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Book Review Inorganic Crystal Structures. By B. G. Hyde and S. Andersson

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Inorganic Crystal Structures. By B. C. Hyde and S . Andersson. Wiley, Chichester 1988. xv, 430 pp., hard cover,
.E 41.55.--ISBN 0-471-62897-2
In the last few decades the determination of chemical
structures-especially of crystal structures-has become
more important, is carried out more often, and is more useful
as regards the information obtained. A knowledge of the
structure of a compound not only gives very important insights into the spatial arrangement of atoms, clusters, and
molecules, but also provides the starting point for various,
more advanced theoretical studies (e.g. MO or band structure calculations) and experiments (e.g. on structure-property relationships, phase transformations or diffusion processes).
As a result of far-reaching developments in methods for
Karle and H .
structure determination, such as the work of .
Hauptmann (as described in their Nobel Prize address:
Angew. Chem. 98 (1986) 600, 61 1 ; Angew. Chem. Int. Ed.
Engl. 25 (1986) 603, 614), the majority of crystal structure
determinations can now be carried out rapidly and easily.
Every year many new structures or new variations of older
structural types are described. Consequently it is becoming
increasingly difficult to keep track of the whole field of structural chemistry.
To maintain an overview of the field, it is very important
to classify crystal structures and to recognize cross-correlations between them. Where can one find information about
whether a “new structure” is in fact completely new, or
whether and in what way it is related to known structural
types? Again and again cases occur where this question is
relevant, but is disregarded or simply overlooked. For example, who would guess that LiGaO,, Li,SiO, and Li,PO, are
practically isostructural, or that the Fe,P structure is closely
related to that of Li,ZrF,?
Despite the existence of some important more or less upto-date resources for systematizing and standardizing structures (e.g. standardization according to Partht, categorization according to Pearson, and data banks), this is still a
difficult task, and sometimes only specialists can hope to
succeed. An exhaustive treatment of the topic, including new
structures, could in fact only be undertaken by a large team
of experienced scientists. That such a work is needed, and
would remain in demand for a long time if it were available,
is shown by the fact that monographs which are partly already quite old, such as those by Wells, Pearson, and Schubert, to name only a few, are still frequently used. Where else
could one find cross-correlations between structures?
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mhH. 0.6940 Wemheini. 1990
The monograph by B. G. Hyde and S. Andersson is dedicated to this task; the title “Inorganic Crystal Structures” is
at the same time both ambitious and modest. In fact the
book only treats a selection of inorganic structures, and the
authors do not make any claim of completeness. Both authors are old hands at the business of investigating complex
crystal structures and analyzing structural relationships.
There are many places in the book where it becomes clear
that many years of experience are being brought to bear and
very interesting aspects are illuminated. Both, especially S .
Andersson, are known for their extraordinary insights into
apparently familiar topics, something which they have often
proved in their publications (e.g. Angew. Chem. 95 (1983) 67;
Angew. Chem. Int. Ed. Engl. 22 (1983) 69). The concepts of
“chemical twinning” and of block and shear structures are
especially thoroughly explained, and are used widely for elucidating structural correlations. The authors have concentrated throughout on a method of describing structures
which uses the coordination polyhedra as basic units. Each
of the 15 chapters constructs relationships between simple
basic types and structures of increasing complexity, using
diagrams which are mostly of excellent quality. Unfortunately though, a few of the diagrams suffer a loss of clarity
due to too much scale reduction.
In the first six chapters structures are put into directly
comparable forms by the use of suitably chosen projection
directions. At the beginning of each chapter the different
types of polyhedra are described in the appropriate projections. The variants of these with cubic and hexagonal symmetry having the highest spherical packing densities are
then studied in detail in different viewing directions. Combinations of the most densely packed cubic and hexagonal
structures are also treated. In these sections the basis structures are discussed in a variety of representations and in
different relationships; this procedure is very useful both for
beginners and for advanced readers, and it makes the book
a valuable learning aid.
Two chapters are also devoted to the derivatives of the
cubic and hexagonal primitive arrangements; these include
discussions of the large families of structures that have the
fluorite and AIB, structures as their basis.
Another chapter deals, in a very interesting way throughout, with the steric effects of electron lone pairs and their
influence on crystal structures. The authors have themselves
developed some interesting models to help in understanding
these effects, as well as topological transformations, which
are first described for polyhedra and networks, and are then
carried over to various structural types. A longer section
deals with some selected deformed variants of the perovskite
The next chapter is devoted to crystal forms containing
noncommensurate partial structures. The so-called chimney-ladder, layer misfit, and vernier structures are discussed,
illustrated by excellent diagrams. A treatment of derivatives
of body-centered cubic and cubic primitive structures with
tetrahedral stars (Schubert stars) as structural elements leads
into the structures of intermetallic phases. Here again the
size of the monograph allows only a few structures to be
discussed; however, some of the aspects considered are not
found in the older treatments by Schubert or Pearson.
The final chapter is concerned with a selection of silicate
structures, but regrettably the discussion is very brief. The
diagrams given here compete with those seen in the earlier
treatments by Wells or Liebau. Here, however, the interpre-
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tations of complex structures in terms of chemical twinning
of Anby translational or rotational operations-one
derson’s specialities-again provide new insights.
As a whole, the book discusses a selection of compounds
which spans the whole of inorganic chemistry, from fluorides
to intermetallic phases. At the end one is left with the feeling
that the book could have been much more detailed, especially in the last two chapters. This is not so much a criticism of
the book’s content as of its length, and is an expression of the
desire for a modern treatment of inorganic structures which
would be, as far as possible, complete.
I t is also noticeable that the book appears to have been
started several years ago, and in some places the literature
coverage is out of date. This shortcoming, together with a
few errors, should be corrected in a subsequent edition.
On the other hand there are other parts of the book where
one finds “brand-new” information, e.g. on the new hightemperature superconductors. One must also single out for
special praise the fact that for most of the structures discussed the complete structural parameters are given. This
gives the reader direct access to more advanced studies, and
avoids the often tedious searching out of data.
For beginners the “polyhedral” view of structures may at
first seem strange and difficult. However, after a little practice the consistent projections used (Chapters 2-6) allow one
to recognize correlations quickly. For experienced structural
chemists too, polyhedral models are very important; they
can even be used as a sort of “analog computer” ( H . G. von
Schnering) for “calculating” ideal structures and structural
parameters, as is done frequently in this book.
The book undoubtedly enriches the literature in this field,
and it also motivates the reader to look at structures from
different points of view, to understand them, and to look for
cross-correlations. It is useful both for teaching purposes
and for those engaged in structural chemistry research.
Reinhard Nesper [NB 1029 IE]
Max-Planck-Institut fur Festkorperforschung,
Stuttgart (FRG)
Houben-Weyl. Methoden der Organischen Chemie. 4th Edition, supplementary volumes. Carbene(oide),Carbine, Teil
1 und 2. (Volumes E 19b). Edited by M . Regitz. Thieme,
Stuttgart 1989. Part 1: xxxvi, pp. 1-3021; Part 2: xxi,
pp. 1022-2214; hardcover, DM 2680.00 (subscription
price: DM 2412.00).--ISBN 3-13-219704-1
Whereas previously the main emphasis in Houben-Weyl
was on functional groups and compound classes, the editors
have now also turned their attention to reactive intermediates. A two-volume work on free radicals (E 19a) was followed at the end of 1989 by the present work on carbene(oid)s. which is also in two volumes. As the most recent
monograph on carbenes was published in 1975 (reviews since
then have treated only parts of the topic), a serious information gap had appeared. This shortcoming was especially felt
by the synthetic organic chemist wishing to use carbene(oid)s
as building blocks for synthesizing target molecules. A welcome resource in this respect is now available in the amazingly comprehensive, reliable and up-to-date Houben-Weyl volumes.
The introduction ( W W Schoeller, 56 pages) unfortunately does not succeed in clearly presenting the basic principles
of carbene chemistry. Instead it describes what the theory of
carbenes and their reactions has to offer. The contributions
Angew. Chm?.Inl. Ed. En$ 29 (1990) No. 11
of the theory are treated thoroughly and competently, but
the relationship to experiment is often not adequately covered. For example, the four pages of theory on the 1,4-cycloaddition of carbenes are not accompanied by a single
practical example. Strangely, the authoritative studies by
Bickelhaupt and Mayr are presented as unsuccessful attempts
at 1,4-cycloaddition (p. 34). Schoeller explains the negative
activation energies of some carbene addition reactions as
being due to the formation of x-complexes (p. 16), and in
support of this cites Houk, despite the fact that he is responsible for the much more plausible explanation in terms of
entropy control. Other factual errors are on page 49, where
the protonation of I occurs after the carbene rearrangement
of 11, not before it as stated, and on page 55, where neither
the educts (cycloalkylcarbenes) nor their reaction path b are
given correctly. Although it contains useful information on
the capabilities and limitations of the theory, this article is
not a good “calling card” for the work as a whole.
A chapter on carbynes ( H . Heydt, 36 pages) includes everything that is worth knowing about the R-C: bonding
arrangement, which combines the properties of carbenes and
free radicals. The subject matter ranges from the gas phase
reactions of methylidyne and halocarbynes to the formation
of carbynes from their (transition) metal complexes and by
The entire field of carbene(oid) chemistry is then treated in
about 1800 pages. The subject matter is arranged according
to the substitution patterns of the intermediates. These main
chapters and their authors are as follows: alkylidenecarbenes, alkenylidenecarbenes, etc. (P. Stang, 80 pp.); methylene and alkyl- and dialkylcarbenes (K. P. Zeller, H. Gugel,
171 pp.); cycloalkylcarbenes and cycloalkylidenes (U.-H.
Brinker with J: Arct, J. Backes, W. Erdle, M . Fermann, L. K.
Sydnes, 328 pp.); alkenyl- and alkynylcarbenes ( U . Misslitz,
A . de Meijere, 110 pp.); cycloalkenylcarbenes and cycloalkenylidenes ( H . Diirr, 48 pp.); aryl-, diaryl- and heteroarylcarbenes (C. Wentrup, 198 pp.); acylcarbenes (C. Maas,
388 pp.); silylcarbenes, etc. ( H . Tomioka, 49 pp.); halocarbenes (E. I/: Dehmlov, 166 pp.); oxycarbenes ( H . Heydt, M .
Regitz, 55 pp.); sulfocarbenes (K. Schank, 63 pp.); nitrogensubstituted carbenes ( H . Heydt, M . Regitz, 77 pp.); phosphocarbenes ( H . Heydt, M . Regitz, G. Bertrand, 78 pp.). The
way in which these chapters are subdivided according to
second substituent, complexity, etc. largely prevents overlapping and makes it easy to find a particular carbene without
referring to the subject index. An exception: dihalo- and
trihaloalkylcarbenes appear in the chapter on acylcarbenes,
where they belong according to their oxidation state but not
their reaction properties.
All the chapters show a high level of expert knowledge,
orientated according to the authors’ own fields of research.
A few carbene(oid) types that are of preparative importance
(e.g. dihalocarbenes) are not given as much space as one
would expect, as their reactions are already covered in earlier
volumes of the Houben-Weyl series (e.g. 4/3 on cyclopropanes). However, the cross-references are always supplemented by new knowledge and further developments. As the
preparation of reactive intermediates is necessarily linked to
their further reaction, it is not possible in discussing the
various types of carbenes to stick to the traditional HoubenWeyl scheme of presentation (A. Preparation, B. Reactions).
Where some of the authors have nevertheless tried to do so,
it seems artificial and leads to repetition. The most sensible
arrangement, and also the one most often used, is according
to the co-reactants, thus: “preparation o f . . . in the presence
o f . . _ ”The
_ value of the numerous tables with their detailed
information cannot be too highly praised. Sometimes the
6) VCH firlagsgeseltschafi mhH. 0-6940 Wrinheim,1990
0570-0R33!90jfltf-1369 $3.50+.25/0
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crystals, inorganic, structure, book, review, hyde, andersson
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