Table Of ContentChemical Crystallography with
Pulsed Neutrons and Synchrotron X-Rays
NATO ASI Series
Advanced Science Institutes Series
A Series presenting the results of activities sponsored by the NA TO Science Committee,
which aims at the dissemination of advanced scientific and technological knowledge,
with a view to strengthening links between scientific communities.
The series is published by an international board of publishers in conjunction with the
NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B PhysiCS London and New York
C Mathematical D. Reidel Publishing Company
and Physical Sciences Dordrecht, Boston, Lancaster and Tokyo
D Behavioural and Social Sciences Martinus Nijhoff Publishers
E Applied Sciences Dordrecht, Boston and Lancaster
F Computer and Systems Sciences Springer-Verlag
G Ecological Sciences Berlin, Heidelberg, New York, London,
H Cell Biology Paris, and Tokyo
Series C: Mathematical and Physical Sciences Vol. 221
Chemical Crystallography with
Pulsed Neutrons and
Synchrotron X-Rays
edited by
Maria Armenia Carrondo
Centro de Ouimica Estrutural,
Instituto Superior Tecnico, Lisboa, Portugal
and
George A. Jeffrey
Department of Crystallography,
University of Pittsburgh, Pennsylvania, U.S.A.
D. Reidel Publishing Company
Dordrecht / Boston / Lancaster / Tokyo
Published in cooperation with NATO Scien1ific Affairs Division
Proceedings of the NATO Advanced Study Institute on
Chemical Crystallography with Pulsed Neutrons and Synchrotron X-Rays
Alvor, Algarve, Portugal
March 17-27, 1987
Library of Congress Cataloging in Publication Data
NATO Advanced Study Institute on Chemical Crystallography with Pulsed Neutrons and
Synchrotron X-Rays (1987: Alvor, Portugal)
Chemical crystallography with pulsed neutrons and synchrotron X-rays I edited by Maria
Armenia Carrondo and George A. Jeffrey.
p. cm. - (NATO ASI series. Series C, Mathematical and physical sciences; vol. 221.)
"Proceedings of the NATO Advanced SLdy Institute on Chemical Crystallography with
Pulsed Neutrons and Synchroton X-Rays, Alvor, Algarve, Portugal, March 17-27, 1987"-t.p.
verso.
"Published in cooperation with NATO Scientific Affairs Division."
Includes index.
ISBN-13: 978-94-010-8287-7 e-ISBN-13: 978-94-009-4027-7
001: 10.1007/978-94-009-4027-7
1. Crystallography-4Angresses. 2. Pulsed neutron techniques-Congresses.
3. X-Ray crystallography-Congresses. I. Carrondo, Maria Armenia, 1948-
II. Jeffrey, George A., 1915- . III. Title. IV. Series: NATO ASI series. Series C,
Mathematical and physical sciences; no. 221.
QD951.N38 1987
548'.3--c!c 19 87-26853
CIP
Published by D. Reidel Publishing Company
P.O. Box 17, 3300 AA Dordrecht, Holland
Sold and distributed in the U.S.A. and Canada
by Kluwer Academic Publishers,
101 Philip Drive, Assinippi Park, Norwell, MA 02061, U.S.A.
In all other countries, sold and distributed
by Kluwer Academic Publishers Group,
p.o. Box 322, 3300 AH Dordrecht, Holland
D. Reidel Publishing Company is a member of the Kluwer Academic Publishers Group
All Rights Reserved
© 1988 by D. Reidel Publishing Company, Dordrecht, Holland.
Softcover reprint of the hardcover 1s t edition 1988
No part of the material protected by this copyright notice may be reproduced or utilized
in any form or by any means, electronic or mechanical, including photocopying, recording
or by any information storage and retrieval system, without written permission from the
copyright owner.
Contents
Preface IX
G.A. JEFFREY - « Chemical Crystallography: Past, Present and Future»
Discussion 7
G.H. LANDER - « Scientific Opportunities With Neutron Scattering" 9
Discussion 25
W.LF. DAVID - « The Scope and Possibilities of Crystallography
With Pulsed Neutrons» 27
Discussion 58
B. T.M. WILLIS - « Some Aspects of Diffraction Physics With
Pulsed Neutrons» 61
Discussion 75
H. FUESS - « Applications of Neutron Scattering in Chemistry:
Pulsed and Continuous Sources in Comparison » 77
Discussion 115
J. B. FORSYTH - « Single Crystal Pulsed Neutron Diffraction» 117
Discussion 134
A. K. CHEETHAM - • Pulsed Neutron Powder Diffraction» 137
Discussion 157
J. D. JORGENSEN - « Pulsed Neutron Diffraction in Special Sample
Environments» 159
Discussion 185
A. KVICK - « Applications of Synchrotron X-rays to Chemical
CrystallograpllY " 187
Discussion 203
W. SAENGER and - « Synchrotron X-Ray and Neutron Radiation in Protein
C. BETZEL CrystallograpllY - Present and Future» 205
Discussion 216
P. J. BECKER - « Synchrotron Radiation For Electron Density Studies» 217
Discussion 244
J. GOULON, M. Laos, - « Structural Applications of X-ray Absorption
P. FRIANT, and Spectroscopy (EXAFS and XANES) in Coordination
M. RUlz- LOPEZ Chemistry" 247
Discussion 292
A. ALBINATI • « Use of tile Rietveld Profile Analysis for Crystal
Structure Determination and Refinement» 295
Discussion 311
J. PANNETIER - « Real-Time Neutron Powder Diffraction" 313
Discussion 355
H. B. STUHRMANN - « Chemical Crystallography With Pulsed Neutrons
and SYllcluotron Radiation» %7
Discussion :n5
J. KARLE - « Recent Theoretical Advances in Macromolecular Structure
Determina.tion » 379
Discussion 385
vi
I.L. KARLE - « Solving Difficult Structures" 419
Discussion 441
C. RIEKEL - « Real Time Synchrotron Radiation Diffraction Experiments
on Polymers" 443
Discussion 485
H. D. BARTUNIK - « Time-Resolved Applications of Synchrotron
Radiation in Protein Crystallography" 487
Discussion S06
P. LINDLEY - « Crystallographic Studies of Biological Macromolecules
Using Synchrotron Radiation" 509
Discussion S36
M. M. HARDING - « The Use of Synchrotron Radiation for Laue
Diffraction and for the Study of Very Small Crystals" .537
Discussion .560
FINAL PANEL DISCUSSION S6:~
Posters
C. BETZEL et al - « Structure of Proteinase K Using Synchrotron
Radiation, and Binding of two Dipeptide Chloromethyl
Ketone Inhibithors to the Active Site" 567
C. BETZEL et al - « Protein CrystallograpllY Using Synchrotron
Radiation at the EMBL Oustation Hamburg" 568
P. LIGHTFOOT et al - « The Structure of MnP04 .H"!.O by SynclLrotron
X-ray Powder Diffraction" 569
E. HOVERSTREYDT et al - « ENDIX - a Computer Program to Simulate
Energy Dispersive X-ray and Syncllrotron Powder
Diffraction Diagram" 571
R.W. DATE etal - « An Investigation of the Structure and Molecular
Ordering of Liquid Crystal Phases" 573
L. VAN MEERVELT et al - « Relation Betwen The Crystalline
Structure and the S E Phase of
Vinyl - P - (PI - N - H exyloxyphenyl)benzoate " 575
J .A. ALONSO et al - « On TILe Influence of tiLe Non-bonded Pair
of Pb(I/) in the Novel Ordered Perovskite
Pb[ScodTio.2[,Tefl.2[,)I 0 3 ' 57i
1.A. ALONSO et al - « Synthesis and Crystal Structure of Ta? Te20~ , 579
W. DEPMEIER - « Remarks on the Structures and Pilase Transitions
in Aluminate Sodalites " 582
M. PERRIN et al - « Relationship Between CILemical Reactivity and Crystal
Structure in the Organic Solid State" 583
P. ESTEBAN et al - « Study by EXAFS of Pt - Ru/ Al203 Catalysts" 585
M. COSTA et al - « Electron Distribution in the Laves Phase, TiFe? " 586
W. T. A. HARRISON et al - « The Structure of Squaric Acid by Powder ~eutron
Diffraction" 587
J. RODRIGUEZ et al - « Data Analysis in Time Resolved Powder
Diffractometry , 589
J. RODRIGUEZ et al - « Phase Transition; in Sr2C020,.,: A Neutron
Diffraction Study" 590
A. GlBAUD - « A Rietveld Profile Analysis Treatment of
Line-Bro<l:dening in K AlF4 layered compound" 592
Organizing Committee
P. Becker Laboratoire de Cristallographie,
C.N.R.S., Grenoble, France
M.A. Carrondo t Centro de Qufmica Estrutural
Complexo I, Instituto Superior Tecnico
Lisboa, Portugal
M.B. Hursthouse Department of Chemistry, Queen Mary College,
University of London, U.K
G.A. Jeffrey t Department of Crystallography
University of Pittsburgh, Pittsburgh, U.S.A.
G.H. Lander European Institut for Transuranian Elements,
Karlsruhe
W. Saenger Institur fur Kristallographie, Freie Universitat
Berlin, F .R.G.
t Co-Directors
* We deeply regret the absence of Prof. Simonetta from the Universita. di
Milano, Italy, who had agreed to be a member of the Organizing Committee
just before his death, in January 1986.
Preface
X-ray and neutron crystallography have played an increasingly impor-
tant role in the chemical and biochemical sciences over the past fifty years.
The principal obstacles in this methodology, the phase problem and com-
puting, have been overcome. The former by the methods developed in the
1960's and just recognised by the 1985 Chemistry Nobel Prize award to
Karle and Hauptman, the latter by the dramatic advances that have taken
place in computer technology in the past twenty years.
Within the last decade, two new radiation sources have been added to
the crystallographer's tools. One is synchrotron X-rays and the other is
spallation neutrons. Both have much more powerful fluxes than the pre-
vious sources and they are pulsed rather than continuos. New techniques
are necessary to fully exploit the intense continuos radiation spectrum and
its pulsed property. Both radiations are only available from particular
National Laboratories on a guest-user basis for scientists outside these Na-
tional Laboratories.
Hitherto, the major emphasis on the use of these facilities has been in
solid-state physics, and the material, engineering and biological sciences.
We believe that there is equivalent potential to applications which are pri-
marily chemical or biochemical.
We have combined synchrotron X-rays and pulsed spallation neutrons
in this ASI for two reasons. One is because they have important common
properties such that concepts developped by the instrumental scientists us-
ing one radiation could be useful to those using the other. The other reason
is that both sources have new major facilities which have very recently be-
come operational as for example, the Daresbury and Brookhaven dedicated
X-ray synchrotrons and the Rutherford, Argonne and Los Alamos spalla-
tion neutron sources. For the near future more sources of both types are
planned or in construction in Europe (ESRF), USA (6 GeV synchrotron
source), Japan (ALS) and U.K. (ISIS II at RAL).
We have therefore brought to this meeting scientists who know the fun-
damental properties, advantages and limitations of both the pulsed neu-
trons and the synchrotron X-rays to interact with chemists, specially che-
mical crystallographers. The majority of these scientists have had no actual
experience in using these national facilities. The portuguese and spanish
ix
x
scientific communities, in particular, shoul benefit not only from the lec-
tures and tutorials but also from the opportunities to make direc~ contact
with some of these instrumental scientists.
Since the participants are mainly chemists, the first part of the course
had a strong educational component with emphasis on the basic physics
involved in the production and use of these radiations.
The second part was aimed at discussing these techniques, at the fron-
tiers of their applications, such as the exciting potential for real-time struc-
tural studies.
The book is organised with the lectures in the same sequence as pre-
sented. Each lecture was followed by a discussion, the main points of which
are summarized after the lecture.
Prof. Jeffrey has always showed a great enthusiasm for spreading the
knowledge of Chemical Crystallography among young researchers providing
they are willing to learn the relevant Physics and Mathematics required to
be masters of their science. He deplores the crescent trend towards "black-
box" science.
This course was designed to overcome this type of deficiency. Prof
Jeffrey's long-standing love for Portugal and the Portuguese people, was
the "seed" of our association on the organization of this course. The very
special climate and scenary of the Algarve, particularly in the early spring,
proved to be ideal for the site of the course.
Historically the sea was always an inspiration for creative ideias in the
human minds. And so it was in the XV century with Infante D. Henrique,
son of the Portuguese King D. Joao I, who devoted his life to the great
enterprise of the Portuguese discoveries departing from the Algarve. The
scientific backgrOund for these explorations was developped in Sagres, in
what is now considered as one of the first Naval Research Laboratories,
created by D. Henrique. Appropriately, this was chosen as the site of our
excursion.
We wish to thank the sponsors, NATO Scientific Affairs Division in
Brussels, and to Instituto Nacional de Investiga<;ao Cientifica, Junta Na-
cional de Investiga<;ao Cientifica e Tecnol6gica and Funda<;ao Calouste Gul-
benkian in Lisbon, for their generous contributions.
We also thank the Organizing Committee for their help and guidance
on the choice of lecturers. We are grateful to Prof. Skyes from Queen Mary
