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Crystal Engineering of Molecular and Ionic Cocrystals by Tien Teng Ong

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Crystal Engineering of Molecular and Ionic Cocrystals by Tien Teng Ong Crystal Engineering of Molecular and Ionic Cocrystals by Tien Teng Ong A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Chemistry College of Arts and Sciences University of South Florida Major Professor: Michael J. Zaworotko, Ph.D. Ning Shan, Ph.D. Örn Almarsson, Ph.D. Shengqian Ma, Ph.D. Date of Approval: March 25, 2011 Keywords: Aqueous Solubility, Ellagic Acid, Lithium Salts, Amino Acids, Lithium Diamondoid Metal-Organic Materials © Copyright 2011, Tien Teng Ong Dedication To my dearest parents and esteemed mentor who is apt to judge and appraise this artefact Acknowledgements First and foremost, I will seize this opportunity to express my deepest gratitude to my Ph.D. mentor, Dr. Michael J. Zaworotko, for providing me with the physical and mental space to nucleate and crystallize into who I am today. I must thank the members of my graduate committee: Dr. Ning Shan, Dr. Örn Almarsson, Dr. Shengqian Ma, for their scientific inputs, guidance and support throughout my doctoral research, and Dr. R. Douglas Shytle for kindly agreeing to serve as the chairperson of my examination committee. I thank all past and present members in the research groups of Dr. Zaworotko and Dr. Eddaoudi for their informative discussions, especially the cocrystal team whose earlier work highlighted the trials that lie ahead of me. I especially like to acknowledge and thank Dr. Kapildev K. Arora, Dr. Łukasz Wojtas and Jason A. Perman for imparting their knowledge in the practice of single crystal X-ray crystallography as an indispensable tool in my doctoral research. I thank Dr. Wenge Qiu for lending his ear and more during a testing period of my candidature. And I thank Alexander Schoedel for his help in many ways during the preparation of this dissertation. Thank you all. Table of Contents List of Tables …………………………………………………………………………....vii List of Figures ………………………………………………………………………...….ix Abstract ………………………………………………………………………………….xv Chapter 1. Molecular crystal forms .............................................................................. 1 1.1 Preamble ..................................................................................................... 1 1.2 From molecules to crystals ......................................................................... 2 1.3 Allotropism ................................................................................................. 3 1.4 Polymorphism of molecular crystals .......................................................... 4 1.5 Concomitant polymorphism........................................................................ 7 1.6 Enantiotropy and Monotropy ...................................................................... 9 1.7 Remarks .................................................................................................... 11 Chapter 2. The Impact of Cocrystal on Aqueous Solubility ....................................... 12 2.1 Preamble ................................................................................................... 12 2.2 Biopharmaceutical Classification System (BCS) ..................................... 13 i 2.3 Noyes-Whitney Equation .......................................................................... 14 2.4 Thermodynamic versus apparent solubility .............................................. 15 2.5 Solubility and Melting Point ..................................................................... 16 2.6 Trends in Aqueous Solubility of Cocrystals ............................................. 17 2.7 Conclusion ................................................................................................ 36 Chapter 3. Molecular Cocrystals: Crystal Forms of Ellagic Acid .............................. 38 3.1 Preamble ................................................................................................... 38 3.1.1 CSD Survey of Ellagic Acid ..................................................................... 44 3.1.2 Cocrystals of Polyphenols with Group 1 Basic Cocrystal Formers (Pyridine, Imidazole, Pyrazole) ................................................................ 45 3.1.3 Cocrystals of Polyphenols with Group 2 Zwitterionic Cocrystal ................ Formers ..................................................................................................... 48 3.1.4 Cocrystals of Polyphenols with Group 3 Neutral Cocrystal Formers (Carbonyl) ................................................................................................. 49 3.2 Results and Discussion ............................................................................. 50 3.2.1 Crystal Forms of Ellagic Acid with Group 1 Basic Cocrystal ..................... Formers (Pyridine, Imidazole, Pyrazole) .................................................. 50 3.2.2 Crystal Forms of Ellagic Acid with Group 2 Zwitterionic Cocrystal Formers ..................................................................................................... 58 ii 3.2.3 Crystal Forms of Ellagic Acid with Group 3 Neutral Cocrystal .................. Formers (Carbonyl) ................................................................................... 60 3.2.4 Solvates of Ellagic Acid ............................................................................ 62 3.3 Conclusion ................................................................................................ 67 3.4 Materials and Methods .............................................................................. 70 3.4.1 Synthesis of Crystal Forms of Ellagic Acid .............................................. 71 3.4.2 Crystal Form Characterization .................................................................. 74 Chapter 4. Ionic Cocrystals: Crystal Forms of Lithium Salts..................................... 82 4.1 Preamble ................................................................................................... 82 4.1.1 Amino acids as the ideal cocrystal formers .............................................. 83 - - - 4.1.2 CSD survey of ionic cocrystals of LiX (X = Cl , Br and NO3 ) and ............ amino acids ............................................................................................... 84 - - - 4.1.3 1:2 ionic cocrystals of LiX (X = Cl , Br and NO3 ) and amino acids ......... as structural analogues of zeolites and silica ............................................ 86 4.2 Results and Discussion ............................................................................. 93 4.2.1 1:1 ionic cocrystals of LiX and amino acids: A discrete ............................. supermolecule and linear chains ............................................................... 94 4.2.2 1:2 ionic cocrystals of LiX and amino acids: Square grids, ........................ Diamondoids and a Zeolitic ABW net .................................................... 103 4.3 Conclusion .............................................................................................. 112 iii 4.4 Materials and Methods ............................................................................ 114 4.4.1 Synthesis of Crystal Forms of Lithium Salts .......................................... 114 4.4.2 Crystal Form Characterization ................................................................ 118 Chapter 5. Conclusions and Future Directions ......................................................... 126 5.1 Conclusions ............................................................................................. 126 5.2 Future Directons ...................................................................................... 128 5.3 Crystal Engineering and Crystallization ................................................. 130 References ..................................................................................................... 132 Appendices ..................................................................................................... 159 Appendix 1. Solid state characterization data for ELANAM .......................... 160 Appendix 2. Solid state characterization data for ELAINM•1.7H2O .............. 161 Appendix 3. Solid state characterization data for ELAINM•4NMP ............... 162 Appendix 4. Solid state characterization data for ELAINM•4DMA ............... 163 Appendix 5. Solid state characterization data for ELACAF•H2O ................... 164 Appendix 6. Solid state characterization data for ELATPH•0.13H2O ............ 165 Appendix 7. Solid state characterization data for ELATPH•2DMA ............... 166 iv Appendix 8. Solid state characterization data for ELADMP .......................... 167 Appendix 9. Solid state characterization data for ELASAR ........................... 168 Appendix 10. Solid state characterization data for ELADMG .......................... 169 Appendix 11. Solid state characterization data for ELACAP ........................... 170 Appendix 12. Solid state characterization data for ELAURE•2NMP ............... 171 Appendix 13. Solid state characterization data for ELADMA4 ........................ 172 Appendix 14. Solid state characterization data for ELADMA2 ........................ 173 Appendix 15. Solid state characterization data for ELADMSO2 ...................... 174 Appendix 16. Solid state characterization data for ELANMP2 ........................ 175 Appendix 17. Solid state characterization data for ELAPG2 ............................ 176 Appendix 18. Solid state characterization data for LICSAR ............................
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