NMR Crystallography E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: EMR Books
• Sprache: Englisch

Seitenzahl: 1213

Veröffentlichungsjahr: 2012

Beschreibung

The content of this volume has been added to eMagRes (formerly Encyclopedia of Magnetic Resonance) - the ultimate online resource for NMR and MRI.

The term "NMR Crystallography" has only recently come into common usage, and even now causes raised eyebrows within some parts of the diffraction community. The power of solid-state NMR to give crystallographic information has considerably increased since the CPMAS suite of techniques was introduced in 1976. In the first years of the 21st century, the ability of NMR to provide information to support and facilitate the analysis of single-crystal and powder diffraction patterns has become widely accepted. Indeed, NMR can now be used to refine diffraction results and, in favorable cases, to solve crystal structures with minimal (or even no) diffraction data. The increasing ability to relate chemical shifts (including the tensor components) to the crystallographic location of relevant atoms in the unit cell via computational methods has added significantly to the practice of NMR crystallography. Diffraction experts will increasingly welcome NMR as an allied technique in their structural analyses. Indeed, it may be that in the future crystal structures will be determined by simultaneously fitting diffraction patterns and NMR spectra.

This Handbook is organised into six sections. The first contains an overview and some articles on fundamental NMR topics, followed by a section concentrating on chemical shifts, and one on coupling interactions. The fourth section contains articles describing how NMR results relate to fundamental crystallography concepts and to diffraction methods. The fifth section concerns specific aspects of structure, such as hydrogen bonding. Finally, four articles in the sixth section give applications of NMR crystallography to structural biology, organic & pharmaceutical chemistry, inorganic & materials chemistry, and geochemistry.

About EMR Handbooks / eMagRes Handbooks 

The Encyclopedia of Magnetic Resonance (up to 2012) and eMagRes (from 2013 onward) publish a wide range of online articles on all aspects of magnetic resonance in physics, chemistry, biology and medicine. The existence of this large number of articles, written by experts in various fields, is enabling the publication of a series of EMR Handbooks / eMagRes Handbooks on specific areas of NMR and MRI. The chapters of each of these handbooks will comprise a carefully chosen selection of articles from eMagRes. In consultation with the eMagRes Editorial Board, the EMR Handbooks / eMagRes Handbooks  are coherently planned in advance by specially-selected Editors, and new articles are written (together with updates of some already existing articles) to give appropriate complete coverage. The handbooks are intended to be of value and interest to research students, postdoctoral fellows and other researchers learning about the scientific area in question and undertaking relevant experiments, whether in academia or industry.

Have the content of this Handbook and the complete content of eMagRes at your fingertips!
Visit: www.wileyonlinelibrary.com/ref/eMagRes

View other eMagRes publications here

Leseprobe

EMR Handbooks

Based on the Encyclopedia of Magnetic Resonance (EMR), this monograph series focuses on hot topics and major developments in modern magnetic resonance and its many applications. Each volume in the series will have a specific focus in either general NMR or MRI, with coverage of applications in the key scientific disciplines of physics, chemistry, biology or medicine. All the material published in this series, plus additional content, will be available in the online version of EMR, although in a slightly different format.

Forthcoming EMR Handbooks

Multidimensional NMR Methods for the Solution StateEdited by Gareth A. Morris and James W. EmsleyISBN 978-0-470-77075-7

Solid State NMR Studies of BiopolymersEdited by Ann E. McDermott and Tatyana PolenovaISBN 978-0-470-72122-3

Handbook of RF Coils for MRI and NMREdited by John T. Vaughan and John R. GriffithsISBN 978-0-470-77076-4

Ultrafast Echo-time ImagingEdited by Graeme M. Bydder, Felix W. Wehrli and Ian R. YoungISBN 978-0-470-68835-9

Encyclopedia of Magnetic Resonance

Edited by Robin K. Harris, Roderick E. Wasylishen, Edwin D. Becker, John R. Griffiths, Vivian S. Lee, Ian R. Young, Ann E. McDermott, Tatyana Polenova, James W. Emsley, George A. Gray, Gareth A. Morris, Melinda J. Duer and Bernard C. Gerstein.

The Encyclopedia of Magnetic Resonance (EMR) is based on the original printed Encyclopedia of Nuclear Magnetic Resonance, which was first published in 1996 with an update volume added in 2000. EMR was launched online in 2007 with all the material that had previously appeared in print. New updates have since been and will be added on a regular basis throughout the year to keep the content up to date with current developments. Nuclear was dropped from the title to reflect the increasing prominence of MRI and other medical applications. This allows the editors to expand beyond the traditional borders of NMR to MRI and MRS, as well as to EPR and other modalities. EMR covers all aspects of magnetic resonance, with articles on the fundamental principles, the techniques and their applications in all areas of physics, chemistry, biology and medicine for both general NMR and MRI. Additionally, articles on the history of the subject are included.

For more information see: http://www.mrw.interscience.wiley.com/emr

This edition first published 2009© 2009 John Wiley & Sons Ltd

Registered office

John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom

For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at www.wiley.com.

The right of the authors to be identified as the authors of this work has been asserted in accordance with the Copyright, Designs and Patents Act 1988.

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher.

Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books.

Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold on the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional should be sought.

Library of Congress Cataloging-in-Publication Data

NMR crystallography / editors, Robin K. Harris, Roderick E. Wasylishen, Melinda J. Duer.

    p. cm.

Includes bibliographical references and index.

ISBN 978-0-470-69961-4

1. Crystallography. 2. Nuclear magnetic resonance spectroscopy. I. Harris, Robin

Kingsley. II. Wasylishen, Roderick E. III. Duer, Melinda J.

QD906.7.N83N67 2009 548—dc22

2009031427

A catalogue record for this book is available from the British Library.

ISBN-13: 978-0-470-69961-4

Set in 9.5/11.5 pt Times by Laserwords (Private) Limited, Chennai, India Printed and bound in Singapore by Markono Print Media Pte Ltd

Encyclopedia of Magnetic Resonance

Editorial Board

Editors-in-Chief

Robin K. HarrisUniversity of DurhamDurhamUK

Roderick E. WasylishenUniversity of AlbertaEdmonton, AlbertaCanada

Section EditorsSOLID-STATE NMR & PHYSICS

Melinda J. DuerUniversity of CambridgeCambridgeUK

Bernard C. GersteinAmes, IAUSA

SOLUTION-STATE NMR & CHEMISTRY

James W. EmsleyUniversity of SouthamptonSouthamptonUK

George A. GrayVarian Inc.Palo Alto, CAUSA

Gareth A. MorrisUniversity of ManchesterManchesterUK

BIOCHEMICAL NMR

Ann E. McDermottColumbia UniversityNew York, NYUSA

Tatyana PolenovaUniversity of DelawareNewark, DEUSA

MRI & MRS

John R. GriffithsCancer Research UK   Cambridge Research   InstituteCambridgeUK

Vivian S. LeeNYU Langone Medical   CenterNew York, NYUSA

Ian R. YoungImperial CollegeLondonUK

HISTORICAL PERSPECTIVES

Edwin D. BeckerNational Institutes of HealthBethesda, MDUSA

International Advisory Board

David M. Grant (Chairman)University of UtahSalt Lake City, UTUSA

Isao AndoTokyo Institute   of TechnologyTokyoJapan

Adriaan BaxNational Institutes of HealthBethesda, MDUSA

Chris BoeschUniversity BernBernSwitzerland

Paul A. BottomleyJohns Hopkins UniversityBaltimore, MDUSA

William G. BradleyUCSD Medical CenterSan Diego, CAUSA

Graeme M. BydderUCSD Medical CenterSan Diego, CAUSA

Paul T. CallaghanVictoria University   of WellingtonWellingtonNew Zealand

Richard R. ErnstEidgenössische Technische   Hochschule (ETH)ZürichSwitzerland

Ray FreemanUniversity of CambridgeCambridgeUK

Lucio FrydmanWeizmann Institute   of ScienceRehovotIsrael

Maurice GoldmanVillebon sur YvetteFrance

Harald G üntherUniversität SiegenSiegenGermany

Herbert Y. KresselHarvard Medical SchoolBoston, MAUSA

C. Leon PartainVanderbilt University Medical   CenterNashville, TNUSA

Alexander PinesUniversity of California   at BerkeleyBerkeley, CAUSA

George K. RaddaUniversity of OxfordOxfordUK

Hans Wolfgang SpiessMax-Planck Institute   of Polymer ResearchMainzGermany

Charles P. SlichterUniversity of Illinois   at Urbana-ChampaignUrbana, ILUSA

John S. WaughMassachusetts Institute   of Technology (MIT)Cambridge, MAUSA

Bernd WrackmeyerUniversität BayreuthBayreuthGermany

Kurt WüthrichThe Scripps Research   InstituteLa Jolla, CAUSAandETH ZürichZürichSwitzerland

Contents

Title

Copyright

Contributors

Series Preface

Volume Preface

Part A: Introduction

1 Crystallography & NMR: an Overview

1.1 Introduction

1.2 Limitations of Diffraction Techniques

1.3 NMR and its Crystallographic Significance

1.4 Required Information

1.5 Concluding Remarks

References

2 Tensors in NMR

2.1 Introduction

2.2 Cartesian to Spherical Tensors

2.3 Hamiltonians in Terms of Spherical Tensors of Rank 0, 1, 2

2.4 Matrix Elements for Spherical Tensors

References

3 Computation of Magnetic Resonance Parameters for Crystalline Systems: Principles

3.1 Introduction

3.2 Overview of the Planewave-Pseudopotential Approach

3.3 Shielding in a Periodic System

3.4 Other Magnetic Resonance Parameters

3.5 Examples

References

4 Experimental Characterization of Nuclear Spin Interaction Tensors

4.1 Introduction

4.2 Measurements from Wideline Spectra

4.3 Spinning Sideband Analysis

4.4 Single Crystals

4.5 Reliability

4.6 Conclusion

References

Part B: Chemical Shifts

5 Magnetic Shielding & Chemical Shifts: Basics

5.1 Introduction

5.2 Symmetry Properties of the Shielding Tensor

5.3 Theory of Magnetic Shielding

5.4 Calculations of Magnetic Shielding

References

6 Symmetry Effects at the Local Level

6.1 Introduction

6.2 Spin Systems and Interactions

6.3 Magnetic Shielding Tensors in Single Crystals

6.4 Magnetic Shielding Tensors in Polycrystalline Powders

6.5 Summary and Miscellaneous

References

7 Chemical Shift Computations for Crystalline Molecular Systems: Practice

7.1 Computational Details

7.2 General Aspects

7.3 Practical Uses of the Computations

7.4 Conclusions

References

8 Chemical Shifts & Solid-state Molecular-level Structure

8.1 Introduction

8.2 Molecular Structure

8.3 Tautomeric Form

8.4 Bond Lengths

8.5 Bond Angles

8.6 Dihedral Angles

8.7 Steric Crowding

8.8 Concluding Remarks

References

9 Chemical Shift Anisotropy & Asymmetry: Relationships to Crystal Structure

9.1 Introduction

9.2 Direct Encoding of Lattice Structure in Shift Tensors

9.3 Indirect Reflections of Lattice Structure in NMR Tensor Data

9.4 Refinement of Established Crystal Structures

9.5 Deriving Full Crystal Structures

References

Part C: Coupling Interactions

10 Dipolar & Indirect Coupling: Basics

10.1 Introduction

10.2 Characterization of Indirect Spin–Spin Coupling Interactions in Solids

10.3 Characterization of Dipolar Spin–Spin Coupling Interactions in Solids

10.4 Conclusions

References

11 Dipolar Recoupling: Heteronuclear

11.1 Introduction

11.2 MAS Hamiltonian

11.3 Heteronuclear Dipolar Recoupling in Spin Pairs

11.4 Heteronuclear Dipolar Recoupling in Multispin Systems

11.5 Conclusions

References

12 Dipolar Recoupling: Homonuclear

12.1 Introduction

12.2 Theoretical Background and Notation

12.3 Dipolar Recoupling by RF Pulses Alone

12.4 Chemical-Shift-Dependent Dipolar Recoupling

12.5 Symmetry Principles in Homonuclear Dipolar Recoupling

12.6 Frequency-Selective Homonuclear Dipolar Recoupling

12.7 Other Recent Developments

References

13 Dipolar Coupling: Molecular-level Mobility

13.1 Introduction

13.2 Basics

13.3 Averaged Dipolar Couplings—Fast Motions

13.4 Dynamic Lineshape–Intermediate Motions

13.5 Site-Resolved Heteronuclear and Homonuclear Dipolar Couplings

13.6 Double-Quantum Experiments

13.7 Dipolar Exchange NMR—Slow Motions

13.8 Summary

References

14 Spin Diffusion in Crystalline Solids

14.1 Introduction

14.2 The Mechanism of Spin Diffusion

14.3 Experiments to Measure Spin Diffusion

14.4 Modeling Spin Diffusion

14.5 Applications of Spin Diffusion to NMR Crystallography

14.6 Conclusion

References

15 Indirect Coupling & Connectivity

15.1 Introduction

15.2 Homonuclear Through-Bond Correlation Spectroscopy

15.3 Heteronuclear Through-Bond Correlation Spectroscopy

15.4 Conclusions

References

16 Nuclear Quadrupole Coupling: An Introduction & Crystallographic Aspects

16.1 Introduction

16.2 Theory of Quadrupolar Coupling

16.3 Computation of Quadrupolar Parameters

16.4 Effect on NMR Spectra

16.5 Measurement by NMR

16.6 Use in NMR Crystallography

16.7 Conclusions

References

Part D: Crystal Structure Determination using NMR

17 Fundamental Principles of NMR Crystallography

17.1 Introduction

17.2 NMR Physical Measurements

17.3 Resolving Structures by NMR

17.4 NMR Crystallography and Beyond Periodic Structures

References

18 Interplay between NMR & Single-crystal X-ray Diffraction

18.1 Introduction

18.2 Background Concepts

18.3 Solid-State NMR and X-Ray Diffraction

18.4 Examples

18.5 Conclusion

References

19 Combined Analysis of NMR & Powder Diffraction Data

19.1 Introduction

19.2 Introduction to Structure Determination from Powder Diffraction Data

19.3 Structure Determination from Powder Diffraction Data Augmented by Information from Solid-State NMR

19.4 Structure Determination Directly from Solid-State NMR Data

References

20 Tensor Interplay

20.1 Introduction

20.2 Tensor Interplay

20.3 Concluding Remarks

References

Part E: Properties of the Crystalline State

21 Intermolecular Interactions & Structural Motifs

21.1 Introduction

21.2 Host–Guest Interactions: Zeolites

21.3 Aromatic π–π Stacking and Ring-Current Effects

21.4 Interactions in Nanostructures

21.5 Polymorphs

21.6 Ab Initio Calculations

21.7 Conclusion

References

22 Hydrogen Bonding in Crystalline Organic Solids

22.1 Introduction

22.2 NMR Chemical Shifts

22.3 Dipolar Couplings

22.4 Hydrogen Bond-Mediated J Couplings

22.5 Hydrogen-Bond Dynamics

22.6 Outlook

References

23 Inorganic Non-stoichiometric Crystalline Systems & Atomic Ordering

23.1 Introduction

23.2 NMR Interactions and Data Analysis

23.3 Example Applications

23.4 Conclusions

References

24 Rotational & Translational Dynamics

24.1 Introduction

24.2 NMR and Dynamics

24.3 Rotational Barriers and Symmetry

24.4 Dynamics and Dipolar Coupling

24.5 Deuterium NMR Lineshapes

24.6 Shielding and Dynamics

24.7 Noninteger Quadrupolar Dynamic Averaging

24.8 Concluding Remarks

References

25 Intramolecular Motion in Crystalline Organic Solids

25.1 Introduction

25.2 Dynamics and Structure

25.3 Effects of Dynamics on NMR Spectra

25.4 Characterization of Dynamics in Solids

25.5 Overview

References

26 Structural Phase Transitions

26.1 Introduction

26.2 The Classification of Phase Transitions

26.3 NMR Identification of Phase Changes

26.4 The Landau Theory

26.5 Pure Quadrupole Resonance

26.6 Dynamics at Structural Phase Transitions

26.7 Summary

References

Part F: Applications of NMR to Crystalline Solids

27 Structural Biology

27.1 Introduction

27.2 Sample Preparation

27.3 Assignment Strategies

27.4 Structural Restraints

27.5 Alternative Isotope Labeling Patterns

27.6 Structure Calculation and Refinement

27.7 Dynamics

27.8 Prospects

References

28 Organic & Pharmaceutical Chemistry

28.1 Introduction

28.2 Search for the Stereochemistry of Organic Compounds and Pharmaceuticals in the Solid State by Means of XRD and SSNMR

28.3 Polymorphism of Organic Compounds and Pharmaceuticals

28.4 Molecular Disorder

28.5 Cryocrystallography and Solid-State NMR

28.6 Conclusions

References

29 Inorganic & Materials Chemistry

29.1 Introduction

29.2 Space-Group Assignment

29.3 Toward Full Structural Determination using NMR

References

30 Geochemistry

30.1 Introduction

30.2 Al, Si Order/Disorder

30.3 Al Coordination in Minerals

30.4 Anion Order/Disorder in Minerals

30.5 Order/Disorder of Cations Other than Al, Si

30.6 Vacancy Defects

30.7 Speciation and the Structural Role of H

30.8 Structural Environment of other Minor Components

30.9 Potential Future Applications

References

Index

Contributors

Sharon E. Ashbrook

School of Chemistry and EaStCHEM, University of St Andrews, St Andrews KY16 9ST, UK

Chapter 16: Nuclear Quadrupole Coupling: An Introduction & Crystallographic Aspects

Matthias Bechmann

Department of Chemistry, University of York, Heslington YO10 5DD, UK

Chapter 6: Symmetry Effects at the Local Level

Darren H. Brouwer

Department of Chemistry, Redeemer University College, Ancaster, Ontario L9K 1J4, Canada

Chapter 18: Interplay between NMR & Single-crystal X-ray Diffraction

Steven P. Brown

Department of Physics, University of Warwick, Coventry CV4 7AL, UK

Chapter 22: Hydrogen Bonding in Crystalline Organic Solids

David L. Bryce

Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada

Chapter 20: Tensor Interplay

Lindsay S. Cahill

Department of Physics, University of Warwick, Coventry CV4 7AL, UK

Chapter 21: Intermolecular Interactions & Structural Motifs

Ray Dupree

Physics Department, University of Warwick, Coventry CV7 4AL, UK

Chapter 29: Inorganic & Materials Chemistry

Lyndon Emsley

Centre de RMN à Très Hauts Champs (CNRS / ENS-Lyon / UCB Lyon 1), Université de Lyon, 69100 Villeurbanne, France

Chapter 14: Spin Diffusion in Crystalline Solids

Julio C. Facelli

Department of Biomedical Informatics and Center for High Performance Computing, University of Utah, Salt Lake City, UT 84112-0190, USA

Chapter 5: Magnetic Shielding & Chemical Shifts: BasicsChapter 8: Chemical Shifts & Solid-state Molecular-level Structure

Gillian R. Goward

Department of Chemistry, McMaster University, Hamilton, Ontario L8S 4M1, Canada

Chapter 21: Intermolecular Interactions & Structural Motifs

James K. Harper

Department of Chemistry, University of Utah, Salt Lake City, UT 84112, USA

Chapter 9: Chemical Shift Anisotropy & Asymmetry: Relationships to Crystal Structure

Kenneth D. M. Harris

School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK

Chapter 19: Combined Analysis of NMR & Powder Diffraction Data

Robin K. Harris

Department of Chemistry, University of Durham, Durham DH1 3LE, UK

Chapter 1: Crystallography & NMR: an OverviewChapter 7: Chemical Shift Computations for Crystalline Molecular Systems: Practice

Paul Hodgkinson

Department of Chemistry, University of Durham, Durham DH1 3LE, UK

Chapter 7: Chemical Shift Computations for Crystalline Molecular Systems: PracticeChapter 25: Intramolecular Motion in Crystalline Organic Solids

Christopher P. Jaroniec

Department of Chemistry, Ohio State University, Columbus, OH 43210, USA

Chapter 11: Dipolar Recoupling: Heteronuclear

Kenneth R. Jeffrey

Department of Chemistry, University of Guelph, Guelph, Ontario N1G 2W1, Canada

Chapter 26: Structural Phase Transitions

Alexej Jerschow

Department of Chemistry, New York University, New York, NY 10003, USA

Chapter 2: Tensors in NMR

Anne Lesage

Laboratoire de Chimie, Ecole Normale Superieure de Lyon, 69364 Lyon 07, France

Chapter 15: Indirect Coupling & Connectivity

David A. Middleton

School of Biological Sciences, University of Liverpool, Liverpool L69 7ZB, UK

Chapter 27: Structural Biology

Anita M. Orendt

Center for High Performance Computing, University of Utah, Salt Lake City, UT 84112-0190, USA

Chapter 5: Magnetic Shielding & Chemical Shifts: BasicsChapter 8: Chemical Shifts & Solid-state Molecular-level Structure

Glenn H. Penner

Department of Chemistry, University of Guelph, Guelph, Ontario N1G 2W1, Canada

Chapter 26: Structural Phase Transitions

Brian L. Phillips

Department of Geosciences, Stony Brook University, Stony Brook, NY 11794-2100, USA

Chapter 30: Geochemistry

Chris J. Pickard

School of Physics & Astronomy, University of St. Andrews, St. Andrews KY16 9SS, UK

Chapter 3: Computation of Magnetic Resonance Parameters for Crystalline Systems: PrinciplesChapter 7: Chemical Shift Computations for Crystalline Molecular Systems: Practice

Marek J. Potrzebowski

Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-362 Łódź, Poland

Chapter 28: Organic & Pharmaceutical Chemistry

Christopher I. Ratcliffe

Steacie Institute for Molecular Sciences, National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada

Chapter 24: Rotational & Translational Dynamics

Detlef Reichert

Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, D-06108 Halle, Germany

Chapter 13: Dipolar Coupling: Molecular-level Mobility

Kay Saalwächter

Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, D-06108 Halle, Germany

Chapter 13: Dipolar Coupling: Molecular-level Mobility

Angelika Sebald

Department of Chemistry, University of York, Heslington YO10 5DD, UK

Chapter 6: Symmetry Effects at the Local Level

S. Chandra Shekar

Department of Chemistry, New York University, New York, NY 10003, USA

Chapter 2: Tensors in NMR

Mark E. Smith

Department of Physics, University of Warwick, Coventry CV4 7AL, UK

Chapter 23: Inorganic Non-stoichiometric Crystalline Systems & Atomic Ordering

Francis Taulelle

Lavoisier Institute, University of Versailles-Saint-Quentin-en-Yvelines, 78035 Versailles, France

Chapter 17: Fundamental Principles of NMR Crystallography

Jeremy J. Titman

School of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK

Chapter 4: Experimental Characterization of Nuclear Spin Interaction Tensors

Robert Tycko

Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, MD 20892-0520, USA

Chapter 12: Dipolar Recoupling: Homonuclear

Roderick E. Wasylishen

Department of Chemistry, Gunning/Lemieux Chemistry Centre, University of Alberta, Edmonton, Alberta T6G 2G2, Canada

Chapter 10: Dipolar & Indirect Coupling: Basics

Stephen Wimperis

Department of Chemistry and WestCHEM, University of Glasgow, Glasgow G12 8QQ, UK

Chapter 16: Nuclear Quadrupole Coupling: An Introduction & Crystallographic Aspects

Mingcan Xu

School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK

Chapter 19: Combined Analysis of NMR & Powder Diffraction Data

Jonathan R. Yates

TCM Group, Cavendish Laboratory, University of Cambridge, Cambridge CB3 OHE, UK

Chapter 3: Computation of Magnetic Resonance Parameters for Crystalline Systems: PrinciplesChapter 7: Chemical Shift Computations for Crystalline Molecular Systems: Practice

Vadim Zorin

Department of Chemistry, University of Durham, Durham DH1 3LE, UK

Chapter 7: Chemical Shift Computations for Crystalline Molecular Systems: Practice

Series Preface

The Encyclopedia of Nuclear Magnetic Resonance was published in eight volumes in 1996, in part to celebrate the fiftieth anniversary of the first publications in NMR in January 1946. Volume 1 contains an historical overview and ca. 200 short personal articles by prominent NMR practitioners, while the remaining seven volumes comprised ca. 500 articles on a wide variety of topics in NMR (including MRI). Two “spin-off” volumes incorporating the articles on MRI and MRS (together with some new ones) were published in 2000 and a ninth volume was brought out in 2002. In 2006, the decision was taken to publish all the articles electronically (i.e. on the World Wide Web) and this was carried out in 2007. Since then, new articles have been placed on the web every three months and a number of the original articles have been updated. This process is continuing. The overall title has been changed to the Encyclopedia of Magnetic Resonance to allow for future articles on EPR and to accommodate the sensitivities of medical applications.

The existence of this large number of articles, written by experts in various fields, is enabling a new concept to be implemented, namely the publication of a series of printed handbooks on specific areas of NMR and MRI. The chapters of each of these handbooks will comprise a carefully chosen selection of Encyclopedia articles relevant to the area in question. In consultation with the Editorial Board, the handbooks are coherently planned in advance by specially selected editors. New articles are written and existing articles are updated to give appropriate complete coverage of the total area. The handbooks are intended to be of value and interest to research students, postdoctoral fellows, and other researchers learning about the topic in question and undertaking relevant experiments, whether in academia or industry.

Robin K. Harris

University of Durham, Durham, UK

Roderick E. Wasylishen

University of Alberta, Edmonton, Alberta, Canada

November 2009

Volume Preface

Since the earliest days of NMR, it has been recognized that the technique can provide information on matters concerning the disposition of atoms in the unit cells of crystals. Thus, the distance between protons in the water molecules of gypsum, CaSO4 · 2H2O, was determined by Pake and reported as 1.58 Å in 1948. However, the term NMR crystal-lography has only recently come into common usage, and even now causes raised eyebrows within some parts of the diffraction community. On the other hand, the power of solid-state NMR to give crystallo-graphic information has considerably increased since the CPMAS suite of techniques was introduced in 1976. In the first years of the 21st century, the ability of NMR to provide information to support and facilitate the analysis of single-crystal and powder diffraction patterns has become widely accepted. Indeed, NMR can now be used to refine diffraction results and, in favorable cases, to solve crystal structures with minimal (or even no) diffraction data. The increasing ability to relate chemical shifts (including the tensor components) to the crystallographic location of relevant atoms in the unit cell via computational methods has added significantly to the practice of NMR crystallography. Of course, NMR will never replace diffraction techniques in the determination of atomic positions in crystal structures, but diffraction experts will increasingly welcome NMR as an ally in their structural analyses. Indeed, it may be that in future crystal structures will be determined by simultaneously fitting diffraction patterns and NMR spectra.

However, NMR can also supply information on crystal structures which is inaccessible or very difficult to obtain by diffraction methods. Prominent among such investigations is the determination of dynamics at the molecular level in crystalline materials. There are many NMR methods for studying such motion, including relaxation measurements as well as spectral features, and they cover a vast range of motional rates. NMR can frequently distinguish between static and dynamic disorders.

Thus NMR crystallography can and should be considered as both complementary and supplementary to diffraction crystallography. At the time of writing there are few reviews and no books on NMR crystallography. It therefore seems to be timely to produce this handbook. The chapters herein, though taken from articles in the electronic version of the Encyclopedia of Magnetic Resonance, were commissioned specifically with this handbook in mind. The editors have attempted to produce a coherent set of chapters covering most aspects of NMR crystallography in a reasonably uniform way. Of course, since each chapter has its specific authors (expert in the topics in question) there will undoubtedly be some small degree of overlap between them and possibly a few lacunae. However, the handbook should be of value not only to students and practitioners of solid-state NMR but also to the wider crystallo-graphic community.

Some care has been taken to achieve consistency of symbols and notation, but there remain a few variations between chapters (for example, in the symbols used for dipolar coupling constants).

Finally, it may be noted that single-crystal NMR work, though feasible, is relatively unusual, so most studies involve microcrystalline/polycrystalline samples. Little information is sacrificed by this usage. Heterogeneous systems containing crystalline components are also amenable to study. Moreover, structural information at the molecular level (including geometrical data) can be obtained by NMR from amorphous and glassy materials, again with little loss. Although that situation is hinted at in various parts of the handbook, it is not specifically covered, though matters such as defect and other nonstoichiometric structures are discussed.

The handbook is organized into six parts. The first contains an overview and some chapters on fundamental NMR topics. Next comes a part concentrating on chemical shifts, followed by one on coupling interactions. Part D contains chapters describing how NMR results relate to fundamental crystallography concepts and to diffraction methods. The fifth part concerns specific aspects of structure, such as hydrogen bonding, and also has chapters on questions of molecular-level mobility and phase transitions. Finally, the four chapters in the last part give applications of NMR crystallography to structural biology, organic and pharmaceutical chemistry, inorganic and materials chemistry, and geochemistry.

As mentioned above, the articles are also to be found, with minimal differences but changed format, in the online Encyclopedia of Magnetic Resonance, which is at: http://www.mrw.interscience.wiley.com/emr. The online versions also contain brief autobiographies of the article authors, a list of related Encyclopedia articles, and, in a number of cases, acknowledgements by the authors. They also have cross-references to Encyclopedia articles which are not part of this handbook. Additionally, article abstracts and key words can be found online.

We are grateful to all the authors involved in this handbook for their agreements to write the online articles which preceded the handbook, for their expert texts and for their cooperation in reaching this stage. We also thank the people at Wiley and at Laserwords for all their hard work in bringing the handbook to the point of publication.

We offer this handbook in the hope that it will not only provide valuable information for a wide range of scientists but that it will also stimulate further advances in NMR crystallography.

Robin K. Harris

University of Durham, Durham, UK

Roderick E. Wasylishen

University of Alberta, Edmonton, Alberta, Canada

Melinda J. Duer

University of Cambridge, Cambridge, UK

November 2009

NMR Abbreviations and Acronyms

ABMS

Anisotropy of the Bulk Magnetic Susceptibility

ADRF

Adiabatic Demagnetization in the Rotating Frame

APT

Attached Proton Test

ARP

Adiabatic Rapid Passage

BIRD

BIlinear Rotation Decoupling

BLEW

A windowless multiple-pulse decoupling sequence

BR-24

Burum & Rhim (pulse sequence)

CIDNP

Chemically Induced Dynamic Nuclear Polarization

CIS

Complexation-Induced Shift

CODEX

Centerband only Detection of Exchange Experiment

COSY

Correlation Spectroscopy

CP

Cross Polarization

CPMAS

Cross Polarization with Magic Angle Spinning

CPMG

Carr-Purcell pulse sequence, Meiboom-Gill modification

CRAMPS

Combined Rotation and Multiple-Pulse Spectroscopy

CS

Chemical Shift

CSA

Chemical Shift Anisotropy

CST

Chemical Shift Tensor

CT

Central Transition

CT

Contact Time

CW

Continuous Wave

CYCLOPS

CYCLically Ordered Phase Sequence

D

Dipolar

DANTE

Delays Alternating with Nutations for Tailored Excitation

DAS

Dynamic Angle Spinning

DD

Dipole-Dipole

DEPT

Distortionless Enhancement by Polarization Transfer

DNP

Dynamic Nuclear Polarization

DOR

Double Rotation

DQ

Double Quantum

DQC

Double-Quantum Coherence

DQF

Double-Quantum Filtered

DRSE

Dipolar-Rotational Spin Echoes

DUMBO

Decoupling Using Mind-Boggling Optimization

EFG

Electric Field Gradient

ENDOR

Electron-Nucleus DOuble Resonance

EPR

Electron Paramagnetic Resonance

ESR

Electron Spin Resonance

EXSY

EXchange SpectroscopY

FC

Fermi-Contact

FFT

Fast-Fourier Transform

FID

Free Induction Decay

FIREMAT

Five π Replicated Magic Angle Turning

FSLG

Frequency-Switched Lee Goldburg

FT

Fourier Transform

HDOR

Heteronuclear Dipolar-Order Rotor-Encoding

HETCOR

Heteronuclear Correlation

HMQC

Heteronuclear Multiple Quantum Coherence

HOHAHA

HOmonuclear HArtman-HAhn

HSQC

Heteronuclear Single-Quantum Correlation

IBMS

Isotropic Bulk Magnetic Susceptibility

INADEQUATE

Incredible Natural Abundance Double Quantum Transfer Experiment

INEPT

Insensitive Nuclei Enhanced by Polarization Transfer

INEPT-HSQC

Insensitive Nuclei Enhanced By Polarization Transfer-Heteronuclear Single-Quantum Correlation

LG-CP

Lee-Goldberg CP

MAS

Magic Angle Spinning

MAS-J-HMQC

Magic Angle Spinning-JHeteronuclear Multiple Quantum Correlation

MAS-J-HSQC

Magic Angle Spinning-J-Single Quantum Correlation

MLEV-4

A broadband decoupling sequence

MQ

Multiple-quantum

MQMAS

Multiple-Quantum Magic-Angle Spinning

MREV

Mansfield, Rhim, Elleman, & Vaughan (pulse sequence)

MRI

Magnetic Resonance Imaging

NICS

Nucleus Independent Chemical Shift

NOE

Nuclear Overhauser Effect

NOESY

(Two-dimensional) NOE SpectroscopY

NQCC

Nuclear Quadrupole Coupling Constant

NQR

Nuclear Quadrupole Resonance

ODESSA

One-Dimensional Exchange Spectroscopy by Sideband Alternation

PAS

Principal Axis System

PDSD

Proton-Driven Spin Diffusion

PFG

Pulsed Field Gradient

PMLG

Phase-Modulated Lee Goldburg

PRESTO-II

Phase-Shifted Recoupling Effects a Smooth Transfer of Order

PSD

Proton Spin-Diffusion

Q

Quadrupolar

QF

Quadrupole moment/Field gradient (interaction or relaxation mechanism)

2QF-COSY

Double-Quantum-Filtered Correlation Spectroscopy

REAPDOR

Rotational Echo Adiabatic Passage Double Resonance

REDOR

Rotational-Echo Double-Resonance

RELM

Rotor-Encoding of Longitudinal Magnetization

REPT-HMQC

Recoupled Polarization-Transfer Heteronuclear Multiple-Quantum Correlation

REREDOR

Rotor-Encoded Rotational Echo

RF

Radio Frequency

RFDR

Radio Frequency Driven Recoupling

SA

Shielding Anisotropy

SD

Spin-Dipolar

SECSY

Spin Echo Correlation SpectroscopY

SEDOR

Spin Echo DOuble Resonance

SEFT

Spin Echo Fourier Transform

SLF

Separated-Local Field

SPI

Selective Population Inversion

SPT

Selective Population Transfer

SR

Spin-Rotation (interactive or relaxation mechanism)

ssb

Spinning Sidebands

SSNMR

Solid-State Nuclear Magnetic Resonance

STMAS

Satellite Transition Magic-Angle Spinning

TEDOR

Transferred Echo Double Resonance

TOCSY

Total Correlation Spectroscopy

TOSS

TOtal Suppression of Sidebands

TRAPDOR

Transfer of Population in Double Resonance

UC2QF-COSY

Uniform-Sign Cross-Peak Double-Quantum-Filtered Correlation Spectroscopy

UE

Unpaired Electron relaxation mechanism

VAS

Variable Angle Spinning

WAHUHA

WAugh, HUber, & HAeberlen (pulse sequence)

WALTZ-16

A broadband decoupling sequence

WISE

Wide-Line Separation

ZQ(C)

Zero Quantum (Coherence)

PART A

Introduction

Chapter 1

Crystallography & NMR: an Overview

Robin K. Harris

Department of Chemistry, University of Durham, Durham DH1 3LE, UK

1.1 INTRODUCTION

Although there is no problem defining nuclear magnetic resonance (NMR), different people interpret the term crystallography differently. In particular, experts in diffraction studies of crystals frequently use the term as though it is synonymous with structural information obtained by diffraction methods. However, historically, crystals were studied and classified by their morphology alone. It became recognized, for example, that different habits can result from the same underlying symmetry.

The term crystallography is derived from the Greek words crystallon, meaning cold drop/frozen drop, and graphein, meaning “write”. It refers to the experimental science of determining the arrangement of atoms in solids, specifically for what are now called solids. In older usage, it is simply the scientific study of crystals. The use of the words “atoms in solids” implies that amorphous solids may be included in “crystallography”, but this is contentious and such systems will not, in general, be dealt with here. Moreover, the original usage of the word (dating from eighteenth century Latin “crystallographic” and French “cristallographie”) referred to the external shape of crystals (morphology) rather than the internal structure, and this is still included in the normal meaning. Dictionaries define “crystallography” in various ways. Some include both internal arrangement and external morphology of crystals. Others discuss the properties of crystals and/or their classification. One of the simplest definitions states merely “the study of crystal form and structure”. Most dictionaries (as opposed to encyclopedias) do not mention diffraction in the definition.