The Importance of Pi-Interactions in Crystal Engineering

Preface xiii List of Contributors xv 1 The CH/À Hydrogen Bond: Implication in Crystal Engineering 1 Motohiro Nishio, Yoji Umezawa, Hiroko Suezawa and Sei Tsuboyama 1.1 Introduction 1 1.2 Cooperative Effect of the CH/À Hydrogen Bond 7 1.3 CH/À Hydrogen Bonds in Supramolecular Chemistry 14 1.4 Crystallographic Database Analyses 25 1.5 Systematic CSD Analyses of the CH/À Hydrogen Bond 28 1.6 Summary and Outlook 31 2 New Aspects of Aromatic À. À and C-H. À Interactions in Crystal Engineering 41 Roger Bishop 2.1 Introduction 41 2.2 Three-Dimensional Aromatic Structures 44 2.3 Endo,Endo-Facial Dimers 46 2.4 Multiply Halogenated Heteroaromatic Molecules 49 2.5 Expansion of the Endo,Endo-Facial Dimer 56 2.6 (EF)6 Brick-Like Building Blocks 59 2.7 Other Novel Multiple Edge-Face Assemblies 64 2.8 Other Types of Aryl-Aryl Contacts 68 2.9 Conclusions 75 3 CH.À and À.À Interactions as Contributors to the Guest Binding in Reversible Inclusion and Encapsulation Complexes 79 Dr. Pablo Ballester and Dr. Shannon M. Biros 3.1 Introduction 79 3.2 Probing Aromatic-Aromatic (À-À) Interactions and CH-À Interactions with Solid-State Structures of Reversible Inclusion and Encapsulation Complexes 83 3.2.1 Inclusion Complexes 83 3.3 Summary and Outlook 104 4 A Rudimentary Method for Classification of À···À Packing Motifs for Aromatic Molecules 109 Leigh Loots and Leonard J. Barbour 4.1 Introduction 109 4.2 Theoretical Models 110 4.3 À···À Interactions 111 4.4 Structure Prediction and Comparisons 113 4.5 À···À Interactions in Heteroaromatic Molecules 113 4.6 À···À Interactions in Cocrystals 119 4.7 Summary 123 5 Conformational Flexibility and Selectivity in Host-Guest Systems 125 Nikoletta B. Bathori and Luigi R. Nassimbeni 5.1 Introduction 125 5.2 Selectivity 129 5.3 Concluding Remarks 139 6 Organic À-Radicals in the Solid-State: from Localised to Delocalised Ã-Bonding 143 Marc Fourmigue 6.1 Introduction 143 6.2 Molecules for À-Radical Formation 144 6.3 Dimers of Radicals versus Radical Dimers (Pimers) 149 6.4 Solid-State Magnetic and Conducting Properties 154 6.5 Conclusions 159 7 Arene-Perfluoroarene Interactions in Coordination Architectures 163 Akiko Hori 7.1 Introduction 163 7.2 Background 165 7.3 Guest Recognition by Coordination Networks 169 7.4 Fluorinated Coordination Complexes 172 7.5 Cocrystals of Coordination Complexes 179 7.6 Self-Assembly in Solution 181 7.7 Conclusions 182 8 Halogen.À Interactions as Important Contributors to Binding Affinity in Medicinal Chemistry 187 Hans Matter, Marc Nazare, and Stefan Gussregen 8.1 Introduction 187 8.2 General Aspects of Halogen Atoms in Medicinal Chemistry 189 8.3 Fluorine: a Unique Halogen Atom 190 8.4 Interactions of Higher Halogen Atoms 196 8.5 Interactions of Higher Halogen Atoms to Aromatic Rings 204 8.6 Conclusions 226 9 Fuzzy Electron-Density Fragments as Building Blocks in Crystal-Engineering Design 233 Paul G. Mezey 9.1 Introduction 233 9.2 A Brief Review of a Fuzzy Electron-Density Fragmentation Scheme Suitable for Molecular Design 235 9.3 The Low-Density "Glue" Range of Globular Macromolecules, Functional Groups, and the Role of À-Interactions in Fuzzy Fragment Selection 238 9.4 Summary 239 10 Noncovalent Interactions of À-systems in Crystal Structures of Transition-Metal Complexes 243 Goran V. Janjic and Snezana D. Zaric 10.1 Introduction 243 10.2 Interactions with Organic À-Systems 244 10.3 Interactions with À-Systems of Chelate Rings 254 11 Intermolecular C-H * * * À(Chelate) Interactions - Prevalence in the Crystal Structures of Metal 1,1-Dithiolates 275 Julio Zukerman-Schpector and Edward R.T. Tiekink 11.1 Introduction 275 11.2 Methodology and Preliminary Survey 277 11.3 Supramolecular Architectures Based on C-H* * ·À Interactions 280 11.4 Discussion and Conclusions 295 12 Supramolecular Aggregation Patterns and Stereochemical Consequences of Tellurium(Lone Pair)* * ·À(Aryl) Interactions 301 Ionel Haiduc, Edward R.T. Tiekink and Julio Zukerman-Schpector 12.1 Introduction 301 12.2 Methodology 302 12.3 Results 303 12.4 The Influence of Te(Lone Pair)* * ·À(Aryl) Synthons Upon Coordination Geometry 318 12.5 Summary and Conclusions 319 13 Supramolecular Assembly of Silver(I) Complexes with Argentophilic and Silver.Carbon Interactions 323 Thomas C. W. Mak, Liang Zhao and Xiao-Li Zhao 13.1 Introduction 323 13.2 Silver Double/Multiple Salts Containing Ag2C2 326 13.3 Supramolecular Assembly of Silver(I) Double/Triple Salts with Potentially Exo-Bidentate Ligands 332 13.4 Silver(I) Multiple Salts of 1,3-Butadiynediide (C4²-) 337 13.5 Supramolecular Assembly with Silver tert-Butylethynide 338 13.6 Double/Multiple Salts of Silver Arylethynides 342 13.7 Assembly of Silver-Heteroaromatic Ethynide Supramolecular Synthons R-C=C Agn (n = 4, 5) (R = Thienyl, Pyridyl, Pyrazinyl, Pyrimidyl) 346 13.8 Assembly of Silver-Ethynide Supramolecular Synthon Assisted by Silver.Aromatic Interaction 350 13.9 Assembly of Silver-Ethynide Supramolecular Synthon Assisted by Intermolecular Silver.Halogen Interaction 352 13.10 Coordination Networks Constructed of Multinuclear C2@Agn Aggregates and Polyoxometalate Species 353 13.11 Supramolecular Assembly of Large Silver-Ethynide Clusters 355 13.12 Conclusion and Outlook 363 Acknowledgments 363 References 364 Index 367