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Crystal Design: Structure and Function Crystal Design: Structure and Function. Volume 7 Edited by Gautam R. Desiraju Copyright  2003 John Wiley & Sons, Ltd. ISBN: 0-470-84333-0 Editorial Board Founding Editor J M. Lehn, Colle Á ge de France, Chimie des Interactions Mole  culaires, 11 Place Marcelin Berthelot, 75005 Paris, France Editors C.J. Burrows, Of®ce 3152 HEB, Department of Chemistry, University of Utah, 315 S. 1400 East, RM Dock, Salt Lake City, UT 84112, Utah, USA G.R. Desiraju, University of Hyderabad, School of Chemistry, Hyderabad 500046, India A.D. Hamilton, Yale University, Department of Chemistry, New Haven, CT 06520, USA D. Hilvert, Laboratorium fu È r Organische Chemie, ETH Zentrum, Universita È ts- strasse 16, 8092 Zu È rich, Switzerland D.N. Reinhoudt, University of Twente, Faculty of Chemical Technology, P.O. Box 217, NL-7500 AE Enschede, The Netherlands J P Sauvage, Universite  Louis Pasteur, Institut le Bel, 4 Rue Blaise Pascal, F-67070 Strasbourg, France Former Editors J P. Behr, Faculte  de Pharmacie. Universite  Louis Pasteur, Strasbourg, B.P. 24, F-67401 Illkirch, France T. Kunitake, Kyushu University, Faculty of Engineering. Hakozaki, Fukuoka 812, Japan Crystal Design: Structure and Function Perspectives in Supramolecular Chemistry Volume 7 EDITED BY GAUTAM R. DESIRAJU University of Hyderabad, Hyderabad, India Copyright # 2003 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England Telephone (44) 1243 779777 E-mail (for orders and customer service enquiries): cs-books@wiley.co.uk Visit our Home Page on www.wileyeurope.com or www.wiley.com 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, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London W1T 4LP, UK, without the permission in writing of the Publisher. Requests to the Publisher should be addressed to the Permissions Department, John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England, or e-mailed to permreq@wiley.co.uk, or faxed to (44) 1243 770620. 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. Other Wiley Editorial Offices John Wiley & Sons Inc., 111 River Street, Hoboken, NJ 07030, USA Jossey-Bass, 989 Market Street, San Francisco, CA 94103±1741, USA Wiley-VCH Verlag GmbH, Boschstr. 12, D-69469 Weinheim, Germany John Wiley & Sons Australia Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Asia) Pte Ltd, 2 Clementi Loop #02±01, Jin Xing Distripark, Singapore 129809 John Wiley & Sons Canada Ltd, 22 Worcester Road, Etobicoke, Ontario, Canada M9W 1L1 Library of Congress Cataloging-in-Publication Data Crystal design: structure and function / edited by Gautam R. Desiraju. p. cm. ± (Perspectives in supramolecular chemistry; v. 6) Includes bibliographical references and indexes. ISBN 0-470-84333-0 (alk. paper) 1. Molecular crystals. 2. Crystal growth. 3. Crystallography. I. Desiraju, G. R. (Gautam R.) II. Series. QD921 .C787 2003 548 H .5±dc21 2002193382 British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN 0 470 84333 0 Typeset in 10/12pt Times by Kolam Information Services Pvt. Ltd, Pondicherry, India. Printed and bound in Great Britain by TJ International, Padstow, Cornwall. This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees are planted for each one used for paper production. Contents Contributors vii Preface ix 1 Hydrogen Bonds in Inorganic Chemistry: Application to Crystal Design 1 Lee Brammer 2 Molecular Recognition and Self-Assembly Between Amines and Alcohols (Supraminols) 77 Raffaele Saladino and Stephen Hanessian 3 Very Large Supramolecular Capsules Based on Hydrogen Bonding 153 Jerry L. Atwood, Leonard J. Barbour and Agoston Jerga 4 Molecular Tectonics: Molecular Networks Based on Inclusion Processes 177 Julien Martz, Ernest Graf, Andre  De Cian and Mir Wais Hosseini 5 Layered Materials by Design: 2D Coordination Polymeric Networks Containing Large Cavities/Channels 211 Kumar Biradha and Makoto Fujita 6 The Construction of One-, Two- and Three-Dimensional Organic±Inorganic Hybrid Materials from Molecular Building Blocks 241 Robert C. Finn, Eric Burkholder and Jon A. Zubieta 7 A Rational Approach for the Self-Assembly of Molecular Building Blocks in the Field of Molecule-Based Magnetism 275 Melanie Pilkington and Silvio Decurtins 8 Polymorphism, Crystal Transformations and Gas±Solid Reactions 325 Dario Braga and Fabrizia Grepioni 9 Solid±Gas Interactions Between Small Gaseous Molecules and Transition Metals in the Solid State. Toward Sensor Applications 375 Michel D. Meijer, Robertus J. M. Klein Gebbink and Gerard van Koten Cumulative Author Index 387 Cumulative Title Index 393 Index 397 vi Contents Contributors Jerry L. Atwood, Department of Chemistry, University of Missouri±Columbia, Columbia, MO 65211, USA Leonard J. Barbour, Department of Chemistry, University of Missouri±Columbia, Columbia, MO 65211, USA Kumar Biradha, Graduate School of Engineering, Nagoya University, Chikusaku, Nagoya 464±8603, Japan Dario Braga, Dipartimento di Chimica ``G. Ciamician'', Via F. Selmi 2, I-40126, Bologna, Italy Lee Brammer, Department of Chemistry, University of Shef®eld, Shef®eld S37HF, UK Eric Burkholder, Department of Chemistry, Syracuse University, Syracuse, NY 13244, USA Andre  De Cian, Laboratoire de Chimie de Coordination Organique, Tectonique Mole  culaire des Solides (CNRS FRE 2423), Universite  Louis Pasteur, Institut Le Bel, F-67070 Strasbourg, France Silvio Decurtins, Department of Chemistry and Biochemistry, University of Berne, Freiestrasse 3, CH-3012 Berne, Switzerland Robert C. Finn, Department of Chemistry, Syracuse University, Syracuse, NY 13244, USA Makoto Fujita, Graduate School of Engineering, Nagoya University, Chikusaku, Nagoya 464±8603, Japan Ernest Graf, Laboratoire de Chimie de Coordination Organique, Tectonique Mole  culaire des Solides (CNRS FRE 2423), Universite  Louis Pasteur, Institut Le Bel, F-67070 Strasbourg, France Fabrizia Grepioni, Dipartimento di Chimica, Via Vienna 2, I-07100, Sassari, Italy Stephen Hanessian, Department of Chemistry, Universite  de Montre  al, C.P. 6128, Succ. Centre-Ville, Montre  al, QC, H3C 3J7, Canada Mir Wais Hosseini, Laboratoire de Chimie de Coordination Organique, Tectoni- que Mole  culaire des Solides (CNRS FRE 2423), Universite  Louis Pasteur, Institut Le Bel, F-67070 Strasbourg, France Agoston Jerga, Department of Chemistry, University of Missouri±Columbia, Columbia, MO 65211, USA Robertus J. M. Klein Gebbink, Department of Metal-Mediated Synthesis, Debye Institute, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands Julien Martz, Laboratoire de Chimie de Coordination Organique, Tectonique Mole  culaire des Solides (CNRS FRE 2423), Universite  Louis Pasteur, Institut Le Bel, F-67070 Strasbourg, France Michel D. Meijer, Department of Metal-Mediated Synthesis, Debye Institute, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands Melanie Pilkington, Department of Chemistry and Biochemistry, University of Berne, Freiestrasse 3, CH-3012 Berne, Switzerland Raffaele Saladino, Dipartimento di Agribiologia e Agrochimica, Universita Á degli Studi della Tuscia, Via S. Camillo de Lillis, s.n.c., 01100 Viterbo, Italy Gerard van Koten, Department of Metal-Mediated Synthesis, Debye Institute, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands Jon A. Zubieta, Department of Chemistry, Syracuse University, Syracuse, NY 13244, USA viii Contributors Preface Supramolecular chemistry, or chemistry beyond the molecule, has provided a wide canvas for a variety of studies of molecular materials in the solid state. The most orderly manifestations of the solid state are single crystals, and the earlier volume in this series with the present Editor, The Crystal as a Supramolecular Entity, sought to establish that the crystal is the perfect example of a supramolecular assembly, justifying as it were the earlier statements of Dunitz and Lehn in this regard. Six years down the line, the supramolecular paradigm has continued to supply a reliable rubric for establishing the grammar of a new and rapidly growing subject, crystal engineering. The present volume is about crystal engineering, or design, and tries to establish connections between the structures of molecular materials and their properties. Crystal engineering links the domains of intermo- lecular interactions, crystal structures and crystal properties. Without interactions there cannot be structures, and without worthwhile properties as a goal, there cannot be suf®cient reason for designing structures. In the process, many advances have been made in fabricating the nuts and bolts of crystal engineering. This is what is summarised in the present volume. So, if the earlier volume was conceptual in its theme, the present one has more to do with methodology and practice. A major conclusion that emerges from this work is the great utility of de®ning a crystal structure as a network. This is true for all varieties of molecular crystals ranging from simple organics to labyrinthine coordination polymers that incorp- orate both inorganic and organic components. I hesitate to use the term `building block' here, although several of the authors have done so, if only because in the softest of molecular solids, namely the pure organics, the building blocks are themselves pliable. This pliability is chemical rather than mechanical ± a given organic molecule presents many faces to its neighbours and the slightest of modi- ®cations may mean that its recognition pro®le changes drastically. Accordingly, the term `building block' is inappropriate for pure neutral organics, but it may be employed with increasing degrees of con®dence as the intermolecular interactions become stronger and more directional. This, then, is the winning advantage of coordination polymers. The well de®ned coordination environment around the metal atom and the strong, directional nature of its interactions with the organic ligands that surround it mean that not only may a coordination polymer be designed reliably but also that its topological depiction as a network is the most natural one. If coordination bonds to metal centres are robust design elements, the hydrogen bond or hydrogen bridge does not lag far behind. This master key of molecular recognition combines strength with suppleness and can be employed in a great many chemical situations. These interactions have been treated in some detail in this volume, in their organic, inorganic and ionic variations. Every stage in the development of the chemical sciences has witnessed much progress with respect to understanding hydrogen bonding and the supramolecular era is no exception. In addition to its use as an exclusive design element, a hydrogen bond may be used along with coordination bonds and even more precise structural control is obtained. Such combinations of interactions are always more effective than single interactions, however strong the latter may be. In the most favourable synergies, supramolecular synthons are obtained that may used with the highest levels of con®dence in crystal engineering. What now of properties? Does crystal engineering lose its innate character when the designed materials do not have any obvious property? Surely not ± for how does one write a poem if one does not know how to arrange words together? The grammar of crystal design is devilishly complex. Most crystal structures, even those of coordination polymers, are not modular. The building blocks continue to twist and turn and interaction interference is always a danger. This, then, is the real goal of the subject ± to identify systems that are modular, wherein a family of related molecules will yield a family of related crystal structures. Hierarchy is still elusive in most cases because of the supramolecular nature of the systems employed, and with the further complication that crystallisation is a kinetically controlled process rather than a thermodynamic one, issues of modularity and hierarchy will be the most dif®cult challenges for the crystal engineer for some time to come. Despite these limitations, and they are formidable ones, consider- able progress has been made with respect to property design. The present volume describes materials that act as sensors, catalysts, microporous substances and molecular magnets. Polymorphism is addressed in this volume, although it is still deemed by most to be too intractable an issue with respect to design of either form or function. Crystal engineering, which has now grown comfortably out of its organic origins to include inorganic compounds within its ambit, will no doubt further extend its scope from single crystals to micro- and nanocrystalline materials and to crystals of lower dimensionalities, and with this the transition from structure to x Preface