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Structural InorganicChemistry

A . F . W E L L SFIFTH EDITION

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CLARENDON PRESS OXFORD

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ABBREVIATIONS xx ixP A R T I1. INTRODUCTION 3Th e im po rta nc e of the solid State 3

Struc tural formulae of inorganic Com pounds 11Geometrical and topological l imitations on the s tructures ofmo lecules and crystals 20The com plete s tructura l chem istry of an eleme nt or Com pound 23Str uc tur e in the solid State 24Stru ctura l changes on melting 24Str uc tur al changes in th e liquid State 25Struc tural changes on boil ing or Sublimation 26A Classification of cry stals 27Crystals consis t ing of inf inite 3-dimensional com plexes 29Layer s truc ture s 30Chain s truc tures 33Crystals con taining f inite com plexes 36Relat ions betwe en crys ta l s t ructures 36

2. SYMMETRY 38Sym metry e lements 38Rep eating pa tter ns , unit cells, and lat t ices 38On e- and two-dim ensional lat t ice s; poin t groups 39Three-dim ensional lat t ices ; space groups 42Point grou ps; crystal Systems 47Equivalent posit ions in space group s 50Examples of ' anom alou s ' sym me try 5 1Isomerism 52Struc tural ( topolo gical) isomerism 54Geo me trical isomerism 56Optical activity 57

3. POLYHEDRA AND NETS 63Introduct ion 63The basic Systems of con nec ted poin ts 65

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viii ContentsPolyhedra 68Coordination polyhed ra: polyhedral d'omains 68The regulr solids 69Semi-regular polyhedra 71Polyhedra related to the pentagonal dodecahedron andicosahedron 72Some less-regular polyhedra 745-coordination 767-coordination 778-coordination 789-coordination 79

10-a nd 11-coordination 80Plane nets 81Derivation of plane nets 81Configurations of plane nets 84Three-dimensional nets 86Derivation of 3D nets 86Further characterization of 3D nets 90Nets with polyhedral cavities 92Interpenetrating nets 92Polyhedral molecules and ions 93Tetrahed ral complexes 93Oc tahed ral molecules and ions 95Cubic molecules and ions 96Miscellaneous polyhedral complexes 96Cyclic molecules and ions 96Infinite linear molecules and ions 98Crystal structures based on 3-connected nets 101Types of structural unit 101

The plane hexagon net 102Structures based on othe r plane 3-connected nets 109Structures based on 3D 3-connected nets 110Crystal structures based on 4-connected nets 116Types of structural unit 116Structures based on the plane 4-gon net 118Layers of type A. Layers of type AX. Layers of type AX 2 .Layers of type A X 4 . 118-20Structures based on the diamond net 120AX2 structures. Structures based on Systems ofinterpenetrating diamond nets 124-7Structures based on more complex 4-connected nets 129More complex tetrahedral nets. Nets with planar and tetrahedral coo rdina tion. Nets with polyhedral cavities or tunnels . 130-3

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Space-fi ll ing arrange me nts of poly hed ra 136Space-fillings of regulr and Arc him ede an solids 137Space-fi ll ings of dod ecah edra and related pol yhe dra 1394 . SPHER E PACKI NGS 141Periodic packing s of equal sph eres 141Simple cubic packing 141The bod y-ce ntred cubic packing 143Tetrag onal close packing 145Th e do ses t packing of equal spheres 145Icosahedral sphere packings. 146Sphere packings based on closest-packed layers 148Interst ices betw een close-packed layers 151Stru cture s with some pairs of adjacent layers of typ e A 151Hexagon al and cubic do ses t packing of equa l spheres 154More com plex type s of do se st packing 156Close-packed arrang em ents of atom s of tw o kinds 158Close-packed struc tures with ato m s in tetrah edra l in terst ices 161Close-packed struc tures with atom s in octahe dral in terst ices 167Some re la ted MX 2 , M M ' X 4 , and M 2 M 'X 6 structures 174

Close-packed structures with atoms in tetrahedral and octahedralinterst ices 176An al ternat ive repre sen tat ion of close-packed struc tures 178Structures buil t f rom close-packed AX 3 layers 179A B X 3 s t ruc tu res 182A 3 B 2 X 9 s t ruc tu res 184A 2 B X 6 structures 1865. T E T R A H E D R A L A N D O C T A H E D R A L S T R U C T U R E S 1 87

Struc tures as assemblies of coo rdina tion poly hedr a 187Lim itat ions on bon d angles at shared X ato m s 190Th e ma xim um num ber o f po lyhe dra wi th a com m on ver tex 192Tetra hedra l struc tures 194Vertex-shar ing struc tures 194Edge-shar ing struc tures 198Ve rtex- and edge-shar ing struc tures 199Octahedra l s t ruc tu res 199Som e f inite group s of octa hed ra 200Inf inite Systems of l inked octa hed ra 203Vertex-shar ing struc tures 205Edge-sharing struc tures 211Ve rtex- and edge-shar ing struc tures 218Face-shar ing struc tures 229

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Ve rtex- and face-sharing s truc ture s 230Edge- and face-sharing s tructu res 232Vertex - , edge- , and face-sharing s truc ture s 233Structures bui l t f rom te t rahed ra and octahed ra 233

6. SOME SIMPLE AX STR UC TU RES 238Th e sodium Chloride s truc ture 238The caesium Chloride s truc ture 245The ruti le s truc ture 247C o m p o u n d s A B X 4 , A 2 B X 6 , et c. with ruti le- l ike s truc tures 250The f luor i te (AX 2 ) and antif luorite (A 2 X) s t ructures 252Addition of anions to the f luorite s tructure: the F e 3 AI s truc ture 254Defect f luorite s truc ture s 256The py roch lo re s t ruc tu re 258The Cd l 2 and re la ted s t ructures 258M X 2 and M 2X s t ructures 260Anions or cations of more than one kind in each MX 2 layer 261Replacem ent of ca t ions t o / o rm charged layers , 262Replacement of some OH in M(OH) 2 layer by O atoms of

oxy-ions 262A ttac hm en t of addit io nal me tal atom s to the surface of a layer 263The Re3 and related s truct ures 265Struc tures with s imilar analytical description s 269The PbO and PH 4 I s tructu res 269T h e L i N i 0 2 , N a H F 2 , and CsICl2 s t ructures 270The CrB, yellow TU ( 33 ), and related s tructu res 272The PbCl2 s t ructure 273The PdS 2 , Ag F 2 , and 0-HgO 2 s tructures and their relat ion to thepyrites s tructu re 275Relat ions between the s t ructures of some ni t r ides and oxy -com pou nds 277Superstruc tures and oth er related s truc tures 279

BONDS IN MO LECU LES AND CRY STAL S 283Introduct ion 283The lengths of covalent bo nd s 287The shapes of s imple mo lecules and ions of non-tra nsit ion elem ents 291Linear 16-electron mo lecules and ions 294Triangulr arrang em ent of 3 electron pairs 295The 18-elect ron gro up. The 24-electron gro up. 295Tetrahe dral arrang em ent of 4 electron pairs 296The 20-elect ron group. The 26-elect ron group. The 32-elect ron gro up. 29 6-7

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Trigonal bipyram idal arrange me nt of 5 electron pairs 297The 22-elect ron group. The 28-elect ron group. The 34-elect ron grou p. The 40-elect ron group 298Octa hedra l arrange me nt of 6 electron pairs 298The 36-elect ron group. The 42-elect ron group. The 48-elect ron grou p. 29 8-9The arrang em ent of 7 and 9 electro n pairs 299The 10-1 4 e lect ron groups 300Odd-electron Systems AX 2 and their dimers X 2A A X 2 301Th e van der Waals bon d 30 3Me tal -meta l bonding 304I. Molecules ( ions) conta ining directly bon ded metal ato m s

wi tho ut bridging l igands 305I I . Molecules ( ions) containing directly bonded metal atomsand bridging ligands 309I I I . Crystals con taining f inite, 1-, or 2-dimensional com plexe sbonded th rough meta l -meta l bondsThe ionic bondIonic radiiRadius rat io and shape of coordination groupEnvironment of an ionsLimita t ions on coordinat ion numbersLigand field theoryPreference for te t rahedral or octahedral coordinat ion .Dis tor ted coordinat ion groupsThe s tructures of complex ionic crystalsThe s tructures and s tabil i t ies of anhydrous oxy-salts M m ( X O ) p

PART IITh e periodic table of the elem ents 341

8 . HYD ROG EN: THE NOBLE GASES 342HYDROGEN 342In t roduc to ry 342Hydr ides 343

Molecular hyd rides 343Salt- like hyd rides 34 4Trans i t ion-metal hydr ides 346The 4f and 5f hydrides . Hydrides of the 3d, 4d, and5d metals 34 8-9

311312312315318319321

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Ternary hydride s 351Hydrido com plexes of transit io n me tals 35 3The hydrogen bond 355The proper t ies of hydrog en bond s 356Bond energies and leng ths 357Posit ion of the H ato m 358F - H - F b on ds . O - H - 0 b on ds . 35 9The hydrog en bond in crystals 360Hydrides 361Normal f luorides 362Bifluorides (acid f luorides) , MHF 2 364

Oth er fluorides M H F n + ! 3 6 5O t h e r i o n s ( X - H - X ) - 366Acids and acid salts 36 7Acids 367Acid salts 368The stru ctu res of acid salts and crystalline oxy-a cids 369H:XO ra tio l :2 .H :X O ra t io 2 : 3 . H :XO ra tio 1 :1 .H 'XO ra t io 3 :2 . H :XO ra tio 2 : l . H :X O ra t io 3 :1 369 -75COMPOUNDS OF TH E NOBLE GASE S 376Fluoride s of xen on 376Fluoro-cat ions 378Xenon anions 380Oxides and oxy-ion s 380Oxyf luo r ides and KXe0 3 F 381Com pounds of k ryp ton 382

T H E H A L O G E N S - S I M P L E H A L I D E S 3 8 4In t roduc t ion 384The s tereochem is t ry of ch lor ine , brom ine, and iodine 387The s tructu res of the elem ents 387Interhalogen Com pounds 389 The s truc ture s of interhalogen molecu les 389Molecules XX 3 ' . Molecules XX S '. Molecules X X ,. 39 0- 2Halogen and interha logen cations 392Ions X. Ions X j . Ions lf and I ; . Ions XX 2 + . Ions XF4.I o n s X F j . 3 9 2 - 4Polyhalides 394The s truct ures of polyh alide anions 395Polyiodide ions 396Hydrogen hal ides and ions HX2 , H2X3, e tc . 399Metal hyd ride halides 40 0

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Ox y-com pound s o f the ha logens 400Oxides 400Oxy fluorides and oxyfluo ride ions 401Oxy-ca t ions 402Oxy-ac ids and oxy-an ions 40 3Ac id s HOX. Ac id s H X 0 2 and the i r sa l t s . Acids H X 0 3 andtheir sal ts . Acids HXO4 and their sal ts . Per iodates containingoctahedra l ly coord ina ted iod ine . 40 3-5Halides of metals 40 7The struc tures of crystal l ine hal ides MX 408Monohal ides 410Alkal i ha l ides . Cu prous ha l ides . Argen tous ha l ides . A urous

hal ides . Subgroup HIB mon ohal ides 41 0- 11Dihalides 412Tetrahedra l s t ruc tu res . Octahedra l s t ruc tu res (Mg and the 3dmetals) . Dihalides of second and third ser ies t ransi t ion metals .Dihalides of alkal ine-ear ths, Cd, Pb, 4f , and 5f eleme nts. B subgroup d iha lides 41 2- 16Trihal ides 417Octahedra l MX 3 s t ruc tu res . S t ruc tu res o f h igher coord ina t ion .A number of structures peculiar to cer tain B subgrouph a l id es 4 17 - 2 3Tetraha l ides 424Pentaha l ides 427Hexahal ides 429Heptaha l ides 429Polynuclear complexes con ta in ing me ta l -me ta l bon ds 429Binuclear hal ide com plexes formed by Mo, Tc , and Re 42 9Trinuc lear hal ide com plexes of Re 431Halide complexes of Nb, Ta, Mo, W, Pd, and Pt containingme tal 'Clusters ' 43 2Sub-halides of elem ents of Gro ups I I IA and IVA 43 7Metal halides in the fused and vap ou r states 4 40

10. COMPLEX, OXY- , AND HYD ROX Y- HALI DES 4 4 5Com plex hal ides 44 5Halides ABX 2 4 4 9Halides A m B X 3 4 5 045 14 5 3Halides A m B X 6 4 5 4A B X 6 s t ruc tu res . A 2 B X 6 structures. The cryoli te familyof structures for Compounds A 3 B X 6 or A 2 ( B ' B " ) X 6 .Halides A 4 B X 6 . 4 5 7 - 6 2

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Halides A m B X 7 4 6 3Halides A m B X 8 4 6 3Co mp lex hal ides contain ing f ini te polyn uclea r com plex ions 464Complex hal ides containing complex anions of more thanone k ind 466Miscellaneous com plex hal ides 46 7Complex Chlor ides CsMCl3 , C s 2 M C l 4 , and Cs3M C ls fo rmedby 3d meta ls 46 7Co mp lex f luorides of AI and Fe 46 8Som e com plex f luor ides of group IVA and VA elem ents 47 0Metal n i tr ide hal ides and related Com pounds 47 5Thiohal ides 476Oxyhal ides 477Oxy hal ide ions 478The s t ruc tu res o f meta l oxyhal ides 480Ionic oxyfluo rides 48 0Su perst ructu res of f luor i te 48 2Ox yhalides of t ransi t ion me tals in high oxid ation states 48 3Oxy halides MOC1, MOB r, and MOI 485Other oxyha l ide s t ruc tu res 488Hydroxyhal ides 489Hyd roxyhal ides MX(OH) 489Hydroxyhal ides M 2 X ( O H ) 3 4 8 9Other hydrox yhal ides 491Hydra ted hydroxyChlor ides 491Amminohalides 492

11 . OXYGEN 4 9 4The stereochem istry of oxyge n 49 4Differences betw een oxygen and sulphu r 495Simple molecules and ions 49 8The oxygen mo lecule and dioxy genyl ion 49 8Ozone and ozonides 499Peroxides, Superoxides, and sesquioxides 49 9Molecules O R 2 5 00Hydrogen pero xide 501Oxygen fluorides 502Per-acids of non -m etals 50 3Peroxo- and superoxo-der ivat ives of metals 504Metal oxo-ions and mo lecules 507Metal oxo -com pou nds conta ining MOM bridges 508Oxy- ions 510Ty pes o f complex oxy- ion 512

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Mononuclear ions . Finite polynuclear ions . Infinite polynuclear oxy- ions 512 -13Isopoly ions 514I o ns o f V . N b , a n d T a 5 1 4Ions of Mo and W 515The ions (M o 6 0 1 9 ) 2 ~ and (W 6 0 1 9 ) 2 ~. The ion Mo 7 O t 4 .The ions Mo 8 0 2 6 and H 2 M o 8 0 2 g. The ion Wi^O^.Molybdic and tungstic acids . The paratungstate andmeta tungs ta te ions 517-1 9Heteropoly ions 520Tetrahe dral coord inat ion of hetero-a tom 521T h e P W 1 2 0 | ^ i o n . T h e P M o g C ^ H i " a n d P 2M o1 8O Jj2 ions .

The H 2 A sW I8 0J ion . 521 -5Octahedral coord inat ion of hetero-a tom 525The ions TeMo 60 2 4~. The MnMo 9 0 ^ 2 i o n . T h e M n N b 1 2 0 3 8 ~ion. The H 4 C o 2 M o 1 0 O 3 8 ion . 525-7Ant ipr ismat ic coordina t ion of hetero a tom 528T h e C e W ^ O a s H l " io n . T h e [ U ( G e W n 0 3 9 ) 2 ] 1 2 ~ion. 528Icosahedral coordin at ion of hete ro a tom 528The H 6 C e M o , 2 0 4 2 ion . 528He terop oly ions con tainin g Mo and V (or P) 52812. BINARY META L OXIDES 531In t roduc t ion 531Th e s truc ture s of binary oxid es 533Sub oxide s of Rb and Cs 534Oxides M 3 0 536Oxides M 2 0 537Oxides MO 537Oxides M0 2 540Oxides M0 3 543Oxides M0 4 543Oxides M 2 0 3 543Oxides M 2 0 5 547Oxides M 2 0 7 549Oxid es M3O4 550Th e oxides of iron 551The oxides of a luminium 552

Th e oxides of man ganese 553Fram ewo rk s t ructures 555Layer s truc tures 556Th e oxid es of lead 556Lead m ono xid e , PbO 557

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Red lead, Pb 3 0 4 558Lead sesquioxide, P b 2 03 558Lead dioxide, Pb0 2 559Some comp lex oxides of Pb(IV ) 559The oxygen chem istry of som e transi t ion elem ents 560The oxides of t i tanium 562The oxyge n chem istry of Vanadium 565Lower oxides. Vanadium pentoxide and vanadates. Vanadiumo x y h y d r o x id es 5 6 5 - 9The ox ides o f m olyb denu m and tungsten 569Dioxides and tr ioxides. Interm ediate oxides 572

13. COMPLEX OX IDES 575Introduction 575Oxides AB0 2 575Ox id es A B 0 3 5 7 7Str uc ture s based on close-packed AO3 layers 580The perovsk i te s t ruc tu re 584Sup erstructu res of perovskite 584Oxides ABO4 589Th e wolframite structu re 591Th e scheeli te and fergusonite structu res 592Oxides AB 2 0 4 592Th e norm al and Inve rse ' spinel structure s 593Spinel superstructures 596'Fe rr i te s ' e tc . with structu res related to spinel 597T h e C a F e 2 0 4 , C a T i 2 0 4 , and related structure s 600The K 2 N i F 4 s t tuc tu re 602Fu r the r complex ox ide s t ruc tu res 603The pseudobrooki te s t ruc tu re , A 2BOs 6 0 3Oxides AB 2 0 6 6 0 3The pyroch lore s t ruc tu re , A 2 B 2 0 7 6 0 4Layer structures Am B 2 X 7 related to perovskite 605The garnet structure 605Miscellaneous com plex oxid es 606Co mp lex oxides containing Ti , V, N b, Mo, or W 608Bronzes and related Com pounds 612Tungsten bronzes 613The te t ragonal b ronze s t ruc tu re 61 5Molybdenum bronzes 617Vanadium bronzes 618Complex oxides buil t of octahedral A0 6 and te t rahedra l B0 4 groups 619

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1 4 . M E T A L H Y D R O X I D E S , O X Y H Y D R O X I D E S , A N DHYDROXY-S ALTS 626Meta l hydrox ides 626The s t ruc tures of hydro xides M(OH) 628Hydrox ide s MOH, M(OH) 2 , and M(OH) 3 wi th no hydroge nbonding. Hydroxides M(OH)2 a nd M(OH) 3 with hydrogenb o n d s . 6 2 9 - 3 7Comple x hydrox ide s 637Oxyhydrox ide s 638The YO.OH s t ruc ture 638The InO.OH s t ruc ture 639The a -MO.OH s t ruc ture 639The 7-MO.OH s t ruc ture 641T h e a- C rO .O H ( H C r 0 2 ) s t ruc ture 642Hy dro xy (basic) sa l ts 643Th e crystal stru ctu res of basic salts 64 4Fini te hy dro xy -m eta l complexes 6451-dimensional hyd roxy -me ta l c omple xes 6472-dimens iona l hy dro xy -m eta l comp lexes 649

15. W A T E R A N D H Y D R A T E S 6 5 3Th e st ructu res of ice and water 65 3Ice 653Pro ton posi t ions in ice po lym orp hs. 655Water 656Aq ueous Solu tions 658Hydra tes 659Cla thra te hydra tes 660Polyhed ral framewo rks 661Hy drates of oxy-sal ts , hy dro xid es, and hal ides 666Hydrates of Class A: z/xn > 1 673H ydr ates of Class B: 1 > z/xn> Vi 675Hydrates of Class C: z/xn < Vi 6 81Hydrates of 3d hal ides. Hydrates of complex hal ides. Hydratesof C a C l j . Hydrates of Ca oxy-sal ts . Hydrates of vanadylsu lpha t e . 686-9H ydra ted acids and acid sa l ts 69 0The locat ion of H atom s of hyd roge n bo nd s; residual ent rop y 695Am mines and hydra tes 696Ox y-salts. Halides / 69 6

16. S U L P H U R , S E L E N I U M , A N D T E L L U R I U M 6 9 8The stereochem istry of sulphur 698

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Elem entary sulph ur, se lenium, and te l lurium 698S u lphur 700Selenium 702Tel lur ium 703Cyclic and polyh edral S, Se , and Te cat ions 703Molecules SR 2 , SeR 2 , and TeR 2 : cyclic mo lecules 70 4Th e hal ides of sulph ur, se lenium , and te l lurium 705Halides SX 2 etc . 707Halides S2X2 e tc . 708Halides SX 4 etc . ; molecules R 2S eX 2 and R 2 T e X 2 708Hexaha l ides 710Disulphur decafluoride , S2Fi0 711Ox yha lides of S, Se, and Te 711Th e oxid es of S, Se, and Te 713Disulphur monoxide , S 2 0 713S u lphur mo nox id e , S O 713Disulphur d ioxide , S 20 2 7 1 3S u lphur d iox ide , S 0 2 7 1 3Se lenium dioxide , Se0 2 714Tel lur ium dioxide , Te0 2 715Sulphur t r ioxide , S0 3 716Se lenium t r ioxide , Se0 3 717Te l lu r ium t r i ox ide , T e 0 3 717The oxides Te 2 O s , T e 4 0 9 , a nd t he oxyhydrox ide Te 2 0 4 ( O H ) 2 717Ox y-ions and mo lecules formed by S, Se , and Te 718Pyram idal ions and molecules 719Tetra hed ral ions and molecules 720The pyr osu lpha te and re la ted ions 724Dithioni tes 726Disulph i tes ( 'm etab isulp hi tes ' ) , dise leni tes , and di te l luri tes 726The stereochemistry of molecules and ions containing Sn chains 727Molecules S2R2 and S3R2 7 30Polysulphides 730Thiona tes and molecules of the type S(S0 2 R ) 2 732The st ruc tural chem istry of se lenium and te l lurium 735S e ( V I ) a n d T e ( V I ) 7 3 5Va le nce g roup (12 ) . 73 5S e ( I V ) a n d T e ( I V ) 7 3 9

Valence group (2,6). Valence group (2,8). Valence group(2 , 10 ) . Va l enc e g roup (2 , 12 ) . 73 9- 46Se(II ) and Te(I I ) 746Valence groups (4,6 ) and (4 ,8) . 746

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17. METAL SULPHI DES AND OXY SULPHI DES 7 4 8The structure s of binary metal sulphides 748I n t r o d u c t io n 7 4 8Sulphides M 2S 750Monosu lph ides 751Monosulphides of t ransi t ion metals . The nickel arsenides t ruc tu re . The PtS (coope r i te ) s t ruc tu re 75 1- 5Disulphides 756In terca la t ion complexes 758The pyri tes and marcasi te struc tures 758Sulphides M 2 S 3 and M 3 S 4 762Class ( i) : M2S3 structures with 3-coordination of M.Class (ii) : structures with close-packed S. Class (iii) :s truc tures with higher coo rdina tion of M. 76 3- 7The sulphides of indium 767The su lph ides o f chrom ium 768The su lph ides o f vanad ium , n iob ium , and tan ta lum 770The sulphides of t i tani um 772Com plex sulphides and thio-sal ts 773Thio-salts 775

Inf ini tely adaptive struc tures 778Sulphides structural ly related to zinc-blende or wu rtzi te 778Com plex sulphides contain ing me tal Clusters 784Oxysu lph ides 78618. N I T R O G E N 7 8 8In t roduct ion 788The stereoche mistry of ni trogen 788Nitrogen forming four te trah edra l bond s 791

Am mo nium and re lated ions 792Nitrogen forming three pyram idal bon ds 793Am mon ia and re la ted Compounds 793Am ides , imides , and n i t r ide hydr ides . 796Hy d r o x y lamin e 7 9 7Sulphonate ions der ived from NH 3 and NH^O H 797The tr ihal ides of ni trogen 799Hydra tes o f amm onia 800Ammines 800Molecules contain ing the system NN 801Hydraz ine , N 3 H 2 801Din i trogen te t ra f luor ide , N 2 F 4 802Nit rogen fo rming two bond s =N 802Di-imide (N 2 H 2 ) and dif luorodiazine (N 2 F 2 ) 804

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Co m pou nds co ntaining the system [N N -N] 805Azides 805The oxyge n chem istry of ni trogen 807Oxides 807Nit rous ox ide , N 2 0. Nitr ic oxide, NO. Nitrogen dioxide, NO2Din i t rogen t r iox ide , N 2 0 3 . Dini t rogen te t rox ide , N2O4.Din i t rogen pen tox ide , N 2 O s 8 0 8 - 1 0Nitrosyl Com pound s: NO ion 811Nit roso Compounds 812Nitros yl derivatives of m etais 81 2Nit ry l ha l ides and n i t ron ium Compounds 815Oxy halogen ions 816Acids and oxy-ions 816Nitrous acid . Metal n i tr i tes and ni tr i to Compounds. Organicn i t ro Compounds . Hyponi t rous ac id . Oxyhyponi t r i te ion .Peroxynitr i te ion. Nitr ic acid and ni trate ion. Metal n i tr i tesand ni trat o com plex es. Covalent ni trates 81 6-2 7The sulphides of ni trogen and related Com pounds 827Nitr ides 832Ionic ni tr ides 832Covalent ni tr ides 834

Nitr ides of t ransi t ion metais 835

19. P H O S P H O R U SThe s te reochemis t ry o f phosphorusElementary phosphorusPhosphides of metaisPo lyphosphanes and re la ted CompoundsThe structures of simple moleculesMolecules PX 3HCP and the PH 2 ionHydrides and molecules P 2 X 4 and P3X SPhosphory l and th iophosphory l ha l idesOther te trahedral molecules and ionsPhosphorus pentahalides, PX4 and PXg ionsMo lecu le s PR 5 , PR s_ t t X w , and mixed halidesThe ox ides and oxysu lph ide

Phosphorus t r iox idePhosphorus pen tox ideP(III)P(V) oxidesPhosphorus oxysu lph ideMolecules of the same geometrical type as P4O10

838838838840845845845846847848850851851853853853855855855

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Th e oxy-acids of pho sph oru s and their sa l ts 856Or thop hospho rous a cid 857Hy poph ospho rous a cid 857Hy poph ospho r ic acid 857Diph ospho rous ac id 858Isohy pop hosp hor ic acid 858Phosph or ic acid and pho spha tes 859Or thoph osph or ic acid and or tho pho sph a tes 859Pyrophospha tesdiphospha tes 859Linear polyph ospha tes 860Poly ions containing P and Cr 861Metaphospha tes 862M ono- and di-f luorop hosp horic acids 86 3P hosphora mida t e s a nd a mido th iopho spha t e s 864P hosphoro th ioa t e s 865Other subs t i tu ted phosp hor ic ac ids , e tc . 865Thiop hosph a tes and re la ted Compounds 867Phosph orus su lphides 867Phospho rus th ioha l ides 869Cyc l ic phosp horus Compounds 870Compounds conta in ing Pn rings 870Co mp oun ds conta in ing Systems of bonded N and P a tom s 870

2 0 . ARS ENIC, ANTIM ONY , AND BISMUTH 876Elemen ta ry a rsenic, an t im ony , and b ismuth 876The st ructura l chem istry of As, Sb, and Bi 876Molecules MX 3 : valence group (2 , 6) 878Tet rahedra l ions M X j: va lence group (8) 879Ions MX4: valence group (2 , 8) 880Pentahal ides and molecules MX 5 : valence grou p (10 ) 88 0Formation of Square pyramidal bonds by Sb(III) and Bi (III) :va lence group 2 ,1 0 881Format ion of oc tahedra l bonds by As(V) , Sb(V) , and Bi (V):valence grou p 2, 12 883Th e crystalline trihalides of A s, Sb , and Bi 884Com plex hal ides of t r ivalent Sb and Bi 884The oxy gen chem istry of trivalent As, Sb , and Bi 888Th e t r ioxide s of As, Sb , and Bi 889Sulphates of Sb(III) 891Meta-arsenites 893Com plex oxides of t r ivalent As and Sb 893Com plex oxides of t r ivalent Bi ^ 894The S yste ms Ca(S r, Ba, Cd , P b ) 0 - B i 2 0 3 . 894

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The oxyh alides of tr ivalent Sb 894Oxyfluorides of Bi 897Com plex oxyh alides of Bi with Li, Na, Ca, Sr , Ba, Cd, and Pb 897Oxides M(I I I )M(V )0 4 899The oxygen chem istry of pentav alent arsenic and anti m ony 900The oxy -com pou nds of pentavalent As 900The oxy -com pou nds of pentavalent Sb 902Salts containing Sb(OH)g ions. Complex oxides basedo n S b 0 6 coord ina t ion g roups . 90 3-4The sulphides of arsenic, an tim on y, and bism uth 907Thio-ions of As and Sb: cacody l disulphide 909

21 . CARBON 911In t roduc t ion 911The s tereoc hem istry of carbon 911The te t rahedral carbon a tom 913Diam ond: sa tura ted organic Compounds 913Carbon f luorides (f luorocarb ons) 915Carbon forming three bonds / 915Bond ar rangement = C 917Carbonyl halides and thiocarbonyl halides . Carboxylic acidsand re lated Compounds 91 7- 18Bond ar rangement C 920Carboxyla te ions . Carbam ate ion . Benzene 920Bond ar rangement C* 920Carbo nate ion . Tr iaz idocarbonium ion . Tr icyanom ethanideion . Urea . Graphi te 92 0-2Derivatives of gra phite 92 3

Graphi t ic oxide . Graphi t ic ' sa l ts ' . Carbon monof luor ide .Compounds of graphi te wi th a lkal i meta ls and bromine.Graph i te comp lexes wi th hal ides. 92 3- 5The oxides and sulphides of carbo n 925Carbon mo noxide 925Carbon dioxid e and disulph ide: carbon yl sulphide 925Carbon suboxide 927Acety lene and derivatives 92 8Cyanogen and related Com pounds 928Cyanogen 928HCN: cyanides and isocyanides of non-m etals 929Cyanogen halides 930C y a n a m i d e , H 2 N . C N 9 3 1Dicyand iamide , NCNC(NH 2 ) 2 931Cyanur ic Compounds 931

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Isocyanic acid and isocyanates 933Isothiocy anic acid , th ioc yan ates, and isothioc yana tes 934Metal th iocy anate s and isothioc yana tes 935lonic th iocyanates. Covalent th iocyanates and isothiocyanates. Thiocyanates containing bridging SCNg r o u p s . 9 3 5 - 6

2 2 . METAL CYA NI DES, CAR BI DES, CAR BON YLS, AND ALKYLS 9 3 8Metal cyanides 938Simple ionic cyanide s 938Cov alent cyanid es conta ining CN 941Covalent cyan ides con tainin g CN 942Prussian blue and related Com pounds 943Miscellaneous Cyanide and isocya nide com plex es 94 6Metal carbides 947Metal carbonyls 953Preparat ion and proper t ies 953The structu res of carbon yls and related Com pounds 95 7Carbonyls M(CO). Carbonyls M 2 (CO) . Carbonyls M 3 ( C O ) n .Carbonyls M4(CO)w . Carbonyls Ms(CO) . Carbonyls

M 6 ( C O ) . 9 5 9 - 6 3Ca rbony ls conta ining larger me tal Clusters 964Carbony l hydrides 966Carbo nyl hal ides 966Nitrosyl carbony ls 967Mixed me tal carbon yls 968Miscellaneous car bon yl derivatives of me tals 968Com pounds o f meta ls wi th hydroc arbons 971Acetylene comp lexes 971Cyclopen tad ieny l complexesCom plexes con ta in ing benzene o r cyc looc ta te t raene 977Metal alkyls 97 8Alkyls of B subgroup metals 979Alkyls of group s I and II me tals and AI 979

2 3 . SILICON 982In t roduct ion 982Th e stere och em istry of Silicon, 984Elem entary Sil icon and carb orun dum 985Silicides 987Silanes 992Silicon halides 99 3Oxyh alides and thiohalides 994

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Cyclic si l th ianes 995Som e s i l icon-n it rogen Com pounds 996Organo-si licon Com pounds and Sil icon polym ers 997Su bsti tu te d chlorosi lanes, s i lanols, and soxan es 998The structu res of si lanols and soxan es 1000Silanols. Disi loxanes. Cyclic polys oxa nes 1000Sil icone chem istry 1001Th e crysta lline form s of silica 1004Stuffed silica stru ctu res 10 08Silicates 1009Hydroxy-s i l ica tes 1010

Th e Classification of Silicate st ru ct ur es 101 1Or thosi l ica tes 1015The garne ts . Por t land cem ent . 101 5-17S icate s co nta ini ng Si2C>7~ ion s 101 9Sica tes con ta in ing cyc l ic (SiC^)" - ions 1021Sicates conta ining chain ions 1022Sicates with layer struc tures 1024Clay min erals 1031Sicates with f ramew ork structu res 1032Felspars. Zeo l i tes , Ul t ramar ines 10 33- 42

2 4 . B O R O N 1045In t roduct ion 1045The stereoc hem istry of bor on 1047Elem entary bo ron and related borides 1049Metal bor ides and boro carbid es 1052Lower hades and d iboron Com pounds 1058H a l i d e s B 2 X 4 1058Su b h a l id esBX 10 5 9Boron- r i i t rogen Com pounds 1060Boro n ni tr ide 1060B oron -nitro gen analogues of carbon Com pounds 1061Bo ron-n i t rogen Compounds re la ted to boranes 1063'Am mo nia te s ' o f boranes . Am inodiborane s . 1064The oxyg en chem istry of boro n 1065Boron tr ioxid e 1066Or th obor ic ac id and or tho bora tes 1067Pyrobora tes 1068M etaboric acid and m etab ora tes 1068Hy droxy bora tes and anhy drou s po lybora tes 1072Other bora te s t ruc tu res con ta in ing te t rahedra l ly coord ina tedboron 1078

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The lengths of B - O b o n d s 10 80Cyclic H 2 B 2 0 3 , boro x ine , H3B3O3, and borano carbona tes 1080Boranes and related Com pounds 1081Preparat ion and prope r t ies 1081The molecu lar structu res of the boranes 1085Diborane , B 2 H 6 . Te t raborane (10) , B 4 H 1 0 . Pen taborane (9 ) ,B S H 9 . Pen taborane (11) , B s H n . Hexaborane (10) , B 6 H i 0 .Oc tab o r an e ( 1 2 ) , B g H I 2 . Enneaborane (15) , B 9 H 1 5 . Deca-borane (14) , Bi 0 H 1 4 . Decaborane (16) , Bi 0 H i 6 . BoranesB i 6 H 2 o , B i 8 H 2 2 , a n d B 2 0 H i 6 . 1086-9Bo rohy dride ions and carboran es 1090The BH4 ion. The B 3H ion. Metal derivatives of car

boranes . 1090-325. COPPER , SILVE R, AND GO LD 1097Valence states 1097Super ion ic cond uctors 1100Co mp ound s o f Cu( I I I ) and Cu( IV) 1101Higher ox ida tion stat es of Ag 1102The structu ral chem istry of Cu (I) , Ag (I) , and Au (I) 1103The formation of two coll inear bonds by Cu(I) , Ag(I) ,

and Au(I) 1104Th e form ation of four te trahed ral bon ds by Cu (I) and Ag(I) 1107The form ation of three bo nds by Cu (I) , Ag (I) , and Au (I) 1112Salts contain ing Cu (I) and Cu (II) 111 6The structu rai chem istry of cupric Com pounds 1117The fo rmat ion o f 4 , (4 + 1 ) , o r (4 +2 ) bonds 1119Stru cture s of chelate cupric Com pounds 1123The struc tures of oxy-sal ts 1127The form ation of t r igonal bipyram idal bo nds by Cu(II) 1132Octahedra l complexes 1133Cupric halidessimple and com plex 1135Cupric hydrox y-sal ts 1141The sulphides of copp er 1142The structura l chem istry of Au (III) 1145

2 6 . THE ELEMENTS OF SUBGR OUPS I I B , HI B, AND I VB 114 9In t roduct ion 1149G a + , I n + , a n d T f 1 1 4 9G e 2 + , S n 2 + , and Pb 2 + 1151The structura l chem istry of zinc 11515-covalent zinc 115 3Cordination Compounds with tetrahedral or octahedral Znbonds 1155

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The structu ral chem istry of me rcury 1156Mercury cat ions 1156M ercurous Com pounds 1157M ercuric Com pounds 1158Mercuric hal idessimple and complex. OxyChlor ides andre la ted Compounds . Mercur ic ox ide and su lph ide . Mercury-n i t rogen Com pounds 11 61-6Th e.stru ctura l chem istry of gal lium and indium 1169The s t ruc tu ra l chem is t ry o f tha l l ium 1170Th e structura l chem istry of germ anium 1173The struc tural chem istry of t in and lead 1175Stann ic and p lumb ic Com pounds 1176Tetrahedra l coord ina t ion . Tr igonal b ipyramidal coord ina t ion .Octahedra l coord ina t ion 7 -and 8-coord ina ted Sn( IV) ;8-coord ina ted Pb( IV) 11 76 -9Struc tures o f some th ios tann ates 1180Stanno us and p lum bous Com pounds 1182

2 7 . GRO UP VI II AND OTH ER TRA NSI TI ON METALS 119 0I n t r o d u c t io n 119 0The stereoc hem istry of Ti(IV ) in som e f inite com plexes 1193The stereo chem istry of V in some coo rdina tion com plexes 1194The struc tura l chem istry of Cr( IV) , Cr(V ), and Cr(V I) 1197C o m p o u n d s o f C r ( I V ) 1 1 9 7C o m p o u n d s o f C r ( V ) 1 1 98C o m p o u n d s o f C r ( V I ) 1 1 9 8Co m pou nds con ta in ing Cr in two ox ida t ion s ta tes 1199Higher coo rdin ation num bers of metals in f ini te com plexes 1199The structu ral chem istry of i ron 1202The structu ral chem istry of cobalt 1207Th e s t e r eo ch emis t r y o f Co ( I I ) - d 7 1208Co(II) forming 4 bonds. Co(II) forming 5 bonds. Co(II)fo rming 6 bon ds . Co ( l l ) fo rming 8 bon ds . 12 09-1 3Co(I I I ) fo rming 6 oc tahedra l bon ds: cobal tamm ines 1214The i somer ism of cobal tammines . The s t ruc tu res o fco b a l t ammin es . 12 15 - 19The structu ral chem istry of nickel 1220Th e s t e r eo ch emis t r y o f N i ( I I ) - d 8 1220

Ni(II) forming 4 coplanar bonds. Ni(II ) forming 4 tetrahedralbonds. Ni(II ) forming 5 bonds. Ni(II ) forming 6 octahedralb o n d s . 12 2 3 - 9Oth er oxid ation states of Ni 1231The structu ral chem istry of Pd and Pt 1232Planar com plexes of Pd(II) and Pt(II ) 1232

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Pd(II) Com pounds 1232Co mp ound s o f Pt ( I I ) 1234Bridged Com pound s of Pd and Pt 1236Som e highly-colou red Com pounds of Pt 1238Pd(II) and Pt(I I) forming 5 bon ds 1239Pd(II) and Pt(II ) forming 6 octahe dral bon ds 1240Octahedra l coord ina t ion o f Pt ( IV) : t r imethy l p la t inumchlor ide and related Com pounds 1241Olef ine Com pounds 1244

28. THE LANTHAN I DES AND ACTI NI DES 12 4 8The crystal chem istry of the lanthanide s ( rare-ear ths) 1248Trivalent lanthanid es 1248Tetravalent lanthanid es 1249Divalent lanth anid es 1249Th e act inides 1250In t roduct ion 1250The crystal chem istry of thor iu m 1252The crystal chem istry of proto actin ium 1253The crystal chem istry of uraniu m 1254

Halides of uranium. Pentagonal bipyramidal coordinationof U in oxyh alides and oxyh alide ion s. Com plex f luoridesof 5f elements. Oxides of uranium. Uranyl Compounds.Uranates and complex ox ides o f u ran ium . 12 54 -70Nitr ides and related Compounds of Th and U; the La 2 0 3 andC e 2 G 2 S structu res 1271S u l p h id e s o f U , T h , a n d C e 1 27 229 . METALS AND ALLOY S 12 7 4Th e structure s of the eleme nts 1274

Th e noble gases 1275Non-m etals and the later B subgrou p elem ents 1276Alu min ium , the elem ents of subgrou ps I IB and HIB , Sn, and Pb 1277The transi t ion elements and those of subgroup IB 1 280Manganese. Tun gsten . The 4f me tals . The 5f metals . 12 82 -4The typical and A subgrou p elem ents of groups I and II 1285Intera tom ic distances in me tals: metal l ic radii 1286Theories of m etalc bond ing 1290Solid Solutions 129 3Order -d isorder phenomena and supers t ruc tu res 1 295j3-Brass 1297Alloys X 3Y 1297The stru ctu res of alloys 130 0The NaTl and related structu res 1300

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xxviii ContentsThe BaCu, Ca Cu s, X Y n , and XY13 structures 1302Transition metal a phases and Laves phases 1304Electron Compounds 1310Some aluminium-rich alloys A2B1 1312Systems A ,B 2 1314Phases A2B2 with the nickel arsenide structu re 1315Some bismuth-rich alloys A2B2 1316Systems BB 1317The formulae of alloys 1318Interstitial carbides and nitrides 1319Iron and steel 1323

FORMULA INDEX 1327SUBJECT INDEX 1375