Inorganic Structural Chemistry, Second Edition

278 Pages·2006·11.855 MB·English

by  Dr. rer. nat. Ulrich Muller(auth.)

Inorganic
Structural Chemistry
Second Edition
InorganicStructuralChemistry,SecondEdition UlrichMu¨ller
© 2006 J ohn Wiley & Sons , L td. ISBN: 978-0-470-01864-4
InorganicChemistry
AWileySeriesofAdvancedTextbooks
EditorialBoard
DerekWoollins,UniversityofSt.Andrews,UK
BobCrabtree,YaleUniversity,USA
DavidAtwood,UniversityofKentucky,USA
GerdMeyer,UniversityofCologne,Germany
PreviouslyPublishedBooksInthisSeries
LanthanideandActinideChemistry
Author:S.A.Cotton
MassSpectrometryofInorganicandOrganometallic
Compounds:Tools–Techniques–Tips
Authors:W.Henderson&J.J.Mclndoe
MainGroupChemistry,SecondEdition
Author:A.G.Massey
SynthesisofOrganometallicCompounds:APracticalGuide
Editedby:S.Komiya
ChemicalBonds:ADialog
Author:J.K.Burdett
MolecularChemistryoftheTransitionElements:AnIntroductoryCourse
Authors:F.Mathey&A.Sevin
StereochemistryofCoordinationCompounds
Author:A.VonZelewsky
BioinorganicChemistry:InorganicElementsintheChemistryofLife–AnIntroductionandGuide
Author:W.Kaim
UlrichMu¨ller
Born in 1940 in Bogota´, Colombia. School attendance in Bogota´, then in Elizabeth, New Jersey, and fi-
nally in Fellbach, Germany. Studied chemistry at the Technische Hochschule in Stuttgart, Germany, ob-
taining the degree of Diplom-Chemiker in 1963. Work on the doctoral thesis in inorganic chemistry was
performed in Stuttgart and at Purdue University in West Lafayette, Indiana, in the research groups of K.
DehnickeandK.S. Vorres, respectively.The doctor’sdegreein naturalsciences(Dr.rer.nat.)was awarded
by the Technische Hochschule Stuttgart in 1966. Subsequent post-doctoral work in crystallography and
crystal structure determinations was performed in the research group of H. Ba¨rnighausen at the Univer-
sita¨tKarlsruhe,Germany.Appointedin1972asprofessorofinorganicchemistryatthePhilipps-Universita¨t
Marburg, Germany, then from 1992 to 1999 at the Universita¨t Kassel, Germany, and since 1999 again in
Marburg.HelpedinstallingagraduateschoolofchemistryasvisitingprofessorattheUniversidaddeCosta
Rica from 1975 to 1977. Courses in spectroscopic methods were repeatedly given at differentuniversities
inCosta Rica, BrazilandChile.Mainareasofscientific interest:syntheticinorganicchemistry,crystallog-
raphyandcrystalstructuresystematics,crystallographicgrouptheory.Co-authorofChemie,atextbookfor
beginners,Schwingungsspektroskopie,a textbookaboutthe applicationof vibrationalspectroscopy,and of
SchwingungsfrequenzenI and II (tablesof characteristicmolecularvibrationalfrequencies);co-authorand
co-editorofInternationalTablesforCrystallography,Vol.A1.
Inorganic
Structural Chemistry
Second Edition
Ulrich Mu¨ller
Philipps-Universita¨t Marburg, Germany
Copyright c 2006 JohnWiley&SonsLtd,TheAtrium,SouthernGate,Chichester,
(cid:0) WestSussexPO198SQ,England
Telephone( 44)1243779777
(cid:0)
Email(forordersandcustomerserviceenquiries):[email protected]
VisitourHomePageonwww.wiley.com
Germanversion
AnorganischeStrukturchemie
Firstedition1991
Secondedition1992
Thirdedition1996
Fourthedition2004
Fifthedition2006
c B.G.TeubnerWiesbaden1991–2006
T(cid:0)heauthorwasawardedthePrizeforChemicalLiteratureforthisbookbytheVerbandderChemischenIndustrie(GermanFederationofChemical
Industries)in1992
AllRightsReserved.Nopartofthispublicationmaybereproduced,storedinaretrievalsystemortransmittedinanyformorbyanymeans,electronic,
mechanical,photocopying,recording,scanningorotherwise,exceptunderthetermsoftheCopyright,DesignsandPatentsAct1988orunderthetermsof
alicenceissuedbytheCopyrightLicensingAgencyLtd,90TottenhamCourtRoad,LondonW1T4LP,UK,withoutthepermissioninwritingofthe
Publisher.RequeststothePublishershouldbeaddressedtothePermissionsDepartment,JohnWiley&SonsLtd,TheAtrium,SouthernGate,Chichester,
WestSussexPO198SQ,England,[email protected],orfaxedto( 44)1243770620.
(cid:0)
Designationsusedbycompaniestodistinguishtheirproductsareoftenclaimedastrademarks.Allbrandnamesandproductnamesusedinthisbookare
tradenames,servicemarks,trademarksorregisteredtrademarksoftheirrespectiveowners.ThePublisherisnotassociatedwithanyproductorvendor
mentionedinthisbook.
Thispublicationisdesignedtoprovideaccurateandauthoritativeinformationinregardtothesubjectmattercovered.Itissoldontheunderstandingthat
thePublisherisnotengagedinrenderingprofessionalservices.Ifprofessionaladviceorotherexpertassistanceisrequired,theservicesofacompetent
professionalshouldbesought.
Thepublisherandtheauthormakenorepresentationsorwarrantieswithrepsecttotheaccuracyofcompletenessofthecontentofthisworkand
specificallydisclaimallwarranties,includingwithoutlimitationanyimpliedwarrantiesoffitnessforaparticularpurpose.Thisworkissoldwiththe
understandingthatthepublisherisnotengagedinrenderingprofessionalservices.Theadviceandstrategiescontainedhereinmaynotbesuitablefor
everysituation.Inviewofongoingresearch,equipmentmodifications,changesingovermentalregulations,andtheconstantflowofinformationrelating
totheuseofexperimentalreagents,equipment,anddevices,thereaderisurgedtoreviewandevaluatetheinformationprovidedinthepackageinsertor
instructionsforeachchemical,pieceofequipment,reagent,ordevicefor,amongotherthings,anychangesintheinstructionsorindicationofusageand
foraddedwarningsandprecautions.ThefactthatanorganizationorWebsiteisreferredtointhisworkasacitationand/orapotentialsourceoffurther
informationdoesnotmeanthattheauthororthepublisherendorsestheinformationtheorganizationorWebsitemayprovideorrecommendationsitmay
make.Further,readersshouldbeawarethatInternetWebsiteslistedinthisworkmayhavechangedordisappearedbetweenwhenthisworkwaswritten
andwhenitisread.Nowarrantymaybecreatedorextendedbyanypromotionalstatementsforthiswork.Neitherthepublishernortheauthorshallbe
liableforanydamagesarisinghereform.
OtherWileyEditorialOffices
JohnWiley&SonsInc.,111RiverStreet,Hoboken,NJ07030,USA
Jossey-Bass,989MarketStreet,SanFrancisco,CA94103-1741,USA
Wiley-VCHVerlagGmbH,Boschstr.12,D-69469Weinheim,Germany
JohnWiley&SonsAustraliaLtd,42McDougallStreet,Milton,Queensland4064,Australia
JohnWiley&Sons(Asia)PteLtd,2ClementiLoop#02-01,JinXingDistripark,Singapore129809
JohnWiley&SonsCanadaLtd,6045FreemontBlvd,Mississauga,ONT,L5R4J3,Canada
Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappears
inprintmaynotbeavailableinelectronicbooks.
BritishLibraryCataloguinginPublicationData
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
ISBN-13:978-0-470-01864-4(HBK) 978-0-470-01865-1(PBK)
ISBN-10:0-470-01864-X(HBK) 0-470-018650-8(PBK)
ProducedfromLaTeXfilessuppliedbytheauthor
ManyfiguresweredrawnwiththeprogramsATOMSbyE.DowtyandDIAMONDbyK.Brandenburg
PrintedandboundinGreatBritainbyAntonyRoweLtd,Chippenham,England
Thisbookisprintedonacid-freepaperresponsiblymanufacturedfromsustainableforestry
inwhichatleasttwotreesareplantedforeachoneusedforpaperproduction.
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 DescriptionofChemicalStructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1 CoordinationNumbersandCoordinationPolyhedra . . . . . . . . . . . . . . . . . . . . . . 3
2.2 DescriptionofCrystalStructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3 AtomicCoordinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.4 Isotypism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.5 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3 Symmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.1 SymmetryOperationsandSymmetryElements . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2 PointGroups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.3 SpaceGroupsandSpace-GroupTypes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.4 Positions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.5 CrystalClassesandCrystalSystems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
3.6 AperiodicCrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.7 DisorderedCrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.8 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4 PolymorphismandPhaseTransitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.1 ThermodynamicStability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.2 KineticStability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
4.3 Polymorphism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
4.4 PhaseTransitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
4.5 PhaseDiagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.6 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
5 ChemicalBondingandLatticeEnergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.1 ChemicalBondingandStructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.2 LatticeEnergy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
6 TheEffectiveSizeofAtoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
6.1 VanderWaalsRadii. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6.2 AtomicRadiiinMetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6.3 CovalentRadii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
6.4 IonicRadii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6.5 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
viii
7 IonicCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
7.1 RadiusRatios . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
7.2 TernaryIonicCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
7.3 CompoundswithComplexIons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
7.4 TheRulesofPaulingandBaur . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
7.5 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
8 MolecularStructuresI:CompoundsofMainGroupElements . . . . . . . . . . . . . . . . . 62
8.1 ValenceShellElectron-PairRepulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
8.2 StructureswithFiveValenceElectronPairs . . . . . . . . . . . . . . . . . . . . . . . . . . 71
8.3 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
9 MolecularStructuresII:CompoundsofTransitionMetals . . . . . . . . . . . . . . . . . . . 73
9.1 LigandFieldTheory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
9.2 LigandFieldStabilizationEnergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
9.3 CoordinationPolyhedraforTransitionMetals . . . . . . . . . . . . . . . . . . . . . . . . . 80
9.4 Isomerism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
9.5 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
10 MolecularOrbitalTheoryandChemicalBondinginSolids . . . . . . . . . . . . . . . . . . . 85
10.1 MolecularOrbitals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
10.2 Hybridization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
10.3 TheElectronLocalizationFunction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
10.4 BandTheory.TheLinearChainofHydrogenAtoms . . . . . . . . . . . . . . . . . . . . . 90
10.5 ThePeierlsDistortion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
10.6 CrystalOrbitalOverlapPopulation(COOP) . . . . . . . . . . . . . . . . . . . . . . . . . . 96
10.7 BondsinTwoandThreeDimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
10.8 BondinginMetals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
10.9 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
11 TheElementStructuresoftheNonmetals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
11.1 HydrogenandtheHalogens. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
11.2 Chalcogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
11.3 ElementsoftheFifthMainGroup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
11.4 ElementsoftheFifthandSixthMainGroupsunderPressure . . . . . . . . . . . . . . . . . 111
11.5 Carbon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
11.6 Boron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
12 Diamond-likeStructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
12.1 CubicandHexagonalDiamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
12.2 BinaryDiamond-likeCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
12.3 Diamond-likeCompoundsunderPressure . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
12.4 PolynaryDiamond-likeCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
12.5 WidenedDiamondLattices.SiO Structures . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2
12.6 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
ix
13 PolyanionicandPolycationicCompounds.ZintlPhases . . . . . . . . . . . . . . . . . . . . . 128
13.1 TheGeneralized8 NRule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
(cid:0)
13.2 PolyanionicCompounds,ZintlPhases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
13.3 PolycationicCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
13.4 ClusterCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
13.5 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
14 PackingsofSpheres.MetalStructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
14.1 Closest-packingsofSpheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
14.2 Body-centeredCubicPackingofSpheres . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
14.3 OtherMetalStructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
14.4 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
15 TheSphere-packingPrincipleforCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . 157
15.1 OrderedandDisorderedAlloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
15.2 CompoundswithClose-packedAtoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
15.3 StructuresDerivedofBody-centeredCubicPacking(CsClType) . . . . . . . . . . . . . . . 160
15.4 Hume–RotheryPhases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
15.5 LavesPhases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
15.6 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
16 LinkedPolyhedra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
16.1 Vertex-sharingOctahedra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
16.2 Edge-sharingOctahedra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
16.3 Face-sharingOctahedra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
16.4 OctahedraSharingVerticesandEdges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
16.5 OctahedraSharingEdgesandFaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
16.6 LinkedTrigonalPrisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
16.7 Vertex-sharingTetrahedra.Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
16.8 Edge-sharingTetrahedra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
16.9 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
17 PackingsofSphereswithOccupiedInterstices . . . . . . . . . . . . . . . . . . . . . . . . . . 190
17.1 TheIntersticesinClosest-packingsofSpheres . . . . . . . . . . . . . . . . . . . . . . . . . 190
17.2 InterstitialCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
17.3 StructureTypeswithOccupiedOctahedralIntersticesinClosest-packingsofSpheres . . . . 195
17.4 Perovskites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
17.5 OccupationofTetrahedralIntersticesinClosest-packingsofSpheres . . . . . . . . . . . . . 206
17.6 Spinels. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
17.7 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
18 SymmetryastheOrganizingPrincipleforCrystalStructures . . . . . . . . . . . . . . . . . 212
18.1 CrystallographicGroup–SubgroupRelations . . . . . . . . . . . . . . . . . . . . . . . . . . 212
18.2 TheSymmetryPrincipleinCrystalChemistry . . . . . . . . . . . . . . . . . . . . . . . . . 214
18.3 StructuralRelationshipsbyGroup–SubgroupRelations . . . . . . . . . . . . . . . . . . . . 215
18.4 SymmetryRelationsatPhaseTransitions.TwinnedCrystals . . . . . . . . . . . . . . . . . 221
18.5 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
x
19 PhysicalPropertiesofSolids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
19.1 MechanicalProperties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
19.2 PiezoelectricandFerroelectricProperties . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
19.3 MagneticProperties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
20 Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
21 PitfallsandLinguisticAberrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
AnswerstotheProblems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
Preface
Giventhe increasingquantityof knowledgein allareasof science,the impartingofthis
knowledgemustnecessarilyconcentrateongeneralprinciplesandlawswhiledetailsmust
be restricted to important examples. A textbook should be reasonably small, but essen-
tial aspectsof the subjectmay notbe neglected,traditionalfoundationsmustbe consid-
ered,andmoderndevelopmentsshouldbeincluded.Thisintroductorytextisanattemptto
presentinorganicstructuralchemistryinthisway.Compromisescannotbeavoided;some
sections maybe shorter,while othersmaybe longerthansome expertsin this area may
deemappropriate.
Chemistspredominantlythinkin illustrativemodels:theylike to “see” structuresand
bonds.Modernbondtheoryhaswonitsplaceinchemistry,andisgivenproperattention
in Chapter 10. However, with its extensive calculations it correspondsmore to the way
ofthinkingofphysicists.Furthermore,albeitthecomputationalresultshavebecomequite
reliable,itoftenremainsdifficulttounderstandstructuraldetails.Foreverydayuse,simple
modelssuchasthosetreatedinChapters8,9and13areusuallymoreusefultoachemist:
“Thepeasantwhowantstoharvestin hislifetimecannotwaitfortheabinitiotheoryof
weather.Chemists,likepeasants,believeinrules,butcunninglymanagetointerpretthem
asoccasiondemands”(H.G. VON SCHNERING[112]).
This book is mainly addressed to advanced students of chemistry. Basic chemical
knowledge concerning atomic structure, chemical bond theory and structural aspects is
required.Parts of the text are based on a course on inorganiccrystalchemistry by Prof.
H. Ba¨rnighausen at the University of Karlsruhe. I am grateful to him for permission to
use the manuscriptof hiscourse,for numeroussuggestions,and for hisencouragement.
FordiscussionsandsuggestionsIalsothankProf.D.Babel,Prof.K.Dehnicke,Prof.C.
Elschenbroich,Prof.D.ReinenandProf.G.Weiser.IthankProf.T.Fa¨sslerforsupplying
figuresoftheelectronlocalizationfunctionandforreviewingthecorrespondingsection.
I thank Prof. S. Schlecht for providing figures and for reviewing the chapter on nano-
structures.IthankMs.J.GregoryandMr.P.C.Westonforreviewingandcorrectingthe
Englishversionofthemanuscript.
In thissecondedition the texthasbeenrevised andnew scientific findingshavebeen
takenintoconsideration.Forexample,manyrecentlydiscoveredmodificationsoftheele-
mentshavebeenincluded,mostofwhichoccurathighpressures.Thetreatmentofsym-
metryhasbeenshiftedtothethirdchapterandtheaspectofsymmetryisgivenmoreatten-
tioninthefollowingchapters.Newsectionsdealwithquasicrystalsandothernotstrictly
crystallinesolids,withphasetransitionsandwiththeelectronlocalizationfunction.There
isanewchapteronnanostructures.Nearlyallfigureshavebeenredrawn.
UlrichMu¨ller Marburg,Germany,April2006