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Molecular Structure by Diffraction Methods Volume 3
A Review of the Literature Published between April 1973 and September 1974
By G.A. Sim, L. E. SuttonThe Royal Society of Chemistry
Copyright © 1975 The Chemical Society
All rights reserved.
ISBN: 978-0-85186-527-0Contents
Part I Electron Diffraction, 1,
Introduction to Part I By L. E. Sutton, 3,
Chapter 1 Electron Diffraction Determination of Gas-phase Molecular Structures By D. W. H. Rankin, 5,
Chapter 2 Recent Developments in Apparatus in America, Canada, and Japan By R. L. Hilderbrandt, 25,
Chapter 3 Gases and Crystals: A Comparative Survey By B. Beagley, 52,
Chapter 4 Augmented Analyses: Method of Predicate Observations By L. S. Bartell, D. J. Romenesko, and T. C. Wong, 72,
Introduction to Parts II and Ill By G. A. Sim, 81,
Part II Neutron Diffraction By J.C. Speakman, 85,
1 Introduction, 85,
2 Experimental Methods, 85,
3 Hydrogen Bonding, 86,
4 Molecular Vibrations, 92,
5 Electrondensity Distributions, 93,
6 Phase Transitions, 94,
7 Organic and Organometallic Compounds, 95,
8 Inorganic Compounds, 98,
Part III X-Ray Diffraction, 101,
Chapter 1 Aromatic and Analogous Unsaturated Molecules By A. F. Cameron, 103,
Chapter 2 Molecular Complexes, Hydrogen-bonded Systems, and other Intermolecular Interactions By A. F. Cameron, 120,
Chapter 3 Non-aromatic Hydrocarbons, Heterocyclic Analogues, and Derivatives By A. F. Cameron, 128,
Chapter 4 Natural Products and Related Compounds By G. A. Sim, 163,
Chapter 5 The Structure of Globular Proteins and Nucleic Acids By T. L. Blundell and I. J. Tickle, 231,
Chapter 6 Titanium, Zirconium, and Hafnium By M. B. Hursthouse, 253,
Chapter 7 Vanadium, Niobium, and Tantalum By M. B. Hursthouse, 257,
Chapter 8 Chromium, Molybdenum, and Tungsten By Lj. Manojlovic-Muir, 263,
Chapter 9 Manganese, Technetium, and Rhenium By Lj. Manojlovic-Muir, 285,
Chapter 10 Iron, Ruthenium, and Osmium By W. S. McDonald, 298,
Chapter 11 Cobalt, Rhodium, and Iridium By Lj. Manojlovic-Muir and K. W. Muir, 320,
Chapter 12 Nickel, Palladium, and Platinum By K. W. Muir, 350,
Chapter 13 Copper, Silver, and Gold By W. S. McDonald, 384,
Chapter 14 Scandium, Yttrium, Lanthanides, and Actinides By M. B. Hursthouse, 407,
Chapter 15 Zinc, Cadmium, and Mercury By M. B. Hursthouse, 422,
Chapter 16 Boron, Aluminium, Gallium, Indium, and Thallium By M. B. Hursthouse, 436,
Chapter 17 Carbon, Silicon, Germanium, Tin, and Lead By M. B. Hursthouse, 450,
Chapter 18 Nitrogen, Phosphorus, Arsenic, Antimony, and Bismuth By M. B. Hursthouse, 461,
Chapter 19 Oxygen, Sulphur, Selenium, and Tellurium By M. B. Hursthouse, 475,
Chapter 20 Fluorine, Chlorine, Bromine, Iodine, and the Noble Gases By M. B. Hursthouse, 484,
Chapter 21 Lithium, Beryllium, Magnesium, and the Alkali and Alkaline-earth Elements By M. B. Hursthouse, 488,
Author Index, 496,
CHAPTER 1
Part I
ELECTRON DIFFRACTION
Introduction to Part I: Electron Diffraction
BY L. E. SUTTON
In this Volume there are four chapters on topics concerning electron diffraction studies on gases and vapours.
The first, as usual, is one on Results, covering structure determinations published during the period October 1973 to August 1974 and written by Dr. D. W. H. Rankin. This is smaller than those of previous years and so is less elaborately sub-divided. Although fewer results are reported, their total interest remains high. Among the new developments are some determinations of the structures of unstable species and conformational studies of large molecules. However, there is no lack of interest in the more usual measurements on newly synthesized compounds and in the re-determinations of the structures of simple molecules with much improved accuracy. Some of the measurements on large molecules throw light on two long-standing questions viz. whether there are definite radii for sp, sp2 and sp3 hybridized carbon atoms, and if conjugation affects the length of a bond between two sp2 hybridized carbon atoms.
Chapter 2 complements that on Theory and Accuracy by Dr. H. M. Seip in Volume 1, for it is the first of two on Developments in Apparatus which is a key matter in the practice of electron diffraction studies. This year we have a review of developments in Canada, Japan, and the United States of America by Professor Richard L. Hilderbrandt. In Volume 4 we hope to complete the picture by reviewing the parallel developments in Europe (including the U.S.S.R.).
Chapter 3 is an exploration of a borderline subject. What can we learn from measurements on a substance in both the vapour phase and the crystalline form? Dr. Brian Beagley has brought together a large number of results from the very scattered literature so that at last we can see what kinds of specific question there are to answer and how far this can be done. Much of interest emerges, especially for inorganic compounds.
Chapter 4 is concerned with the technique of data reduction. In the early determinations it was commonplace to use information gained from studies on simpler molecules to help in the analysis of more complex ones e.g. C — H bond lengths were usually assumed. This was done in a very simple-minded fashion. Now Professor L. S. Bartell, Dr. D. J. Romenesko and Dr. T. C. Wong bring this procedure up-to-date by showing how it can be done in a much more sophisticated and powerful way.
In the Introduction to the Electron Diffraction Part of Volume 1, which was written in late 1972, I said that it was hoped that a bibliographical volume on vapour-phase structure determinations by diffraction and spectroscopic methods, compiled by Mrs. Olga Kennard's group at Cambridge, would appear in the summer of 1973. Production of this volume has, alas, proved far more difficult than was anticipated; and the current news is that it may appear at the end of this year or, more likely, in 1976.
In conclusion, I have once again the pleasant duty of thanking the contributors to this Section for keeping to deadlines and generally being very helpful.
1 Electron Diffraction Determinations of Gas-phase Molecular Structures
BY D. W. H. RANKIN
1 Introduction
This chapter reports the results of structure determinations by electron diffraction published during the period October 1973 to August 1974 inclusive. Some 90 relevant papers appeared during this time, compared with ca. 130 included in the previous volume of this report (ref. 1, Part I), which covered rather more than a year. It seems that this is one area of chemistry where the number of publications is not subject to the galloping inflation that afflicts most others. Perhaps this is due partly to the limited number of molecules that are suitable candidates for study by electron diffraction. Indeed it is instructive to consider the types of molecule studied. Figure 1 shows the distribution of compounds investigated in terms of number of atoms per molecule. Most studies fall into one of five groups: (i) studies of molecules that are very reactive, or are only obtainable as gases at high temperatures. Most of these have not had their structure determined before, and are simple molecules, with 3-7 atoms; (ii) redeterminations of known structures of simple molecules, often by the combination of microwave and electron diffraction data, as well as...
