermogravimetric analysis and single crystal X-ray diffraction, to retain diethyl ether significantly above its boiling point (~35 C). It was possible to obtain a crystal structure of the diethyl ether included metallocycle at 70 C, with a single crystal surviving several cycles between -173 and 70 C. Surprisingly, no clear host-guest interactions which tether the diethyl ether in the metallocycle can be observed. The pentane and tetrahydrofuran (THF) solvates were subsequently studied as comparative systems. The pentane solvate exhibited a similar level of solvent retention as the diethyl ether solvate, despite its lack of heteroatom. Moreover, the THF solvate also demonstrated solvent retention. While the exact mechanism of solvent retention is still under review, this metallocycle shows promise as a volatile solvent trap as well as proving to be an effective solvatochromic sensor. Keywords: metallocycle, diethyl ether, solvent trapping, solvatochromism [1] M. du Plessis, V. J. Smith and L. J. Barbour, Cryst. Eng. Comm., 2014, 16, [2] L. Dobrzańska, G. O. Lloyd, H. G. Raubenheimer and L. J. Barbour, J. Am. Chem. Soc., 2006, 128, 698. [3] M. A. Omary, O. Elbjeirami, C. S. Palehepitiya Gamage, K. M. Sherman and H. V. Rasika Dias, Inorg. Chem., 2009, 48, [4] P. Thanasekaran, R. T. Liao, Y. H. Liu, T. Rajendran, S. Rajagopal and K. L. Lu. Coord. Chem. Rev., 2005, 249, [5] M. Albrecht, M. Lutz, A. L. Spek and G. van Koten. Nature, 2000, 406, 970. [6] L. Dobrzańska, G. O. Lloyd, C. Esterhuysen and L. J. Barbour, Angew. Chem. Int. Ed., 2006, 45, April,

138 P-57 Xylene Isomers Entrapment on Metallocyclic Framework Banele Vatsha and Leonard J. Barbour Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa; Metallocyclic or macrocyclic compounds are increasingly drawing research attention due to exotic solid-state structural properties. The simple chemical structure and composition are important components of metallocyclic framework behaviour. The frameworks constructed from these types of materials continues to exhibit unexpected properties. Herein, we present a 3D framework constructed from 3,3,5,5 -tetramethyl-4,4 - bispyrazole ligand (Me4BPz) and copper (I) chloride (CuCl) in a binary solvent viz, water and acetonitrile (CH 3CN) under solvothermal conditions. Single-crystal X-ray structural analysis reveals that it crystallizes in the orthorhombic crystal system with space group Ima2. In the asymmetric unit, one Cu(I) ion is coordinated to one nitrogen atom from Me 4Bpz, one half of CN -, and half of a guest acetonitrile molecule. The cyanide ligands were generated in situ by cleavage of the CH 3CN C C bond. The framework displays a distorted tetrahedral geometry with a 1D ladder pore channel running along the c axis (as seen below). The desolvated form has a solvent accessible volume of ca % after removal of the free CH 3CN molecules. Our structureproperty studies provide not only a new synthetic route to obtain a new kind of framework for possible separation but also new insights into 3D framework structure-function relationships. Keywords: activation, metallocycle, structure, seperation, April, 2017

139 P-58 Development of Correlative Cryo-soft X-ray Tomography (Cryo- SXT) and Stochastic Reconstruction Microscopy (STORM). A Study of Cholesterol Crystal Early Formation in Cells Neta Varsano a, Tali Dadosh b, Sergey Kapishnikov d, Eva Pereiro e, Eyal Shimoni b, Xueting Jin e, Howard S. Kruth f, Leslie Leiserowitz c and Lia Addadi a * a Department of Structural Biology, b Department of Chemical Research Support, c Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot, Israel. d Soft Matter and Functional Materials, HelmholtzZentrum Berlin, Germany e ALBA Synchrotron Light Source, MISTRAL Beamline Experiments Division, Barcelona, Spain f Experimental Atherosclerosis Section, National Institutes of Health, Bethesda, Maryland neta.varsano@weizmann.ac.il Atherosclerosis, the major precursor of cardiovascular disease, is characterized by the deposition of excessive cholesterol in the arterial intima. [1] Atherosclerotic plaques build up in arteries in a slow process that initiates with uptake of LDL particles by macrophage cells leading to deposition of cholesterol monohydrate crystals and cell death. 1 Precipitation of cholesterol crystals is a crucial part of the pathological progression. [2] We suggested that the initial step in atherosclerosis development may be from cholesterol domains segregating in cell membranes and serving as nucleation sites for the formation of 3-dimensional (3D) cholesterol crystals [3,4]. To verify whether this process can be relevant to in vivo processes, we have developed a high resolution correlative method combining cryo-soft X-ray tomography (cryo-sxt) and stochastic optical reconstruction microscopy (STORM). [5] The approach provides 3D information on large cellular volumes at 70 nm resolution. [5] Cryo-SXT morphologically identifies and localizes aggregations of carbon-rich materials, while STORM identifies specific markers on the desired epitopes, enabling colocalization between the identified objects and the cellular environment. Using a specific antibody (MAB 58B1) which labels cholesterol crystals [6], we identify and image crystals at a very early stage ( nm) on the cell plasma membrane and in intracellular locations. This technique can in principle be applied to other biological samples where specific molecular identification is required in conjunction with high resolution 3D-imaging. Keywords: Cholesterol crystals, phthological crystallization, Template nucleation [1]Kruth, H. S. Curr. Mol. Med. 2001, 1, 633. [2] Tangirala, Rajendra K., W. Gray Jerome, N. L. Jones, Donald M. Small, W. J. Johnson, J. M. Glick, F. H. Mahlberg, and G. H. Rothblat. J. Lipid Res., 1994, 35, 93. [3] Ong, D. S.; Anzinger, J. J.; Leyva, F. J.; Rubin, N.; Addadi, L.; Kruth, H. S. J. Lipid Res. 2010, 51, [4] Ziblat, R.; Fargion, I.; Leiserowitz, L.; Addadi, L. Biophys. J. 2012, 103, 255 [5]Varsano, N., Dadosh T., Kapishnikov S. Pereiro E. Shimoni E. Jin X., Kruth, H. S. Leiserowitz L, and Addadi L. J. Am. Chem. Soc. 2016, DOI: /jacs.6b07584 [6] Addadi, L., Rubin, N., Scheffer, L. and Ziblat, R., Acc. Chem. Res., 2008, 41, April,

140 P-59 Mechanochemical Synthesis of Porous Halogenated Silver Metal-Organic Frameworks Natasha H. Visser and Leonard J. Barbour Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa Metal organic frameworks (MOFs) have gained much interest in recent studies as crystalline porous materials that can be used in a range of applications such as gas storage, separation and catalysis [1]. MOFs are widely studied as adsorption materials due to their large pore sizes and their ability to be functionalized [2]. Much attention has been devoted to the capture of greenhouse gases, mainly focussing on CO 2 capture and storage while there have been few studies on the capture of other gases such as fluorocarbons and chlorofluorocarbons (CFCs) [2,3]. The use of fluorinated metal-organic frameworks (FMOFs) has also become of particular interest in gas storage as the presence of additional functional sites provides added host-guest interaction [4]. This may result in higher uptake of gas molecules within a particular host. Herein we report the mechanochemical synthesis of two halogenated silver-mofs (containing either F or Cl halogens), both via liquid-assisted grinding (LAG) using diethyl-ether as solvent. The material obtained after grinding was characterized by means of PXRD and IR analysis. Crystallization of the fluorinated MOF from a mixture of methanol and THF yielded crystals suitable for single-crystal XRD (SCXRD) analysis. Vapour sorption studies with both halogenated and non-halogenated solvents were also investigated, showing a higher uptake for the halogenated solvents. Keywords: mechanochemical synthesis, halogened metal-organic frameworks, adsorption [1] C. Yang, X. Wang and M. A. Omary, J. Am. Chem. Soc, 2007, 50, [2] C. Serre, Angew. Chem. Int. Ed., 2012, 51, [3] T. Chen, I. Popov, W. Kaveevivitchai, Y. Chuang, Y. Chen, A. J. Jacobson and S. Ognjen, Angew.Chem. Int.Ed., 2015, 54, [4] G. Chang, H. Wen, B. Li, W. Zhou, H. Wang, K. Alfooty, Z. Bao and B. Chen, Cryst. Growth Des., 2016, 16, April, 2017

141 P-60 Direct Determination of Qst Using Pressure-Gradient Differential Scanning Calorimetry Kerry-Anne White, a Charl X Bezuidenhout, a Vincent J. Smith b and Leonard J. Barbour a a Department of Chemistry, University of Stellenbosch, Private Bag X1, Stellenbosch 7600, South Africa; b Department of Chemistry, University of Rhodes, Grahamstown 6139, South Africa. kwhite@sun.ac.za Energy efficient adsorption by porous materials is desirable for improving the energy costs of industrial processes involving adsorption. Metal-organic frameworks (MOFs) have shown great potential for catalysis as well as gas storage, separation and purification.[1] When evaluating the merits of a given porous material for gas sorption it is necessary to consider several important factors. These include working capacity, saturation pressure, hysteresis, kinetics, selectivity, heats of sorption, and the temperature-dependence of all of these phenomena. With the exception of heats of sorption, it is possible to measure these parameters directly using standard sorption isotherms, which provide uptake capacity as a function of gas pressure. The isosteric heat of sorption (Q st) is an approximation of the heat or enthalpy of sorption (ΔH ads or ΔH des).[2] The isosteric method, an indirect Clausius-Clapeyron approach, is most widely used for determining Q st because of the simplicity and general availability of the required instrumentation.[3] Herein we show a direct approach to determine Q st by employing pressure-gradient differential scanning calorimetry (PGDSC). PGDSC uses the direct measurement of heat whereas the widely used isosteric method uses heat values derived from approximated thermodynamic expressions and the assumption that the bulk gas has ideal behaviour. Using PGDSC we have demonstrated that the scanning calorimetric technique produces reliable temperature-independent Qst data. Keywords: pressure-scanning calorimetry, sorption, isosteric heat [1] D. M. D Alessandro, B. Smit and J. R. Long, Angew. Chemie, Int. Ed., 2010, 49, [2] R. Roque-Malherbe, Microporous Mesoporous Mater., 2000, 41, [3] T. Takaishi, Pure Appl. Chem., 1986, 58, April,

142 P-61 Design of Ni(II) Werner Hosts for Selectivity Enhancement and Crystallisation Versatility Merrill M. Wicht, ab Nikoletta B. Báthori a and Luigi R. Nassimbeni a a Department of Chemistry, Cape Peninsula University of Technology, P.O.Box 652, Cape Town 8000, South Africa; b Department of Chemistry, University of Cape Town, Private Bag, Rondebosch 7701, South Africa. wichtm@cput.ac.za Nickel (II) thiocyanato Werner hosts have the ability to enclathrate organic molecules and, with design to their ligands, can be applied to solvent-free crystallisation procedures[1] and selectivity experiments for aromatic isomers[2] in the liquid and vapour phase. The inclusion formation of a Werner host with 4-vinylpyridine was carried out with a selection of seven polycyclic aromatic hydrocarbons via mechanochemical and other solventfree methods. The successful outcomes were related to the vapour pressure of each guest in grinding experiments and to the guest solubility in aqueous slurries. The selectivity toward xylene isomers of two hosts when Ni(NCS) 2 was co-ordinated with isoquinoline, Ni(NCS) 2(isoquinoline) 4, and 4-phenylpyridine, Ni(NCS) 2(4-phenylpyridine) 4 was compared.[3] The difference in the selectivity was explained by the torsional flexibility of the 4-phenylpyridine compared with the rigidity of isoquinoline. A mixed ligand Werner clathrate, Ni(NCS) 2(isoquinoline) 2(4-phenylpyridine) 2 was synthesised to explore possible enhanced selectivity for the xylene isomers. The products of the competition experiments were explained by the torsional motion of the ligands. Keywords: Werner host, selectivity, torsional flexibility [1] M.M. Wicht, H. Su, N.B.Báthori and L.R. Nassimbeni, CrystEngComm, 2016, 18, [2] M.M. Wicht, N.B. Báthori and L.R. Nassimbeni, Dalton Trans., 2015, 44, [3] M. Lusi, and L. Barbour, Angew. Chem., Int. Ed., 2012, 51, April, 2017

143 P-62 Cocrystals of Pyrazinamide with Unusual Stoichiometry, Zʹ and Zʹʹ values Kelly Nzwanai Shunje a and Nikoletta B. Báthori a a Department of Chemistry, Cape Peninsula University of Technology, P. O. Box 652,Cape Town, 8000, South Africa. bathorin@cput.ac.za An estimated 12% of the crystal structures submitted to the Cambridge Structural Database (CSD) contain more than one formula unit in their asymmetric unit [1] thus understanding of their formation is an intricate process. A comprehensive study on their packing behavior was published by Steed and Steed [1] in which 9 factors were listed as possible contributors to their formation. In a recent study, Brock [2] meticulously analyzed a subset of high-z structures (Z > 4) and concluded that the organizing principles of most of the selected structures can be recognized. Our interest lies in the formation of multicomponent crystals of pyrazinamide (PCA), a popular antituberculotic drug. A general search in the CSD for structures of PCA with organic compounds resulted 39 hits. Most of them contain 2 or more unique chemical units but only five of them had a Z > 1. Crystallisation of PCA with 3,5-dinitrobenzoic acid (DNBA) and 3,5-dinitrosalicylic acid (DNSA) resulted in cocrystal formation with unusual stoichiometry and unique combination of Z, Z and Z τ values. PCA formed a 3:1 cocrystal with DNBA (space group P-1) with Z = 1, Z = 4 and Z τ = 2. DNSA crystallized as a 1:1:1 cocrystal hydrate with PCA (space group P-1, Z = 4, Z =12 and Z τ = 3). While in PCA DNBA amide-amide homosynthons are formed by all PCA molecules, in the PCA DNSA H 2O crystal the acid-amide heterosynthon is preferred with incorporated water molecules. The presented two crystal structures are good examples of how synthon frustration [3] may lead to the formation of crystals with higher Z values. Keywords: Z values, multicomponent crystals, pyrazinamide [1] K. M. Steed and J. W. Steed, Chem. Rev., 2015, 115, [2] C. P. Brock, Acta Cryst., 2016, B72, [3] K. M. Steed, A. E. Goeta and J. W. Steed, Cryst. Growth. Des, 2008, 8, April,