The Importance of Pi-Interactions in Crystal Engineering: Frontiers in Crystal Engineering

391 Pages·2012·10.501 MB·English

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The Importance of Pi-Interactions
in Crystal Engineering
i
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The Importance of
Pi-Interactions in
Crystal Engineering
Frontiers in Crystal Engineering
Edited by
EDWARD R. T. TIEKINK
Department of Chemistry, The University of Malaya,
Kuala Lumpur, Malaysia
JULIO ZUKERMAN-SCHPECTOR
Department of Chemistry, Federal University of Sa˜o Carlos,
Sa˜o Carlos, Brazil
A John Wiley & Sons, Ltd., Publication
iii
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Thiseditionfirstpublished2012
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LibraryofCongressCataloging-in-PublicationData
TheimportanceofPi-interactionsincrystalengineering:frontiersincrystalengineering/EditedbyEdwardR.T.Tiekink
AndJulioZukerman-Schpector.
p.cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-68827-4(cloth)
1.Molecularcrystals. 2.Supramolecularorganometallicchemistry. 3.Crystalgrowth. I.Tiekink,EdwardR.T.
II.Zukerman-Schpector,Julio.
QD921.I442012
548(cid:2).3–dc23
2011046055
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
PrintISBN:9780470688274
Setin10/12ptTimesbyAptaraInc.,NewDelhi,India.
iv
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Contents
Preface xiii
ListofContributors xv
1 TheCH/π HydrogenBond:ImplicationinCrystalEngineering 1
MotohiroNishio,YojiUmezawa,HirokoSuezawaandSeiTsuboyama
1.1 Introduction 1
1.1.1 EvidenceandtheNatureoftheCH/π HydrogenBond 3
1.1.2 DirectionalityoftheCH/π HydrogenBond 5
1.2 CooperativeEffectoftheCH/π HydrogenBond 7
1.2.1 CooperativeEffectasEvidencedbyHigh-LevelAbInitioMO
Calculations 7
1.2.2 CooperativeEffectasEvidencedbyPeriodicAbInitioMO
Calculations 7
1.2.3 CooperativeEffectasEvidencedbyStabilisationofMaterials
inAromaticNanochannels 10
1.2.4 OpticalResolution 10
1.3 CH/π HydrogenBondsinSupramolecularChemistry 14
1.3.1 CrystalPacking 15
1.3.2 LatticeInclusionTypeClathrates 17
1.3.3 CavityInclusionTypeClathrates 20
1.4 CrystallographicDatabaseAnalyses 25
1.4.1 CH/π HydrogenBondsasEvidencedbyCSDAnalyses 25
1.4.2 SystematicCSDAnalyses 26
1.5 SystematicCSDAnalysesoftheCH/π HydrogenBond 28
1.5.1 MethodandGeneralSurveyofOrganicMolecules 28
1.5.2 OrganometallicCompounds 31
1.6 SummaryandOutlook 31
Acknowledgments 32
References 32
2 NewAspectsofAromaticπ...π andC-H...π Interactionsin
CrystalEngineering 41
RogerBishop
2.1 Introduction 41
2.1.1 PlanarAromaticMolecules 41
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2.1.2 Edge–Face(EF)andOffsetFace–Face(OFF)Interactions 41
2.1.3 CompetitionbetweenEFandOFFInteractions 42
2.1.4 Edge–Edge(EE)Interactions 44
2.2 Three-DimensionalAromaticStructures 44
2.2.1 Aryl...ArylEmbraceInteractions 44
2.2.2 DesignofHeteroaromaticInclusionHosts 45
2.3 Endo,Endo-FacialDimers 46
2.3.1 TheBasicP4AEInteractionMotif 46
2.3.2 DiscreteEndo,Endo-FacialDimers 47
2.3.3 AggregatedEndo,Endo-FacialDimers 47
2.4 MultiplyHalogenatedHeteroaromaticMolecules 49
2.4.1 Theπ-HalogenDimer(PHD)Interaction 49
2.4.2 ThePHDUnitinStaircaseInclusionStructures 49
2.4.3 ThePHDUnitinLayerStructures 51
2.4.4 SwitchfromEndo,Endo-FacialDimertoPHDUnit 54
2.5 ExpansionoftheEndo,Endo-FacialDimer 56
2.5.1 PenannularGuestEnclosure 56
2.5.2 TypesofMolecularPens 56
2.6 (EF) Brick-LikeBuildingBlocks 59
6
2.6.1 PhenylatedHeteroaromaticMolecules 59
2.6.2 PackingoftheBricks 60
2.6.3 DifferentInclusionFamiliesandTheirConvergence 61
2.7 OtherNovelMultipleEdge–FaceAssemblies 64
2.7.1 The(EF) HandclaspInteraction 64
2
2.7.2 FormationofHexamericInclusionCapsules 65
2.7.3 FormationofHexamericHydrateClusters 66
2.8 OtherTypesofAryl–ArylContacts 68
2.8.1 DifferentOFFPackingGeometries 68
2.8.2 Exo,Endo-FacialOFFInteractions 68
2.8.3 Exo,Exo-FacialOFFInteractions 71
2.8.4 SwivelInteractions 71
2.9 Conclusions 75
Acknowledgments 75
References 75
3 CH–π andπ–π InteractionsasContributorstotheGuestBinding
inReversibleInclusionandEncapsulationComplexes 79
PabloBallesterandShannonM.Biros
3.1 Introduction 79
3.1.1 TheoreticalConsiderationsofAromatic–Aromatic(π–π)
InteractionsandCH–π Interactions 81
3.2 ProbingAromatic–Aromatic(π–π)InteractionsandCH–π
InteractionswithSolid-StateStructuresofReversibleInclusionand
EncapsulationComplexes 83
3.2.1 InclusionComplexes 83
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3.2.2 Hydrogen-Bonded,ElectrostaticallyDrivenand
Metal-MediatedMolecularCapsules 94
3.2.3 ApproachingSupramolecularMaterials–Aromatic
Towers 100
3.3 SummaryandOutlook 104
Acknowledgments 105
References 105
4 ARudimentaryMethodforClassificationofπ···π PackingMotifs
forAromaticMolecules 109
LeighLootsandLeonardJ.Barbour
4.1 Introduction 109
4.2 TheoreticalModels 110
4.3 π···π Interactions 111
4.4 StructurePredictionandComparisons 113
4.5 π···π InteractionsinHeteroaromaticMolecules 113
4.6 π···π InteractionsinCocrystals 119
4.7 Summary 123
References 123
5 ConformationalFlexibilityandSelectivityinHost–GuestSystems 125
NikolettaB.Ba´thoriandLuigiR.Nassimbeni
5.1 Introduction 125
5.2 Selectivity 129
5.3 ConcludingRemarks 139
References 140
6 Organicπ-RadicalsintheSolid-State:FromLocalised
toDelocalisedσ-Bonding 143
MarcFourmigue´
6.1 Introduction 143
6.2 Moleculesforπ-RadicalFormation 144
6.2.1 Arenes 144
6.2.2 Two-StageRedoxSystems 145
6.2.3 NeutralOrganicorHeterocyclicπ-RadicalSpecies 147
6.2.4 NoninnocentLigandsandAssociatedComplexes 148
6.3 DimersofRadicalsversusRadicalDimers(Pimers) 149
6.3.1 Localisedσ-Bonding 149
6.3.2 π-RadicalsFormDelocalisedσ-Bonds 150
6.3.3 RadicalDimers:Pimers 151
6.3.4 GeometricFeaturesofDimersandPimersintheSolidState 153
6.4 Solid-StateMagneticandConductingProperties 154
6.4.1 Isolated,WeaklyInteractingπ-Radicals 154
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6.4.2 IsolatedDimersofRadicals 155
6.4.3 UniformStacksofπ-Radicals 155
6.4.4 StacksofPimers,Mixed-ValenceConductors 157
6.5 Conclusions 159
Acknowledgments 159
References 159
7 Arene–PerfluoroareneInteractionsinCoordinationArchitectures 163
AkikoHori
7.1 Introduction 163
7.2 Background 165
7.2.1 CocrystallisationofOrganicMolecules 165
7.2.2 Designof2:1Cocrystal 168
7.3 GuestRecognitionbyCoordinationNetworks 169
7.4 FluorinatedCoordinationComplexes 172
7.4.1 CrystalStructuresofFluorinatedCoordinationComplexes 172
7.4.2 FullyFluorinatedCu(II)Complex 174
7.4.3 PartiallyFluorinatedCu(II)Complex 175
7.5 CocrystalsofCoordinationComplexes 179
7.6 Self-AssemblyinSolution 181
7.7 Conclusions 182
Acknowledgments 183
References 183
8 Halogen...π InteractionsasImportantContributors
toBindingAffinityinMedicinalChemistry 187
HansMatter,MarcNazare´,andStefanGu¨ssregen
8.1 Introduction 187
8.2 GeneralAspectsofHalogenAtomsinMedicinalChemistry 189
8.3 Fluorine:AUniqueHalogenAtom 190
8.3.1 InfluenceofFluorineonLipophilicityandBasicity 190
8.3.2 InfluenceofFluorineonCH...π andπ...π Interactions 191
8.3.3 FluorineinMultipolarInteractionstoElectrophilicResidues 193
8.4 InteractionsofHigherHalogenAtoms 196
8.4.1 HalogenBonding 196
8.4.2 OrthogonalMultipolarInteractionstoπ-Systems 200
8.5 InteractionsofHigherHalogenAtomstoAromaticRings 204
8.5.1 LiteratureInvestigationsonHalogen···AromaticInteractions 204
8.5.2 Structure–ActivityStudiesofHalogen···π Interactions 209
8.5.3 ExploringtheHalogen···π InteractionbyAb-Initio
Calculations 216
8.5.4 SelectedExamplesfromDrug-DiscoveryProjects 218
8.6 Conclusions 226
References 227
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Contents ix
9 FuzzyElectron-DensityFragmentsasBuildingBlocksin
Crystal-EngineeringDesign 233
PaulG.Mezey
9.1 Introduction 233
9.2 ABriefReviewofaFuzzyElectron-DensityFragmentation
SchemeSuitableforMolecularDesign 235
9.3 TheLow-Density“Glue”RangeofGlobularMacromolecules,
FunctionalGroups,andtheRoleofπ-Interactions
inFuzzyFragmentSelection 238
9.4 Summary 239
Acknowledgment 239
References 239
10 NoncovalentInteractionsofπ-SystemsinCrystalStructures
ofTransition-MetalComplexes 243
GoranV.Janjic´ andSnezˇanaD.Zaric´
10.1 Introduction 243
10.2 InteractionswithOrganicπ-Systems 244
10.2.1 Cation...π InteractionwithTransition-MetalComplexes 244
10.2.2 MLXH...π Interactions 246
10.3 Interactionswithπ-SystemsofChelateRings 254
10.3.1 CH...π Interactionswithπ-SystemsofChelateRings 255
10.3.2 StackingInteractionsInvolvingπ-SystemsofChelateRings 264
References 273
11 IntermolecularC–H···π(Chelate)Interactions–Prevalencein
theCrystalStructuresofMetal1,1-Dithiolates 275
JulioZukerman-SchpectorandEdwardR.T.Tiekink
11.1 Introduction 275
11.2 MethodologyandPreliminarySurvey 277
11.3 SupramolecularArchitecturesBasedonC–H···π Interactions 280
11.3.1 Xanthates 280
11.3.2 Dithiophosphates,Dithiophosphonatesand
Dithiophosphinates 281
11.3.3 Dithiocarbamates 286
11.4 DiscussionandConclusions 295
Acknowledgments 296
References 296
12 SupramolecularAggregationPatternsandStereochemicalConsequences
ofTellurium(LonePair)···π(Aryl)Interactions 301
IonelHaiduc,EdwardR.T.TiekinkandJulioZukerman-Schpector
12.1 Introduction 301
12.2 Methodology 302
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12.3 Results 303
12.3.1 Te(LonePair)···π(Aryl)SynthonsinTellurium(IV)
Structures 303
12.3.2 Te(LonePair)···π(Aryl)SynthonsinTellurium(II)
Structures 306
12.3.3 Te(LonePair)···π(Aryl)SynthonsinChargedTellurium
Species 312
12.4 TheInfluenceofTe(LonePair)···π(Aryl)Synthonsupon
CoordinationGeometry 318
12.5 SummaryandConclusions 319
Acknowledgments 320
References 320
13 SupramolecularAssemblyofSilver(I)ComplexeswithArgentophilic
andSilver...CarbonInteractions 323
ThomasC.W.Mak,LiangZhaoandXiao-LiZhao
13.1 Introduction 323
13.2 SilverDouble/MultipleSaltsContainingAg C 326
2 2
13.2.1 DoubleSalts 326
13.2.2 TripleSalts 326
13.2.3 TheFirstQuadrupleSaltofSilver 327
13.2.4 AssemblyofSilver(I)AggregatesundertheInfluenceof
CrownEthers 328
13.2.5 FormationofSilver(I,II)ComplexesInducedbyTetraaza
Macrocycles 328
13.2.6 ConstructionofHigh-NuclearitySilver(I)Complexes
InducedbyQuaternaryAmmoniumCations 330
13.2.7 AssemblyofNeutralInfiniteSilver(I)ColumnsandChains
InducedbyBetaine 330
13.2.8 DisruptionofPolyhedralC @Ag CageInducedby
2 n
AdditiveLigands 331
13.3 SupramolecularAssemblyofSilver(I)Double/TripleSaltswith
PotentiallyExo-BidentateLigands 332
13.3.1 DiscreteMolecules 332
13.3.2 LinearPolymericStructures 334
13.3.3 Two-DimensionalStructures 334
13.3.4 Three-DimensionalStructures 335
13.4 Silver(I)MultipleSaltsof1,3-Butadiynediide(C 2−) 337
4
13.5 SupramolecularAssemblywithSilvertert-Butylethynide 338
13.5.1 InfluenceofAncillaryNitrileLigands 340
13.5.2 InfluenceofSpectatorQuaternaryAmmoniumCations 342
13.6 Double/MultipleSaltsofSilverArylethynides 342
13.6.1 EffectofSubstituentsonthePhenylRing 342
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13.6.2 AssemblywithIsomericPhenylenediethynide
SupramolecularSynthons 344
13.6.3 StructuralCorrelation 346
13.7 AssemblyofSilver–HeteroaromaticEthynideSupramolecular
SynthonsR C C⊃Ag (n=4,5)(R=Thienyl,Pyridyl,Pyrazinyl,
n
Pyrimidyl) 346
13.8 AssemblyofSilver–EthynideSupramolecularSynthonAssistedby
Silver...AromaticInteraction 350
13.9 AssemblyofSilver–EthynideSupramolecularSynthonAssistedby
IntermolecularSilver...HalogenInteraction 352
13.10 CoordinationNetworksConstructedofMultinuclearC @Ag
2 n
AggregatesandPolyoxometalateSpecies 353
13.11 SupramolecularAssemblyofLargeSilver–EthynideClusters 355
13.11.1 ClustersTemplatedbyEncapsulatedSmallInorganic
Anions 356
13.11.2 ClustersConstructedofSilverEthynideand
PolyoxometalateComponents 358
13.12 ConclusionandOutlook 363
Acknowledgments 363
References 364
Index 367