Organic Crystal Engineering: Frontiers in Crystal Engineering

Organic Crystal Engineering......Page 5
Contents......Page 9
List of Contributors......Page 15
Preface......Page 17
1.1 Introduction......Page 19
1.2 Organisation and Management of Crystallographic Information......Page 20
1.2.1 Validation of New Crystal Structures: Mogul......Page 21
1.2.2 Validation of Structural Discoveries: What is New and What is Not?......Page 23
1.3.1 IsoStar......Page 24
1.3.2 CSDContact......Page 26
1.3.3 CSDSymmetry......Page 28
1.4.1 A General Tool for 3-D Searches of the CSD: 3DSEARCH......Page 31
1.4.2 Ad hoc Software......Page 35
1.5 Search for Functional Group Exchanges: GRX......Page 36
1.6 Search for Solvated and Unsolvated Structures: Solvates......Page 38
1.6.1 Tools to Examine Structural Similarity......Page 40
1.7 Clustering and Classifying CSD Search Results: dSNAP......Page 41
1.8 The PXRD Profile as a Structural Descriptor......Page 43
1.8.1 IsoQuest......Page 44
1.8.2 Self-organising maps......Page 46
1.8.3 Discrimination of polymorphs and redeterminations......Page 48
1.9 Identifying Supramolecular Constructs: XPac......Page 50
1.10 Concluding Remarks: The Future Role of Crystallographic Databases......Page 54
References......Page 56
2.1 Introduction......Page 61
2.2 Methods used to Predict Crystal Structures......Page 63
2.2.1 Search Methods......Page 64
2.2.2 Evaluating the Computer-generated Crystal Structures......Page 65
2.3.1 The Blind Tests......Page 66
2.3.2 Further Assessments of Crystal Structure Prediction......Page 70
2.3.3 Flexible Molecules......Page 75
2.4 Exploration of Crystal Forms. A Case Study: Carbamazepine......Page 76
2.4.1 Polymorphism and the Influence of Small Molecular Changes on Packing......Page 77
2.4.2 Solvate and Co-crystal Formation......Page 79
2.4.3 Computational Solid Form Screening?......Page 81
References......Page 82
3.1 Introduction......Page 85
3.2 Exploring Crystal Form Diversity......Page 86
3.3 High-throughput Experimentation......Page 90
3.4.1 Indinavir sulfate ethanolate – a case of a salt hydrate/solvate......Page 93
3.4.2 Norfloxacin – polymorphs, solvates, salts, complexes and co-crystals......Page 95
3.5 AMG517 and Celecoxib – ‘Spring and Parachute’ Approach......Page 96
3.5.1 β-Lactam antibiotics and hydrates - the importance of crystallinity......Page 100
3.6 Carbamazepine – Stabilization Against a Hydrate......Page 101
3.7 Theophylline:Phenobarbital – Two is Better Than One......Page 105
3.8 Delaviridine Mesylate – Material Misbehaviour......Page 108
3.9 Summary and Outlook......Page 109
References......Page 111
4.1 Introduction......Page 119
4.2.1 Crystal structure of I (CTAB–p-hydroxybenzoic acid)......Page 121
4.2.3 Crystal structure of III (CTAB–p-cresol)......Page 123
4.2.4 Crystal structure of IV (CTAB–hydroquinone)......Page 124
4.2.7 Crystal structures of VII (LTAB–o-iodophenol) and VIII (DTAB–o-iodophenol)......Page 125
4.2.8 Crystal structure of IX (DTAB–p-hydroxybenzoic acid)......Page 126
4.3.2 Crystal structures of XIII (CTAB–dibenzofuran) and XIV (CTAB–carbazole)......Page 127
4.4 Complex Formation of Biphenyl with Cationic Surfactants......Page 128
4.5 Complex Formation of Odd-Number Surfactants with Biphenyl......Page 130
4.6 Common Packing Mode in the Complexes......Page 132
4.7 Complex Formation by Grinding in a Mortar......Page 135
4.8 C-H. . .π interactions......Page 140
4.9 Complex Formation of Anionic Surfactants with Aromatic Compounds......Page 143
4.10 Increased Solubility of Insoluble Drugs......Page 145
4.11 Enhanced Thermal Stability of Perfumes......Page 148
4.12 Complex Formation with Surfactants other than Quaternary Alkylammonium Salts......Page 152
4.13 Hydroquinone Complexes......Page 154
4.14 Application to Whitening Agents......Page 160
References......Page 165
5.1 Introduction......Page 169
5.2 Hydrogen Bonding in Ureas and Amides......Page 172
5.3 Pyridyl Ureas and Amides......Page 174
5.4 Nitrophenyl Ureas and Amides......Page 178
5.5 Molecular Conformation and Hydrogen Bonding......Page 184
5.6 Supramolecular HSAB Interactions......Page 200
5.7 gem-Alkynols......Page 202
5.8 Conclusions......Page 204
References......Page 205
6.1 Introduction......Page 209
6.2.1 Cyclic thiocarbamides – five-membered rings......Page 212
6.2.3 Acyclic thiocarbamides – E configuration......Page 214
6.2.4 Acyclic thiocarbamides – Z configuration......Page 219
6.3 Conclusions......Page 224
References......Page 229
7.1 Introduction......Page 233
7.2 Primary Amides Containing a Pyridine Moiety......Page 235
7.2.1 Amides directly linked to a pyridine moiety......Page 236
7.3 Co-crystals with Primary Amidopyridines......Page 238
7.3.1 Combination of amides for co-crystallization......Page 241
7.4.1 Monoamide and monopyridine derivatives......Page 242
7.5 Bis-Amidopyridine Derivatives......Page 243
7.5.1 C-Terminal bis-amidopyridines......Page 245
7.5.2 N-Terminal bis-amidopyridines (reverse amides)......Page 247
7.6 Two-component Structures Containing Secondary Amides and Pyridine Derivatives......Page 249
7.7.1 2-Pyridyl based systems......Page 250
7.7.2 3-Pyridyl and 4-pyridyl based systems......Page 251
7.8 Conclusions......Page 252
References......Page 254
8.1 Introduction......Page 257
8.2.1 Isostructurality Based on Interchangeability of Supramolecular Synthons......Page 259
8.2.2 Carbonate and Oxalate as Prolific Hydrogen-Bond Acceptors......Page 261
8.2.3 Hydrogen-Bonded Networks Constructed with 5-Nitrobarbiturate......Page 265
8.2.4 Generation and Trapping of Labile Anions......Page 275
8.3.2 Trapping Cyclic Oxocarbon Dianions in the Crystalline State......Page 283
8.3.3 Charge-localized and -delocalized Valence Tautomeric Forms of Cyclic Oxocarbon Dianions......Page 296
8.4.1 Anionic Rosette Ribbon Built of Guanidinium and Hydrogen Carbonate Dimer......Page 307
8.4.2 Anionic Rosette Networks Assembled with Guanidinium and C3-symmetric Oxo-anion Building Blocks......Page 311
8.4.3 Anionic Rosette Layers Formed by Guanidinium and Non-C3 Molecular Building Blocks......Page 319
8.5 Conclusion and Outlook......Page 324
References......Page 325
Index......Page 331