Tài liệu Structural inorganic chemistry 4th edition a.f. wells

Structural Inorganic Chemistry A.F. WELLS CLARENDON PRESS - OXFORD Oxford University Press Ely House, London W1 1975 4th Edition Fsfsdf Oxford University Press, Ely House, London W.1 GLASGOW NEW YORK CAPE TOWN DELHl IBADAN BOMBAY KUALA LUMPUR TORONTO NAIROBI MELBOURNE DAR ES SALAAM CALCUTTA MADRAS KARACHI SINGAPORE HONG KONG WELLINGTON LUSAKA ADDIS ABABA LAHORE DACCA TOKYO I S B N 0 19 8 5 5 3 5 4 4 0 O X F O R D UNIVERSITY PRESS 1975 All rights reserved. No part of this publication may be reproduced, storedin a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission of' Oxford University Press PRINTED IN GREAT BRITAIN BY WILLIAM C L O W E S & S O N S L I M I T E D LONDON, COLCHESTER AND BECCLES Fsfsdf Preface This book has been almosl entirely rewritten, but its purpose and general organization remain the same las those of previous editions. The Introduction t o the first (1945) edition included dhe following paragraph: 'The reasons for writing this book were, firstly, the conviqtion that the structural side of inorganic chemistry cannot be put on a sound basls until the knowledge gained from the study of the solid state has been incorporated into chemistry as an integral part of that subject, and secondly, the equally strolng conviction that it is unsatisfactory merely to add information about the structures of solids to the descriptions of the elements and compounds as usually presented in a systematic treatment of inorganic chemistry.' Now, after a period of thirty years during which considerable advances have been made in solid state chemistry, it is still true to say that the structures and properties of solids receive very little atte~ntionin most treatments of inorganic chemistry, and this in spite of the fact that most elements and most inorganic compounds are solids at ordinary temperaturw. This state of affairs would seem to be sufficient justification for the appearance of yet another edition of this book. Since the results of structurkl studies of crystals are described in crystallographic language the first requirement is that these results be made available in a form intelligible to chemists. It was this challenge that first attracted the author, and it is hoped that this book will continue to provide teachers of chemistry with facts and ideas which can be incorporated into their teaching. However, while any addition of structural information to the donventional teaching of inorganic chemistry is to be welcomed the real need is a radical change of outlook and the recognition that not only is the structure of a substance in all states of aggregation an essential part of its full description (or characterization) but also that the structures and properties of solids form an integral part, pedhaps the major part, of the subject. The general plan of the boqk is as follows. Part I deals with a number of general topics and is intended as an introduction to the more detailed Part 11, which forms the larger part of the book. In Part I1 the structural chemistry of the elements is described systematically, and the arrangement of material is based on the groups of the Periodic Table. The advanlces made during the past decade have necessitated considerable changes in these latter chapters, but the major structural changes have been made in the content of Part I. Since a concise treatment of certain geometrical and topological topics is not readily available elsewhere mode space has been devoted to these than in previous editions at the expense of subjects such as the experimental methods of structural chemistry, which at best can receive only a sketchy treatment in a volume such as Preface this. Many students find difficulty in appreciating the three-dimensional geometry of crystal structures from two-dimensional illustrations (even stereoscopic photographs). In order to acquire some facility in visualising the three-dimensional arrangements of atoms in crystals some acquaintance is necessary with symmetry, repeating patterns, sphere-packings, and related topics. Some of this material could be, and sometimes is, introduced into teaching at an early age. However, there is a tendency in some quarters to regard solid geometry as old-fashioned and to replace it in school curricula by more fashionable aspects of mathematics. This adds to the difficulties of those teachers of chemistry who wish to modernize their teaching by including information about the structures of solids. Unless the student has an adequate grounding in the topics noted above little is gained by adding diagrams of unit cells of crystal structures to conventional chemistry texts. The educational value of building models representing the arrangements of atoms in crystals cannot be over-emphasized; and by this we mean that the student actually assembles the model and does not simply look at a ready-made model, however much more elegant the latter may be. Some very tentative suggestions for model building have been offered in the author's Models in Structural Inorganic Chemistry, to which the abbreviation MSIC in the present volume refers. References. The present volume has never been intended as a reference work, though it may serve as a useful starting-point when information is required on a particular topic. As an essential part of the educational process the advanced student should be encouraged to adopt a critical attitude towards the written word (including the present text); he must learn where to find the original literature and to begin to form his own judgment of the validity of conclusions drawn from experimental data. It is becoming increasingly difficult to locate the original source of a particular item of information, and for this reason numerous references to the scientific literature are included in the systematic part of this book. These generally refer to the latest work, in which references to earlier work are usually included. To save space (and expense) the names of scientific journals have been abbreviated to the forms listed on pp. mi-xxiii. Indexes. There are two indexes. The arrangement of entries in the formula index is not entirely systematic for there is no wholly satisfactory way of indexing inorganic compounds which retains chemically acceptable groupings of atoms. The formulae have been arranged so as to emphasize the feature most likely to be of interest t o the chemist. The subject index is largely restricted to names of minerals and organic compounds and to topics which are not readily located in the list of contents. Acknowledgments. During the writing of this book, which of necessity owes much to the work and ideas of other workers in this and related fields, I have had the benefit of helpful discussions with a number of colleagues, of whom I would particularly mention Dr. B. C. Chamberland. I wish to thank Dr. B. G . Bagley and the editor of Nature (London) for permission to use Fig. 4.3, Dr. H. T. Evans and Preface John Wiley and Sons for Figs Sc, 7, 10, 11, and 12b in Chapter 11, and Drs. G. T. Kokotailo and W. M. Meier for Fig. 23.27. It gives me great pleasure to acknowledge the debt that I owe to my wife for her support and encouragement over a period of many years. A. F. Wells Department o f Chemhtry, University o f Connecticut, Storrs, Connecticut, U.S.A. 1974 vii Fsfsdf Contents PART I 1. INTRODUCTION The importance of the solid state Structural formulae of inorganic compounds Geometrical and topological limitations on the structures of molecules and crystals The complete structural chemistry of an element or compound Structure in the solid state Structural changes o n melting Structural changes in the liquid state Structural changes o n boiling or sublimation A classification of crystals Crystals consisting of infinite 3-dimensional complexes Layer structures Chain structures Crystals containing finite complexes Relations between crystal structures 2. SYMMETRY Symmetry elements Repeating patterns, unit cells, and lattices One- and two-dimensional lattices; point groups Three-dimensional lattices; space groups Point groups; crystal systems Equivalent positions in space groups Examples of 'anomalous' symmetry Isomerism Structural (topological) isomerism Geometrical isomerism Optical activity 3. POLYHEDRA AND NETS Introduction The basic systems of connected points Polyhedra Coordination polyhedra: polyhedral domains The regular solids Semi-regular polyhedra Polyhedra related t o the pentagonal dodecahedron and icosahedron Some less-regular polyhedra Plane nets Derivation of plane nets Configurations of plane nets Three-dimensional nets Derivation of 3D nets Further characterization of 3D nets Nets with polyhedral cavities Interpenetrating nets Polyhedral molecules and ions Tetrahedral complexes Octahedral molecules and ions Cubic molecules and ions Miscellaneous polyhedral complexes Cyclic molecules and ions Infinite linear molecules and ions Crystal structures based on 3-connected nets Types of structural unit The plane hexagon net Structures based on other plane 3-connected nets Structures based o n 3D 3-connected nets Contents Crystal structures based on 4-connected nets 99 Types of structural unit 99 Structures based on the plane 4-gon net 100 Layers of type A. Layers of type AX. Layers of type AX2. Layers of type AX4. 100-1 02 Structures based on the diamond net 102 AX2 structures. Structures based o n systems of interpenetrating diamond nets. 102-107 Structures based on more complex 4connected nets 109 More complex tetrahedral nets. Nets with planar and tetrahedral coordination. Nets with polyhedral 110-1 12 cavities or tunnels. Space-filling arrangements of polyhedra Space-fillings of regular and Archimedean solids Space-fillings of dodecahedra and related polyhedra 4. SPHERE PACKINGS Periodic packings of equal spheres Simple cubic packing The body-centred cubic packing The closest packing of equal spheres Icosahedral sphere packings. Sphere packings based o n closest-packed layers Interstices between close-packed layers Structures with some pairs of adjacent layers of type A Hexagonal and cubic closest packing of equal spheres More complex types of closest packing Close-packed arrangements of atoms of two kinds Close-packed structures with atoms in tetrahedral interstices Close-packed structures with atoms in octahedral interstices Some related MX2, M M ' X ~ , and M2 M ' X ~structures Close-packed structures with atoms in tetrahedral and octahedral interstices An alternative representation of close-packed structures Structures built from close-packed AX3 layers ABX3 structures A3 B2 X9 structures A2 BX6 structures 5 TETRAHEDRAL AND OCTAHEDRAL STRUCTURES Structures as assemblies of coordination polyhedra Limitations on bond angles at shared X atoms The maximum number of polyhedra with a common vertex Tetrahedral structures Tetrahedra sharing vertices only Tetrahedra sharing edges only Tetrahedra sharing edges and vertices Octahedral structures Some finite groups of octahedra Infinite systems of linked octahedra Octahedra sharing only vertices Octahedra sharing only edges Octahedra sharing edges and vertices Octahedra sharing faces only Octahedra sharing faces and vertices Octahedra sharing faces and edges Octahedra sharing faces, edges, and vertices Structures built from tetrahedra and octahedra 6. SOME SIMPLE AX, STRUCTURES 130 l3 135 136 140 147 148 The sodium chloride structure The caesium chloride structure The rutile structure Compounds ABX4, A2 BX6, etc, with rutile-like structures Thefluorite(AX;)andantifluorite(A2 X)structures 204 Addition of anions to the fluorite structure: the Fe,Al structure 206 Defect fluorite structures The pyrochlore structure The Cd12 and related structures 207 209 209 Contents MX2 and M2 X structures Anions or cations of more than one kind in each MX2 layer Replacement of cations to form charged layers Replacement of some OH in M(OH)2 layer by 0 atoms of oxy-ions Attachment of additional metal atoms t o the surface of a layer The R e 0 3 and related structures Structures with similar analytical descriptions The PbO and PH41 structures The LiNiOz, NaHF2, and CsIC12 structures The CrB, yellow T1I ( B 33), and related structures The PbClz structure The PdS2, AgFz, and P-Hg02 structures Relations between the structures of some nitrides and oxy-compounds Superstructures and other related structures 21 1 212 212 2 12 213 214 2 18 218 219 22 1 22 1 223 225 227 7 . BONDS IN MOLECULES AND CRYSTALS 230 Introduction 230 The lengths of covalent bonds 234 The shapes of simple molecules and ions of non-transition elements 238 Linear 16-electron molecules and ions 239 Triangular arrangement of 3 electron pairs 240 The ldelectron group. The 24electron group. 240-1 Tetrahedral arrangement of 4 electron pairs 24 1 The 20electrc:! group. The 26electron group. The 32electron group. 242 Trigonal bipyramidal arrangement of 5 electron pairs 243 The 22electron group. The 28electron group. The 34electron group. The 40electron group. 243 Octahedral arrangement of 6 electron pairs 244 The 36electron group. The 42electron group. The 48-electron group. 244-5 The arrangement of 7 and 9 electron pairs 245 The 10-1 4 e l x t r o n groups 246 Odd-electron systems AX2 and their 247 dimers X2 A-AX2 The van der Waals bond 248 Metal- metal bonding 250 I. Molecules (ions) containing directly bonded metal atoms without bridging ligands 25 1 11. Molec,ules (ions) containing directly bonded metal atoms and bridging ligands 252 111. Crystals containing finite, 1-, or 2-dimensional complexes bonded through metal-metal bonds 254 The ionic bond 255 The lattice energy of a simple ionic 255 crystal Ionic radii 257 The structures of simple ionic crystals 260 Radius ratio and shape of coordination group 26 1 Limitations on coordination numbers 264 The polarizability of ions 266 Monohalides. Dihalides and trihalides. 267-8 The 'anti-layer' and 'anti-chain' structures 270 Ligand field theory 270 Preference for tetrahedral or octahedral coordination. Distorted coordination groups 272-3 The structures of complex ionic crystals 274 The structures and stabilities of anhydrous oxy-salts M,(XO,)p 276 + PART I1 8. HYDROGEN: THE NOBLE GASES Hydrogen Introductory Hydrides Molecular hy drides Salt-like hy drides Transition-metal hydrides The 4f and. Sf hydrides. Hydrides of the 3d, 4d, and 5d metals. Ternary hydrides Contents Hydrido complexes of transition metals The hydrogen bond The properties of hydrogen bonds Bond energies and lengths Position of the H atom The hydrogen bond in crystals Hy drides Normal fluorides Bifluorides (acid fluorides), MHF2 Other fluorides MH,F,+ Other ions (X-H-X)and (H20-HOH2 1' Acids and acid salts Acids Acid salts The structures of acid salts and crystalline oxy-acids Compounds of the noble gases Fluorides of xenon Fluoro-ions Oxides and oxy-ions Oxyfluorides and KXe03 F THE HALOGENS-SIMPLE HALIDES Introduction The stereochemistry of chlorine, bromine, and iodine The structures of the elements Interhalogen compounds The properties of bromine trifluoride The structures of interhalogen compounds Halogen and interhalogen cations Polyhalides . The structures of polyhalide ions Polyiodide ions Hydrogen halides and ions HX;, HZX i , etc. Metal hydrogen halides Oxy-compounds of the halogens Oxides and oxyfluorides Oxy-cations Oxy-acids and oxy-anions xii Acids HXO and their salts. Acids HXOz and their salts. Acids H X 0 3 and their salts. Acids HX04 and their salts. Periodates containing octahedrally coordinated iodine. 341-4 Halides of metals 345 The structures of crystalline halides MX, 347 Monohalides 348 Alkali halides. Cuprous halides. Aurous halides. Subgroup IIIB monohalides. 348-9 Dihalides 350 Tetrahedral structures. Octahedral structures (Mg and the 3d metals). Dihalides of second and third series transition metals. Dihalides of alkaline-earths, etc. B subgroup 3 5 0-4 dihalides. Trihalides 354 Octahedral MX3 structures. Structures of higher coordination. B 354-9 subgroup trihalides. Tetrahalides 359 Pentahalides 362 Hexahalides 3 64 Heptahalides 364 Polynuclear complexes containing metal364 metal bonds Binuclear halide complexes formed by Mo, Tc, and Re 364 Trinuclear halide complexes of Re 366 Halide complexes of Nb, Ta, Mo, W, Pd, and Pt-containing metal 'clusters' 367 Metal halides in the fused and vapour states 372 10. COMPLEX, OXY-, AND HYDROXYHALIDES 377 Complex halides 377 Halides ABXz 380 Halides A, BX3 38 1 Halides A, BX4 382 Halides A, BXS 383 Halides A, BX6 384 ABX6 structures A2 BX6 structures. The cryolite family ,,of structures A3BX6 or AZ (BIB )X6. Halides A4 BX6. 385-90 Contents Halides A, BX7 39 1 Halides A, BX8 39 1 Complex halides containing finite polynuclear complex ions 392 Complex halides containing complex 393 anions of more than one kind Miscellaneous complex halides 393 Complex chlorides CsMC13, Cs2 MC14, and CsJMCls formed by 3d metals 393 Complex fluorides of A1 and Fe(r11) 394 Some complex fluorides of group IVA and VA elements 396 Metal nitride halides and related compounds 399 Thiohalides 400 Oxy halides 40 1 Oxyhalide ions 402 The structures of metal oxyhalides 403 Ionic oxyfluorides 404 Superstructures of fluorite. 404 Oxyhalides of transition metals in high oxidation states 406 407 Oxyhalides MOCl, MOBr, and MOI Other oxyhalide structures 409 Hydroxyhalides 4 10 Hydroxyhalides MX(0H) Hydroxyhalides M2 X(OH)3 Other hydroxyhalides Hydrated hydroxychlorides Amminohalides OXYGEN The stereochemistry of oxygen Differences between oxygen and sulphur Simple molecules and ions The oxygen molecule and dioxygenyl ion Ozone and ozonates Peroxides, superoxides, and sesquioxides Molecules ORz Hydrogen peroxide Oxygen fluorides Per-acids of non-metals 419 410 41 1 412 412 4 15 417 417 418 419 419 420 42 1 42 1 Peroxo- and superoxo-derivatives metals Metal 0x0-ions and molecules Metal 0x0-compounds containing M-0-M bridges Oxy-ions Types of complex oxy-ions of 423 425 426 428 428 Isopoly ions 430 Ions of V, Nb, and Ta 430 Ions of Mo and W 43 1 The heptamolybdate ion. The octamolybdate ion. The paratungstate and metatungstate ions. 432-3 - Heteropoly ions 434 Tetrahedral coordination of heteroatom 434 O ~ The < ~ ~ ~ ~ 8 0 6 6 ; ' The P W ~ ~ ion. ion. 435-7 Octahedral coordination of hetero-atom 437 M ~ M O ;,~ O ~ The ions TeMo6 o:;, M ~ N ~ ~ ~ O : and : - , H ~ C O ~ M O ~ 437-8 OO$~. Icosahedral coordination of heteroatom 438 438 The C ~ M O , 0: 2 ion. 12. BINARY METAL OXIDES Introduction The structures of binary oxides Suboxides of Rb and Cs Oxides M3 0 Oxides M2 0 Oxides MO Oxides M02 Oxides M 0 3 Oxides M04 Oxides M2 O3 Oxides M2 o5 Oxides M2 0, Oxides M3 0 4 The oxides of iron The oxides of aluminium The oxides of manganese Framework structures xiii Contents Layer structures The oxides of lead Lead monoxide, PbO Red lead, Pb3 0 4 Lead sesquioxide, Pb2 O3 Lead dioxide, PbOz Some complex oxides of Pb(1v) 463 The oxygen chemistry of some transition elements 463 The oxides of titanium 465 The oxygen chemistry of vanadium 467 Lower oxides. Vanadium pentoxide and vanadates. Vanadium oxyhydroxides. 467-7 1 The oxides of molybdenum and tungsten 472 Dioxides and trioxides. Intermediate oxides. 473-4 COMPLEX OXIDES Introduction Oxides ABOz Oxides AB03 Structures based on close-packed A 0 3 layers Polymorphism of close-packed oxides AB03 The perovskite structure Superstructures of perovskite. Oxides AB04 The wolframite structure The scheelite and fergusonite structures Oxides AB2 O4 The normal and 'inverse' spinel structures Spinel superstructures 'Ferrites' etc. with structures related t o spinel The C a F e z 0 4 , C a T i z 0 4 , and related structures The K2 NiF4 structure Further complex oxide structures The pseudobrookite structure, Az BO5 Oxides ABz O6 xiv 480 482 483 486 487 488 489 489 490 493 493 496 498 498 498 498 The pyrochlore structure, A2 B20, The garnet structure Miscellaneous complex oxides Complex oxides containing Ti, V, Nb, Mo, or W Bronzes and related compounds Tungsten bronzes The tetragonal bronze structure Molybdenum bronzes Vanadium bronzes Complex oxides built of octahedral A 0 6 and tetrahedral B 0 4 groups 499 5 00 501 502 505 506 508 510 5 10 512 14. METAL HYDROXIDES, OXYHYDROXIDES, AND HY DROXY-SALTS 516 Metal hydroxides 516 The structures of hydroxides M(OH), 5 17 Hydroxides MOH, M(OH)2, and M(OH)3 with n o hydrogen bonding. Hydroxides M(OH)? and M(OH)3 with hydrogen bonds. 518-522 Complex hydroxides 524 Oxyhy droxides 525 The YO(0H) structure 525 The InO(0H) structure 525 The a-MO(0H) structure 526 527 The 7-MO(0H) structure The CrO(0H) or HCrOz structure 528 Other oxyhydroxides 5 29 Hydroxy (basic) salts 529 The crystal structures of basic salts 530 Finite hydroxy-metal complexes 532 1-dimensional hydroxy-metal complexes 532 2-dimensional hydroxy-metal complexes 535 15. WATER AND HYDRATES The structures of ice and water Ice Proton positions in ice polymorphs. Water Aqueous solutions Hydrates Clathrate hydrates 537 537 537 539 540 Contents Polyhedral frameworks 544 Hydrates of oxy-salts, hydroxides, and halides 548 Hydrates of 3d halides and complex halides. 562 Hydrated acids and acid salts 562 The location of H atoms of hydrogen bonds; residual entropy 566 Ammines and hydrates 567 Oxy-salts. Halides. 567-8 16. SULPHUR, SELENIUM, AND TELLURIUM The stereochemistry of sulphur Elementary sulphur, selenium, and tellurium Sulphur Selenium Tellurium Cyclic S, Se, and Te cations Molecules S R z , SeR2, and TeRz Cyclic molecules The halides of sulphur, selenium, and tellurium Halides SX2 etc. Halides S2 Xz etc. Halides SX4 etc.; molecules Rz S e x z and Rz TeX2 Hexahalides Disulphur decafluoride, S2F 1 0 Oxyhalides of S, Se, and Te The oxides of S, Se, and Te Disulphur monoxide, Sz 0 Sulphur monoxide, SO Sulphur dioxide, SO2 Selenium dioxide, S e 0 2 Tellurium dioxide, T e 0 2 Sulphur trioxide, SO3 Selenium trioxide, S e 0 3 Tellurium trioxide, T e 0 3 Oxy-ions and molecules formed by S, Se, and Te Pyramidal ions and molecules Tetrahedral ions and molecules The pyrosulphate and related ions 575 Dithionites 590 Disulphites ('metabisulphites') 590 The stereochemistry of molecules and ions 59 1 containing Sn chains Molecules S2 Rz and S3 R2 592 Polysulphides 593 Thionates and molecules of the type Sn(S02 R)z 594 The structural chemistry of selenium and tellurium 597 Se(v1) and Te(v1) 598 Valence group (1 2) 598 S ~ ( I Vand ) Te(1v): 598 Valence group (2,6). Valence group (2,8). Valence group (2,lO). Valence group (2,12). 598-$03 Se(11) and Te(11) 603 Valence groups (4,6) and (4,8) 603-4 METAL SULPHIDES AND OXYSULPHIDES 605 The structures of binary metal sulphides 605 Introduction Sulphides Mz S Monosulphides Monosulphides of transition metals. The nickel arsenide structure. The PtS (cooperite) structure. 608-1 1 Disulphides 612 The pyrites and marcasite structures. 613 616 Sulphides Mz S3 and M3 S4 Class (i): MzS3 structures with 3coordination of M. Class (ii): structures with close-packed S. Class (iii): structures with higher coordination of M. 617-20 The sulphides of chromium 62 1 The sulphides of vanadium, niobium, and tantalum 623 The sulphides of titanium 625 Complex sulphides and thio-salts 625 Thio-salts 627 Sulphides structurally related to zincblende and wurtzite 629 Other complex sulphides 633 Oxysulphides 635 Contents 18. NITROGEN Introduction The stereochemistry of nitrogen Nitrogen forming four tetrahedral bonds Ammonium and related ions Nitrogen forming three pyramidal bonds Ammonia and related compounds Amides and imides. Hy droxylamine The trihalides of nitrogen Hydrates of ammonia Ammines / Molecules containing the system)^-^, Hydrazine Dinitrogen tetrafluoride Nitrogen forming two bonds =N' Di-imide and difluorodiazine Compounds containing the system [N . . . N . . . Nl Azides The oxygen chemistry of nitrogen Oxides Nitrous oxide, N2 0 . Nitric oxide, NO. Nitrogen dioxide, NOz. Dinitrogen trioxide, N2 03. Dinitrogen tetroxide, N2 0 4 . Di6 50-2 nitrogen pentoxide, Nz 05. Nitrosyl compounds 653 Nitroso compounds 653 Nitrosyl derivatives of metals 654 Nitryl halides and nitronium compounds 656 Acids and oxy-ions 656 Nitrous acid. Metal nitrites and nitrito compounds. Organic nitro compounds. Hyponitrous acid. Oxyhyponitrite ion. Peroxynitrite ion. Nitric acid and nitrate ion. Metal nitrates and nitrato com657-65 plexes. Covalent nitrates. The sulphides of nitrogen and related compounds 665 Nitrides 668 Ionic nitrides 669 Covalent nitrides 67 1 67 1 Nitrides of transition metals xvi PHOSPHORUS The stereochemistry of phosphorus Elementary phosphorus Phosphides of metals The structures of simple molecules Molecules PX3 HCP and the PH; ion Hydrides and molecules P2X4 and p3 x5 Phosphoryl and thiophosphoryl halides Other tetrahedral molecules and ions Phosphorus pentahalides, PX4* and P&ions Molecules PR5 , PR5-,X,, and mixed halides The oxides and oxysulphide Phosphorus trioxide Phosphorus pentoxide Phosphorus oxysulphide Molecules of the same geometrical type as P 4 0 1 0 The oxy-acids of phosphorus and their salts Orthophosphorous acid Hypophosphorous acid Hypophosphoric acid Diphosphorous acid Isohypophosphoric acid Phosphoric acid and phosphates Orthophosphoric acid and orthophosphates Pyrophosphates Linear polyphosphates Metaphosphates Mono- and di-fluorophosphoric acids Phosphoramidates Phosphorothioates Other substituted phosphoric acids etc. Phosphorus sulphides Phosphorus thiohalides Cyclic phosphorus compounds Compounds containing P, rings Compounds containing (PN), rings Contents ARSENIC, ANTIMONY, AND BISMUTH Elementary arsenic, antimony, and bismuth The structural chemistry of As, Sb, and Bi Molecules MX3 : valence group (2, 6) Tetrahedral ions MX; : valence group (8) Ions M X i : valence group (2, 8) Pentahalides and molecules MX5 : valence group ( 10) Formation of octahedral bonds by As(v), Sb(v), and Bi(v): valence group (12) Formation of octahedral bonds by sb(111): valence group (2, 12) Formation of square pyramidal bonds by Sb(111) and Bi(r11): valence group (2, 10) The crystalline trihalides of As, Sb, and Bi Complex halides of trivalent Sb and Bi The oxygen chemistry of trivalent As, Sb, and Bi The trioxides of As, Sb, and Bi Meta-arsenites Complex oxides of trivalent As and Sb Complex oxides of trivalent Bi The systems Ca(Sr, Ba, Cd, Pb)OBi2 03. The oxyhalides of trivalent Sb Oxyfluorides of Bi Complex oxyhalides of Bi with Li, Na, Ca, Sr, Ba, Cd, and Pb The oxygen chemistry of pentavalent arsenic and antimony The oxy-compounds of pentavalent As The oxy-compounds of pentavalent Sb Salts containing Sb(0H); ions. Complex oxides based on SbOd coordination groups. The sulphides of arsenic, antimony, and bismuth 70 1 70 1 701 703 7 04 704 7 04 The tetrahedral carbon atom Diamond: saturated organic compounds 726 726 Carbon fluorides (fluorocarbons) 728 Carbon forming three bonds Bond arrangement =c( Carbonyl halides and thiocarbonyl halides. Carboxylic acids and related compounds. Bond arrangement 705 706 706 706 707 710 710 712 712 713 -c::: Carboxylate ions. Benzene. Bond arrangement ---c::: 729 730 73 1 733 733 733 Carbonate ion. Triazidocarbonium i o n . Tricyanomethanide ion. Urea. Graphite. 734 Derivatives of graphite ' 735 Graphitic oxide. Graphitic 'salts'. C a r b o n monofluoride. Compounds of graphite with alkali metals and bromine. Graphite 736-7 complexes with metal halides. The oxides and sulphides of carbon 738 Carbon monoxide 738 713 7 13 716 Carbon dioxide and disulphide: carbony1 sulphide Carbon suboxide Acetylene and derivatives Cyanogen and related compounds Cyanogen 716 HCN: cyanides and isocyanides of nonmetals 740 7 17 717 718 Cyanogen halides Cyanamide Dicyandiamide 742 742 743 Cyanuric compounds 743 Isocyanic acid and isocyanates Isothiocyanic acid, thiocyanates, and isothiocyanates 744 719 723 738 738 740 740 740 745 Metal thiocyanates and isothiocyanates CARBON Introduction The stereochemistry of carbon 746 Ionic thiocyanates. Covalent thiocyanates and isothiocyanates. Thiocyanates containing bridging -S-C-Ngroups. 746-7 xvii Contents 22. METAL CYANIDES, CARBIDES, CARBONYLS, AND ALKYLS Metal cyanides Simple ionic cyanides Covalent cyanides containing -CN Covalent cyanides containing -CNPrussian blue and related compounds Miscellaneous cyanide and isocyanide complexes Metal carbides Metal carbonyls Preparation and properties The structures of carbonyls and related compounds Carbonyl hydrides Carbonyl halides Nitrosyl carbonyls Mixed metal carbonyls Miscellaneous carbonyl derivatives of metals Compounds of metals with hydrocarbons Acetylene complexes Cyclopentadienyl complexes Complexes containing benzene or cyclooctatetraene Metal alkyls Alkyls of B subgroup metals Alkyls of groups I and I1 metals and A1 23. SILICON Introduction The stereochemistry of silicon Elementary silicon and carborundum Silicides Silanes Silicon halides Oxyhalides and thiohalides Cyclic silthianes Some silicon-nitrogen compounds Organo-silicon compounds and silicon polymers Substituted chlorosilanes, silanols, and siloxanes xviii The structures of silanols and siloxanes 799 Silanols. Linear polysiloxanes. Cyclic polysiloxanes. 799-800 Silicone chemistry 800 The crystalline forms of silica 803 Stuffed silica structures 806 Silicates 806 Orthosilicates 811 Portland cement. 813 Silicates containing Siz 0;- ions 813 Silicates containing cyclic (SiOB)inions 8 15 Silicates containing chain ions 816 Silicates with layer structures 8 18 Clay minerals 823 Silicates with framework structures 824 Felspars. Zeolites. Ultramarines. 826-32 784 784 786 787 789 793 794 794 795 796 796 798 BORON 833 Introduction 833 The stereochemistry of boron 835 Elementary boron and related borides 837 Metal borides and borocarbides 840 Lower halides and diboron compounds 845 845 Halides Bz X4 Halides B4 X4 and Bg X8 847 Boron-nitrogen compounds 847 Boron nitride 847 Boron-nitrogen analogues of carbon compounds 848 Boron-nitrogen compounds related t o boranes 850 'Ammoniates' of boranes. Aminodiboranes. 850-1 The oxygen chemistry of boron 851 Boron trioxide 852 Orthoboric acid and orthoborates 852 Pyroborates 853 Metaboric acid and metaborates 854 Hydroxyborates and anhydrous polyborates 856 Other borates containing tetrahedrally coordinated boron 860 The lengths of B-0 bonds 86 1 Cyclic Hz Bz 0 3 , boroxine, H3 B3O3, and boranocarbonates 862 Boranes and related compounds 862 Preparation and properties 862 The molecular structures of the boranes 866 Diborane, Bz H6. Tetraborane (1 o), B4H10 . Pentaborane (9), B5 H9. Pentaborane (1 l ) , BSH1 1. Hexaborane (1 o), B6H10 . Octaborane (1 2), B8 HI 2 . Enneaborane (1 5), B9 H I 5 . D e c a b o r a n e ( 1 4 ) , B1 O H l 4 . Decaborane (16), B i 0 H 1 6 . Boranes B16Hz0, B18H22, and B20H16. 868-70 Borohydride ions and carboranes 870 The BHi ion. The B 3 H i ion. Polyhedral ions. Metal derivatives of carboranes. 871-4 25. COPPER, SILVER, AND GOLD 875 Valence states 875 877 Compounds of CU(III) 877 Higher oxidation states of Ag The structural chemistry of CU(I), Ag(r), and AN11 879 The formation of 2 collinear bonds by CU(I), A ~ ( I )and , Au(1) 879 The formation of 4 tetrahedral bonds by Cu(1) and Ag(1) 880 The formation of 3 bonds by Cu(r) and &(I) 884 Salts containing CU(I) and CU(II) 886 The structural chemistry of cupric compounds 887 Structures of chelate cupric compounds 892 The structures of oxy-salts 895 The formation of trigonal bipyramidal bonds by CU(II) Octahedral complexes Cupric halides-simple and complex Cupric hydroxy-salts The sulphides of copper The structural chemistry of Au(111) 26. THE ELEMENTS O F SUBGROUPS IIB, IIIB, AND IVB Introduction 91 1 Ga+, In+, and T1' GeZ+,snZ+,and pb2+ 912 913 The structural chemistry of zinc 5-covalent zinc 915 Coordination compounds with tetrahedral or octahedral Zn bonds 916 916 The structural chemistry of mercury Mercurous compounds 9 17 Mercuric compounds 918 Mercuric halides-simple and complex. Oxychlorides and related compounds. Mercuric oxide and sulphide. Mercury-nitrogen com920-6 pounds. The structural chemistry of gallium and indium 926 927 The structural chemistry of thallium 929 The structural chemistry of germanium 931 The structural chemistry of tin and lead 931 Stannic and plumbic compounds Tetrahedral coordination. Trigonal bipyramidal coordination. Octahedral coordination. 7- and 8-coordinated Sn(1v); 8-coordinated Pb(1v). 9 3 1-4 Stannous and plumbous compounds 935 GROUP '(111 AND OTHER TRANSITION METALS Introduction The stereochemistry of Ti(1v) in some finite complexes The stereochemistry of V(IV) in some finite complexes , The structural chemistry of C ~ ( I V ) Cr(v), and C ~ ( V I ) Compounds of Cr(rv) Compounds of Cr(v) Compounds of Cr(v1) Compounds containing Cr in two oxidation states 947 Higher coordination numbers of metals in finite complexes 947 950 The structural chemistry of iron The structural chemistry of cobalt 954 xix Contents The stereochemistry of CO(II)-d7 954 Co(11) forming 4 bonds. Co(11) forming 5 bonds. CO(II) forming 6 bonds. 954-6 Cobaltammines 957 Introductory. The isomerism of cobaltammines. The structures of cobaltammines. 957-62 Other oxidation states of Co 963 The structural chemistry of nickel 964 964 The stereochemistry of N ~ ( I I ) - ~ ' Ni(11) forming 4 coplanar bonds. Ni(11) forming 4 tetrahedral bonds. Ni(11) forming 5 bonds. Ni(11) forming 6 octahedral bonds. 967-72 Other oxidation states of Ni 973 The structural chemistry of Pd and Pt 974 Planar complexes of Pd(11) and Pt(11) 974 Pd(11) compounds 976 Compounds of Pt(11) 977 Bridged compounds of Pd and Pt 978 Some highly-coloured compounds of Pt 980 Pd(11) and Pt(11) forming 5 bonds 980 Pd(11) and Pt(11) forming 6 octahedral bonds 981 Trimethyl platinum chloride and related compounds 982 Olefine compounds 984 28. THE LANTHANIDES AND ACTINIDES 988 The crystal chemistry of the lanthanides (rare-earths) 988 Trivalent lanthanides 988 Tetravalent lanthanides 989 Divalent lanthanides 989 The actinides 990 Introduction 990 The crystal chemistry of thorium 99 1 The crystal chemistry of protoactinium 992 The crystal chemistry of uranium 993 Halides of uranium. Complex fluorides of the 5 f elements. Oxides of uranium. Uranyl compounds. Uranates and complex oxides of uranium. 993-1003 Nitrides and related compounds of Th and U 1004 Sulphides of U, Th, and Ce 1006 29. METALS AND ALLOYS The structures of the elements The noble gases 1009 Non-metals and the later B subgroup elements 1009 Boron, aluminium, the elements of subgroups IIB and IIIB, Sn and Pb 101 1 The transition elements and those of subgroup IB 1014 Manganese. Tungsten. The 4f metals. The 5f metals. 1017-20 The typical and A subgroup elements of 1020 groups I and I1 Interatomic distances in metals: metallic radii 1020 Theories of metallic bonding 1023 Crystal structure and physical properties 1026 Solid solutions 1028 Order-disorder phenomena and superstructures 1029 ,&Brass 1031 Alloys X 3 Y 1031 The structures of alloys 1034 The NaTl and related structures 1035 XY 3 and related The XYS , XYI structures 1036 Transition-metal o phases and Laves phases 1038 Electron compounds 1044 Some aluminium-rich alloys A2Bl 1046 Systems A1 B2 1047 Phases A2 B2 with the nickel arsenide structure 1048 1049 Some bismuth-rich alloys A2B2 Systems BB 1050 The formulae of alloys 1050 Interstitial carbides and nitrides 1051 Iron and steel 1056 ,, FORMULA INDEX 1061 SUBJECT INDEX 1089