Edward R. T. Tiekink is the author of The Importance of Pi-Interactions in Crystal Engineering: Frontiers in Crystal Engineering, 2nd Edition, published by Wiley. Julio Zukerman-Schpector is the author of The Importance of Pi-Interactions in Crystal Engineering: Frontiers in Crystal Engineering, 2nd Edition, published by Wiley.

• Preface xiii List of Contributors xv1 The CH/π Hydrogen Bond: Implication in Crystal Engineering 1Motohiro Nishio, Yoji Umezawa, Hiroko Suezawa and Sei Tsuboyama1.1 Introduction 11.2 Cooperative Effect of the CH/π Hydrogen Bond 71.3 CH/π Hydrogen Bonds in Supramolecular Chemistry 141.4 Crystallographic Database Analyses 251.5 Systematic CSD Analyses of the CH/π Hydrogen Bond 281.6 Summary and Outlook 312 New Aspects of Aromatic π. . . π and C-H . . . π Interactions in Crystal Engineering 41Roger Bishop2.1 Introduction 412.2 Three-Dimensional Aromatic Structures 442.3 Endo,Endo-Facial Dimers 462.4 Multiply Halogenated Heteroaromatic Molecules 492.5 Expansion of the Endo,Endo-Facial Dimer 562.6 (EF)6 Brick-Like Building Blocks 592.7 Other Novel Multiple Edge–Face Assemblies 642.8 Other Types of Aryl–Aryl Contacts 682.9 Conclusions 753 CH. . .π and π. . .π Interactions as Contributors to the Guest Binding in Reversible Inclusion and Encapsulation Complexes 79Dr. Pablo Ballester and Dr. Shannon M. Biros3.1 Introduction 793.2 Probing Aromatic–Aromatic (π–π) Interactions and CH–π Interactions with Solid-State Structures of Reversible Inclusion and Encapsulation Complexes 833.2.1 Inclusion Complexes 833.3 Summary and Outlook 1044 A Rudimentary Method for Classification of π···π Packing Motifs for Aromatic Molecules 109Leigh Loots and Leonard J. Barbour4.1 Introduction 1094.2 Theoretical Models 1104.3 π···π Interactions 1114.4 Structure Prediction and Comparisons 1134.5 π···π Interactions in Heteroaromatic Molecules 1134.6 π···π Interactions in Cocrystals 1194.7 Summary 1235 Conformational Flexibility and Selectivity in Host–Guest Systems 125Nikoletta B. Bathori and Luigi R. Nassimbeni5.1 Introduction 1255.2 Selectivity 1295.3 Concluding Remarks 1396 Organic π-Radicals in the Solid-State: from Localised to Delocalised σ-Bonding 143Marc Fourmigue6.1 Introduction 1436.2 Molecules for π-Radical Formation 1446.3 Dimers of Radicals versus Radical Dimers (Pimers) 1496.4 Solid-State Magnetic and Conducting Properties 1546.5 Conclusions 1597 Arene–Perfluoroarene Interactions in Coordination Architectures 163Akiko Hori7.1 Introduction 1637.2 Background 1657.3 Guest Recognition by Coordination Networks 1697.4 Fluorinated Coordination Complexes 1727.5 Cocrystals of Coordination Complexes 1797.6 Self-Assembly in Solution 1817.7 Conclusions 1828 Halogen. . .π Interactions as Important Contributors to Binding Affinity in Medicinal Chemistry 187Hans Matter, Marc Nazare, and Stefan Gussregen8.1 Introduction 1878.2 General Aspects of Halogen Atoms in Medicinal Chemistry 1898.3 Fluorine: a Unique Halogen Atom 1908.4 Interactions of Higher Halogen Atoms 1968.5 Interactions of Higher Halogen Atoms to Aromatic Rings 2048.6 Conclusions 2269 Fuzzy Electron-Density Fragments as Building Blocks in Crystal-Engineering Design 233Paul G. Mezey9.1 Introduction 2339.2 A Brief Review of a Fuzzy Electron-Density Fragmentation Scheme Suitable for Molecular Design 2359.3 The Low-Density "Glue" Range of Globular Macromolecules, Functional Groups, and the Role of π-Interactions in Fuzzy Fragment Selection 2389.4 Summary 23910 Noncovalent Interactions of π-systems in Crystal Structures of Transition-Metal Complexes 243Goran V. Janjic and Snezana D. Zaric10.1 Introduction 24310.2 Interactions with Organic π-Systems 24410.3 Interactions with π-Systems of Chelate Rings 25411 Intermolecular C–H · · · π(Chelate) Interactions – Prevalence in the Crystal Structures of Metal 1,1-Dithiolates 275Julio Zukerman-Schpector and Edward R.T. Tiekink11.1 Introduction 27511.2 Methodology and Preliminary Survey 27711.3 Supramolecular Architectures Based on C–H· · ·π Interactions 28011.4 Discussion and Conclusions 29512 Supramolecular Aggregation Patterns and Stereochemical Consequences of Tellurium(Lone Pair)· · ·π(Aryl) Interactions 301Ionel Haiduc, Edward R.T. Tiekink and Julio Zukerman-Schpector12.1 Introduction 30112.2 Methodology 30212.3 Results 30312.4 The Influence of Te(Lone Pair)· · ·π(Aryl) Synthons Upon Coordination Geometry 31812.5 Summary and Conclusions 31913 Supramolecular Assembly of Silver(I) Complexes with Argentophilic and Silver. . .Carbon Interactions 323Thomas C. W. Mak, Liang Zhao and Xiao-Li Zhao13.1 Introduction 32313.2 Silver Double/Multiple Salts Containing Ag2C2 32613.3 Supramolecular Assembly of Silver(I) Double/Triple Salts with Potentially Exo-Bidentate Ligands 33213.4 Silver(I) Multiple Salts of 1,3-Butadiynediide (C42−) 33713.5 Supramolecular Assembly with Silver tert-Butylethynide 33813.6 Double/Multiple Salts of Silver Arylethynides 34213.7 Assembly of Silver–Heteroaromatic Ethynide Supramolecular Synthons R-C=C Agn (n = 4, 5) (R = Thienyl, Pyridyl, Pyrazinyl, Pyrimidyl) 34613.8 Assembly of Silver–Ethynide Supramolecular Synthon Assisted by Silver. . .Aromatic Interaction 35013.9 Assembly of Silver–Ethynide Supramolecular Synthon Assisted by Intermolecular Silver. . .Halogen Interaction 35213.10 Coordination Networks Constructed of Multinuclear C2@Agn Aggregates and Polyoxometalate Species 35313.11 Supramolecular Assembly of Large Silver–Ethynide Clusters 35513.12 Conclusion and Outlook 363Acknowledgments 363References 364Index 367

Edward R. T. Tiekink is the author of The Importance of Pi-Interactions in Crystal Engineering: Frontiers in Crystal Engineering, 2nd Edition, published by Wiley. Julio Zukerman-Schpector is the author of The Importance of Pi-Interactions in Crystal Engineering: Frontiers in Crystal Engineering, 2nd Edition, published by Wiley.

• Preface xiii List of Contributors xv1 The CH/π Hydrogen Bond: Implication in Crystal Engineering 1Motohiro Nishio, Yoji Umezawa, Hiroko Suezawa and Sei Tsuboyama1.1 Introduction 11.2 Cooperative Effect of the CH/π Hydrogen Bond 71.3 CH/π Hydrogen Bonds in Supramolecular Chemistry 141.4 Crystallographic Database Analyses 251.5 Systematic CSD Analyses of the CH/π Hydrogen Bond 281.6 Summary and Outlook 312 New Aspects of Aromatic π. . . π and C-H . . . π Interactions in Crystal Engineering 41Roger Bishop2.1 Introduction 412.2 Three-Dimensional Aromatic Structures 442.3 Endo,Endo-Facial Dimers 462.4 Multiply Halogenated Heteroaromatic Molecules 492.5 Expansion of the Endo,Endo-Facial Dimer 562.6 (EF)6 Brick-Like Building Blocks 592.7 Other Novel Multiple Edge–Face Assemblies 642.8 Other Types of Aryl–Aryl Contacts 682.9 Conclusions 753 CH. . .π and π. . .π Interactions as Contributors to the Guest Binding in Reversible Inclusion and Encapsulation Complexes 79Dr. Pablo Ballester and Dr. Shannon M. Biros3.1 Introduction 793.2 Probing Aromatic–Aromatic (π–π) Interactions and CH–π Interactions with Solid-State Structures of Reversible Inclusion and Encapsulation Complexes 833.2.1 Inclusion Complexes 833.3 Summary and Outlook 1044 A Rudimentary Method for Classification of π···π Packing Motifs for Aromatic Molecules 109Leigh Loots and Leonard J. Barbour4.1 Introduction 1094.2 Theoretical Models 1104.3 π···π Interactions 1114.4 Structure Prediction and Comparisons 1134.5 π···π Interactions in Heteroaromatic Molecules 1134.6 π···π Interactions in Cocrystals 1194.7 Summary 1235 Conformational Flexibility and Selectivity in Host–Guest Systems 125Nikoletta B. Bathori and Luigi R. Nassimbeni5.1 Introduction 1255.2 Selectivity 1295.3 Concluding Remarks 1396 Organic π-Radicals in the Solid-State: from Localised to Delocalised σ-Bonding 143Marc Fourmigue6.1 Introduction 1436.2 Molecules for π-Radical Formation 1446.3 Dimers of Radicals versus Radical Dimers (Pimers) 1496.4 Solid-State Magnetic and Conducting Properties 1546.5 Conclusions 1597 Arene–Perfluoroarene Interactions in Coordination Architectures 163Akiko Hori7.1 Introduction 1637.2 Background 1657.3 Guest Recognition by Coordination Networks 1697.4 Fluorinated Coordination Complexes 1727.5 Cocrystals of Coordination Complexes 1797.6 Self-Assembly in Solution 1817.7 Conclusions 1828 Halogen. . .π Interactions as Important Contributors to Binding Affinity in Medicinal Chemistry 187Hans Matter, Marc Nazare, and Stefan Gussregen8.1 Introduction 1878.2 General Aspects of Halogen Atoms in Medicinal Chemistry 1898.3 Fluorine: a Unique Halogen Atom 1908.4 Interactions of Higher Halogen Atoms 1968.5 Interactions of Higher Halogen Atoms to Aromatic Rings 2048.6 Conclusions 2269 Fuzzy Electron-Density Fragments as Building Blocks in Crystal-Engineering Design 233Paul G. Mezey9.1 Introduction 2339.2 A Brief Review of a Fuzzy Electron-Density Fragmentation Scheme Suitable for Molecular Design 2359.3 The Low-Density "Glue" Range of Globular Macromolecules, Functional Groups, and the Role of π-Interactions in Fuzzy Fragment Selection 2389.4 Summary 23910 Noncovalent Interactions of π-systems in Crystal Structures of Transition-Metal Complexes 243Goran V. Janjic and Snezana D. Zaric10.1 Introduction 24310.2 Interactions with Organic π-Systems 24410.3 Interactions with π-Systems of Chelate Rings 25411 Intermolecular C–H · · · π(Chelate) Interactions – Prevalence in the Crystal Structures of Metal 1,1-Dithiolates 275Julio Zukerman-Schpector and Edward R.T. Tiekink11.1 Introduction 27511.2 Methodology and Preliminary Survey 27711.3 Supramolecular Architectures Based on C–H· · ·π Interactions 28011.4 Discussion and Conclusions 29512 Supramolecular Aggregation Patterns and Stereochemical Consequences of Tellurium(Lone Pair)· · ·π(Aryl) Interactions 301Ionel Haiduc, Edward R.T. Tiekink and Julio Zukerman-Schpector12.1 Introduction 30112.2 Methodology 30212.3 Results 30312.4 The Influence of Te(Lone Pair)· · ·π(Aryl) Synthons Upon Coordination Geometry 31812.5 Summary and Conclusions 31913 Supramolecular Assembly of Silver(I) Complexes with Argentophilic and Silver. . .Carbon Interactions 323Thomas C. W. Mak, Liang Zhao and Xiao-Li Zhao13.1 Introduction 32313.2 Silver Double/Multiple Salts Containing Ag2C2 32613.3 Supramolecular Assembly of Silver(I) Double/Triple Salts with Potentially Exo-Bidentate Ligands 33213.4 Silver(I) Multiple Salts of 1,3-Butadiynediide (C42−) 33713.5 Supramolecular Assembly with Silver tert-Butylethynide 33813.6 Double/Multiple Salts of Silver Arylethynides 34213.7 Assembly of Silver–Heteroaromatic Ethynide Supramolecular Synthons R-C=C Agn (n = 4, 5) (R = Thienyl, Pyridyl, Pyrazinyl, Pyrimidyl) 34613.8 Assembly of Silver–Ethynide Supramolecular Synthon Assisted by Silver. . .Aromatic Interaction 35013.9 Assembly of Silver–Ethynide Supramolecular Synthon Assisted by Intermolecular Silver. . .Halogen Interaction 35213.10 Coordination Networks Constructed of Multinuclear C2@Agn Aggregates and Polyoxometalate Species 35313.11 Supramolecular Assembly of Large Silver–Ethynide Clusters 35513.12 Conclusion and Outlook 363Acknowledgments 363References 364Index 367