International Tables for Crystallography, Volume A1: Symmetry relations between space groups [A1, 2 ed.] 9780470660799

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INTERNATIONAL TABLES FOR CRYSTALLOGRAPHY

Volume A1 SYMMETRY RELATIONS BETWEEN SPACE GROUPS

Edited by ¨ LLER H. WONDRATSCHEK AND U. MU Second Edition

Published for

THE INTERNATIONAL UNION OF C RYSTALLOG RAPHY by

2010

Dedicated to Paul Niggli and Carl Hermann

In 1919, Paul Niggli (1888– 1953) published the first compilation of space groups in a form that has been the basis for all later space-group tables, in particular for the first volume of the trilingual series Internationale Tabellen zur Bestimmung von Kristallstrukturen (1935), for International Tables for X-ray Crystallography Volume I (1952) and for International Tables for Crystallography Volume A (1983). The tables in his book Geometrische Kristallographie des Diskontinuums (1919) contained the lists of the Punktlagen, now known as Wyckoff positions. He was a great universal geoscientist, his work covering all fields from crystallography to petrology. Carl Hermann (1898–1961) published among his seminal works four famous articles in the series Zur systematischen Strukturtheorie I to IV in Z. Kristallogr. 68 (1928) and 69 (1929). The first article contained the background to the Hermann–Mauguin space-group symbolism. The last article was fundamental to the theory of subgroups of space groups and forms the basis of the maximalsubgroup tables in the present volume. In addition, he was the editor of the first volume of the trilingual series Internationale Tabellen zur Bestimmung von Kristallstrukturen (1935) and one of the founders of n-dimensional crystallography, n > 3.

Contributing authors M. I. Aroyo: Departamento de Fı´sica de la Materia Condensada, Facultad de Ciencia y Tecnologı´a, Universidad del Paı´s Vasco, Apartado 644, E-48080 Bilbao, Spain. [Computer production of Parts 2 and 3, 1.1, 1.7, 2.1, 2.2, 2.3]

P. B. Konstantinov: Institute for Nuclear Research and Nuclear Energy, 72 Tzarigradsko Chaussee, BG-1784 Sofia, Bulgaria. [Computer production of Parts 2 and 3]

Y. Billiet‡: De´partement de Physique, UFR des Sciences et Techniques, Universite´ de Bretagne Occidentale, F-29200 Brest, France. [2.1.5, 2.2, 2.3]

E. B. Kroumova: Departamento de Fı´sica de la Materia Condensada, Facultad de Ciencia y Tecnologı´a, Universidad del Paı´s Vasco, Apartado 644, E-48080 Bilbao, Spain. [Computer production of Parts 2 and 3]

C. Capillas: Departamento de Fı´sica de la Materia Condensada, Facultad de Ciencia y Tecnologı´a, Universidad del Paı´s Vasco, Apartado 644, E-48080 Bilbao, Spain. [1.7]

U. Mu¨ller: Fachbereich Chemie, Philipps-Universita¨t, D-35032 Marburg, Germany. [Computer production of Parts 2 and 3, 1.1, 1.5, 1.6, 3, Appendix]

F. Ga¨hler: Fakulta¨t fu¨r Mathematik, Universita¨t Bielefeld, Postfach 100131, D-33501 Bielefeld, Germany. [1.3]

G. Nebe: Lehrstuhl D fu¨r Mathematik, Rheinisch-Westfa¨lische Technische Hochschule, D-52062 Aachen, Germany. [1.4]

V. Gramlichx: Laboratorium fu¨r Kristallographie, Eidgeno¨ssische Technische Hochschule, Sonnegstrasse 5, ETH-Zentrum, CH-8092 Zu¨rich, Switzerland. [2.4, 2.5]

J. M. Perez-Mato: Departamento de Fı´sica de la Materia Condensada, Facultad de Ciencia y Tecnologı´a, Universidad del Paı´s Vasco, Apartado 644, E-48080 Bilbao, Spain. [1.7]

A. Kirov: Faculty of Physics, University of Sofia, bulvd. J. Boucher 5, BG-1164 Sofia, Bulgaria. [Computer production of Parts 2 and 3]

H.

Wondratschek: Laboratorium fu¨r Applikationen der Synchrotronstrahlung, Karlsruher Institut fu¨r Technologie (KIT), D-76128 Karlsruhe, Germany. [1.1, 1.2, 1.7, 2, Appendix]

‡ Present address: 8 place des Jonquilles, F-29860 Bourg-Blanc, France. x Present address: Guggachstrasse 24, CH-8057 Zu¨rich, Switzerland.

Acknowledgments and technicians at the Institut fu¨r Kristallographie, Universita¨t Karlsruhe, around 1970. M. I. Aroyo rechecked the graphs and transformed the hand-drawn versions into computer graphics. We are grateful to Dr L. L. Boyle, University of Kent, Canterbury, England, who read, commented on and improved all parts of the text, in particular the English. We thank Professors J. M. Perez-Mato and G. Madariaga, Universidad del Paı´s Vasco, Bilbao, for many helpful discussions on the content and the presentation of the data. M. I. Aroyo would like to note that most of his contribution to this volume was made during his previous appointment in the Faculty of Physics, University of Sofia, Bulgaria, and he is grateful to his former colleagues, especially Drs J. N. Kotzev and M. Mikhov, for their interest and encouragement during this time. We are indebted to Dr G. Nolze, Bundesanstalt fu¨r Materialforschung, Berlin, Germany, for checking the data of Chapter 3.2 using his computer program POWDER CELL. We also thank Mrs S. Funke and Mrs H. Sippel, Universita¨t Kassel, Germany, who rechecked a large part of the relations of the Wyckoff positions in this chapter. Mrs S. E. Barnes and the rest of the staff of the International Union of Crystallography in Chester, in particular Dr N. J. Ashcroft, took care of the successful technical production of this volume. We gratefully acknowledge the financial support received from various organizations which helped to make this volume possible: in the early stages of the project from the Deutsche Forschungsgemeinschaft, Germany, and more recently from the Alexander von Humboldt-Stiftung, Germany, the International Union for Crystallography, the Sofia University Research Fund and the Universidad del Paı´s Vasco, Bilbao.

Work on Parts 1 and 2 of this volume was spread out over a long period of time and there have been a number of colleagues and friends who have helped us in the preparation of this book. We are particularly grateful to Professor Th. Hahn, RWTH Aachen, Germany, not only for providing the initial impetus for this work but also for his constant interest and support. His constructive proposals on the arrangement and layout of the tables of Part 2 improved the presentation of the data and his stimulating comments contributed considerably to the content and the organization of Part 1, particularly Chapter 1.2. Chapter 1.1 contains a contribution by Professor Y. Billiet, Bourg-Blanc, France, concerning isomorphic subgroups. Nearly all contributors to this volume, but particularly Professors J. Neubu¨ser and W. Plesken, RWTH Aachen, and Professor M. I. Aroyo commented on Chapter 1.2, correcting the text and giving valuable advice. Section 1.2.7 was completely reworked after intensive discussions with Professor V. Janovec, University of Liberec, Czech Republic, making use of his generously offered expertise in the field of domains. We thank Professor H. Ba¨rnighausen, Universita¨t Karlsruhe, Germany, for discussions and advice on Chapter 1.6. In the late 1960s and early 1970s, J. Neubu¨ser and his team at RWTH Aachen calculated the basic lattices of non-isomorphic subgroups by computer. The results now form part of the content of the tables of Chapters 2.2 and 2.3. The team provided a great deal of computer output which was used for the composition of earlier versions of the present tables and for their checking by hand. The typing and checking of the original tables was done with great care and patience by Mrs R. Henke and many other members of the Institut fu¨r Kristallographie, Universita¨t Karlsruhe. The graphs of Chapters 2.4 and 2.5 were drawn and checked by Professor W. E. Klee, Dr R. Cruse and numerous students

vi

Contents PAGE

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Computer production of Parts 2 and 3 (P. Konstantinov, A. Kirov, E. B. Kroumova, M. I. Aroyo and U. Mu¨ller) .. .. .. .. .. ..

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List of symbols and abbreviations used in this volume .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

xii

Foreword (Th. Hahn)

Scope of this volume (M. I. Aroyo, U. Mu¨ller and H. Wondratschek)

PART 1. SPACE GROUPS AND THEIR SUBGROUPS .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

2

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2

1.1.2. Symmetry and crystal-structure determination .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

2

1.1. Historical introduction (M. I. Aroyo, U. Mu¨ller and H. Wondratschek) 1.1.1. The fundamental laws of crystallography

1.1.3. Development of the theory of group–subgroup relations .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

3

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1.2. General introduction to the subgroups of space groups (H. Wondratschek) .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.2.1. General remarks .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.2.2. Mappings and matrices .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.2.3. Groups .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.2.4. Subgroups .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.2.7. Application to domain structures .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.2.8. Lemmata on subgroups of space groups .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.1.4. Applications of group–subgroup relations

1.2.5. Space groups

1.2.6. Types of subgroups of space groups

1.3. Computer checking of the subgroup data (F. Ga¨hler) 1.3.1. Introduction

1.3.2. Basic capabilities of the Cryst package

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1.4.3. Groups .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.3.3. Computing maximal subgroups 1.3.4. Description of the checks

1.4. The mathematical background of the subgroup tables (G. Nebe) 1.4.1. Introduction

1.4.2. The affine space

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1.4.5. Maximal subgroups

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1.4.6. Quantitative results

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1.4.7. Qualitative results

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1.5.2. Derivative structures and phase transitions .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.6. Relating crystal structures by group–subgroup relations (U. Mu¨ller) .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.6.5. Handling cell transformations .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.4.4. Space groups

1.4.8. Minimal supergroups

1.5. Remarks on Wyckoff positions (U. Mu¨ller)

1.5.1. Crystallographic orbits and Wyckoff positions

1.5.3. Relations between the positions in group–subgroup relations

1.6.1. Introduction

1.6.2. The symmetry principle in crystal chemistry 1.6.3. Ba¨rnighausen trees

1.6.4. The different kinds of symmetry relations among related crystal structures

vii

CONTENTS .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.6.6. Comments concerning phase transitions and twin domains 1.6.7. Exercising care in the use of group–subgroup relations

1.7. The Bilbao Crystallographic Server (M. I. Aroyo, J. M. Perez-Mato, C. Capillas and H. Wondratschek) 1.7.1. Introduction

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1.7.3. Group–subgroup and group–supergroup relations between space groups .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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1.7.2. Databases and retrieval tools

1.7.4. Relations of Wyckoff positions for a group–subgroup pair of space groups

PART 2. MAXIMAL SUBGROUPS OF THE PLANE GROUPS AND SPACE GROUPS .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

2.1. Guide to the subgroup tables and graphs (H. Wondratschek and M. I. Aroyo)

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2.1.1. Contents and arrangement of the subgroup tables .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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2.1.3. I Maximal translationengleiche subgroups (t-subgroups) .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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2.1.4. II Maximal klassengleiche subgroups (k-subgroups)

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2.1.2. Structure of the subgroup tables

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2.1.5. Series of maximal isomorphic subgroups (Y. Billiet) .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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2.2. Tables of maximal subgroups of the plane groups (Y. Billiet, M. I. Aroyo and H. Wondratschek)

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2.3. Tables of maximal subgroups of the space groups (Y. Billiet, M. I. Aroyo and H. Wondratschek)

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115

2.4. Graphs for translationengleiche subgroups (V. Gramlich and H. Wondratschek) .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

433

2.1.6. The data for minimal supergroups

2.1.7. Derivation of the minimal supergroups from the subgroup tables 2.1.8. The subgroup graphs

2.4.1. Graphs of the translationengleiche subgroups with a cubic summit

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2.4.2. Graphs of the translationengleiche subgroups with a tetragonal summit

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2.4.3. Graphs of the translationengleiche subgroups with a hexagonal summit

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447

2.4.4. Graphs of the translationengleiche subgroups with an orthorhombic summit 2.5. Graphs for klassengleiche subgroups (V. Gramlich and H. Wondratschek)

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450

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453

2.5.1. Graphs of the klassengleiche subgroups of monoclinic and orthorhombic space groups 2.5.2. Graphs of the klassengleiche subgroups of tetragonal space groups 2.5.3. Graphs of the klassengleiche subgroups of trigonal space groups 2.5.4. Graphs of the klassengleiche subgroups of hexagonal space groups

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460

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2.5.5. Graphs of the klassengleiche subgroups of cubic space groups .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

462

PART 3. RELATIONS BETWEEN THE WYCKOFF POSITIONS 3.1. Guide to the tables (U. Mu¨ller) .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

466

3.1.1. Arrangement of the entries .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

466

3.1.2. Cell transformations .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

468

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468

3.1.4. Nonconventional settings of orthorhombic space groups .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

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763

3.1.3. Origin shifts

3.1.5. Conjugate subgroups

3.1.6. Monoclinic and triclinic subgroups

3.2. Tables of the relations of the Wyckoff positions (U. Mu¨ller)

Appendix. Differences in the presentation of Parts 2 and 3 (U. Mu¨ller and H. Wondratschek) Subject index

viii

Foreword By Th. Hahn

subgroup types and for IIc only the subgroups of lowest index were given. All these data were presented in the form known in 1983, and this involved certain omissions and shortcomings in the presentation, e.g. no Wyckoff positions of the subgroups and no conjugacy relations were given. Meanwhile, both the theory of subgroups and its application have made considerable progress, and the present Volume A1 is intended to fill the gaps left in Volume A and present the ‘complete story’ of the sub- and supergroups of space groups in a comprehensive manner. In particular, all maximal subgroups of types I, IIa and IIb are listed individually with the appropriate transformation matrices and origin shifts, whereas for the infinitely many maximal subgroups of type IIc expressions are given which contain the complete characterization of all isomorphic subgroups for any given index. In addition, the relations of the Wyckoff positions for each group–subgroup pair of space groups are listed for the first time in the tables of Part 3 of this volume. In the second edition of Volume A1 (2010), additional aspects of group–subgroup relations are included; in particular procedures for the derivation of the minimal supergroups of the space groups are described. Now the minimal supergroups can be calculated from the data for the maximal subgroups to the full extent, with the exception of the low-symmetry (triclinic and monoclinic) space groups. Two new chapters on trees of group– subgroup relations (Ba¨rnighausen trees) and on the Bilbao Crystallographic Server bring these tools closer to the user. Volume A1 is thus a companion to Volume A, and the editors of both volumes have cooperated closely on problems of symmetry for many years. I wish Volume A1 the same acceptance and success that Volume A has enjoyed.

Symmetry and periodicity are among the most fascinating and characteristic properties of crystals by which they are distinguished from other forms of matter. On the macroscopic level, this symmetry is expressed by point groups, whereas the periodicity is described by translation groups and lattices, and the full structural symmetry of crystals is governed by space groups. The need for a rigorous treatment of space groups was recognized by crystallographers as early as 1935, when the first volume of the trilingual series Internationale Tabellen zur Bestimmung von Kristallstrukturen appeared. It was followed in 1952 by Volume I of International Tables for X-ray Crystallography and in 1983 by Volume A of International Tables for Crystallography (fifth edition 2002). As the depth of experimental and theoretical studies of crystal structures and their properties increased, particularly with regard to comparative crystal chemistry, polymorphism and phase transitions, it became apparent that not only the space group of a given crystal but also its ‘descent’ and ‘ascent’, i.e. its sub- and supergroups, are of importance and have to be derived and listed. This had already been done in a small way in the 1935 edition of Internationale Tabellen zur Bestimmung von Kristallstrukturen with the brief inclusion of the translationengleiche subgroups of the space groups (see the first volume, pp. 82, 86 and 90). The 1952 edition of International Tables for X-ray Crystallography did not contain sub- and supergroups, but in the 1983 edition of International Tables for Crystallography the full range of maximal subgroups was included (see Volume A, Section 2.2.15): translationengleiche (type I) and klassengleiche (type II), the latter subdivided into ‘decentred’ (IIa), ‘enlarged unit cell’ (IIb) and ‘isomorphic’ (IIc) subgroups. For types I and IIa, all subgroups were listed individually, whereas for IIb only the

ix

Scope of this volume By Mois I. Aroyo, Ulrich Mu¨ller and Hans Wondratschek

In this second edition all misprints and errors found up to now have been corrected and the number of illustrating examples has been increased. In addition, a few changes and extensions have been introduced to facilitate the use of the volume and to extend its range:

Group–subgroup relations between space groups, the primary subject of this volume, are an important tool in crystallographic, physical and chemical investigations of solids. These relations are complemented by the corresponding relations between the Wyckoff positions of the group–subgroup pairs. The basis for these tables was laid by the pioneering papers of Carl Hermann in the late 1920s. Some subgroup data were made available in Internationale Tabellen zur Bestimmung von Kristallstrukturen (1935), together with a graph displaying the symmetry relations between the crystallographic point groups. Since then, the vast number of crystal structures determined and improvements in experimental physical methods have directed the interest of crystallographers, physicists and chemists to the problems of structure classification and of phase transitions. Methods of computational mathematics have been developed and applied to the problems of crystallographic group theory, among them to the group–subgroup relations. When the new series International Tables for Crystallography began to appear in 1983, the subgroup data that were then available were included in Volume A. However, these data were incomplete and their description was only that which was available in the late 1970s. This is still the case in the present (fifth) edition of Volume A. The subgroup data for the space groups are now complete and form the basis of this volume. After introductory chapters on group-theoretical aspects of space groups, on group–subgroup relations and on the underlying mathematical background, this volume provides the reader with:

(7) The subgroup tables, in particular those of the isomorphic subgroups, have been homogenized. (8) The data for the minimal supergroups are sufficient to derive all minimal supergroups starting from the subgroup data, with the exception of the translationengleiche supergroups of triclinic and monoclinic space groups. The procedures by which this derivation can be achieved are described in detail. The supergroup data are useful for the prediction of hightemperature phase transitions, including the search for new ferroelectric and/or ferroelastic materials, for the treatment of the problem of overlooked symmetry in structure determination and for the study of phase transitions in which a hypothetical parent phase plays an important role. (9) A new chapter is devoted to the construction of family trees connecting crystal structures (Ba¨rnighausen trees). In a Ba¨rnighausen tree the relations between the Wyckoff positions occupied in the different crystal structures are accompanied by the relations between the corresponding group–subgroup pairs of space groups. Such trees display the additional degrees of freedom for the structural parameters of the low-symmetry phases: (a) the possibility of distortions due to reduction of site symmetries; (b) chemical variations (atomic substitutions) allowed for atomic positions that have become symmetryindependent.

(1) Complete listings of all maximal non-isomorphic subgroups for each space group, not just by type but individually, including their general positions or their generators, their conjugacy relations and transformations to their conventional settings. (2) Listings of the maximal isomorphic subgroups with index 2, 3 or 4 individually in the same way as for non-isomorphic subgroups. (3) Listings of all maximal isomorphic subgroups as members of infinite series, but with the same information as for the nonisomorphic subgroups. (4) The listings of Volume A for the non-isomorphic supergroups for all space groups. (5) Two kinds of graphs for all space groups displaying their types of translationengleiche subgroups and their types of non-isomorphic klassengleiche subgroups. (6) Listings of all the Wyckoff positions for each space group with their splittings and/or site-symmetry reductions if the symmetry is reduced to that of a maximal subgroup. These data include the corresponding coordinate transformations such that the coordinates in the subgroup can be obtained directly from the coordinates in the original space group.

Ba¨rnighausen trees visualize in a compact manner the structural relations between different polymorphic modifications involved in a phase transition and enable the comparison of crystal structures and their classification into crystal-structure types. (10) A new chapter is dedicated to the Bilbao Crystallographic Server, http://www.cryst.ehu.es/. The server offers freely accessible crystallographic databases and computer programs, in particular those related to the contents of this volume. The available computer tools permit the studies of general group–subgroup relations between space groups and the corresponding Wyckoff positions. The data in this volume are indispensable for a thorough analysis of phase transitions that do not involve drastic structural changes: the group–subgroup relations indicate the possible symmetry breaks that can occur during a phase transition and are essential for determining the symmetry of the driving mechanism and the related symmetry of the resulting phase. The group– subgroup graphs describing the symmetry breaks provide information on the possible symmetry modes taking part in the transition and allow a detailed analysis of domain structures and twins.

x

Computer production of Parts 2 and 3 By Preslav Konstantinov, Asen Kirov, Eli B. Kroumova, Mois I. Aroyo and Ulrich Mu¨ller

The different types of data in the LATEX 2" files were either keyed by hand or computer-generated. The preparation of the data files of Part 2 can be summarized as follows:

The tables of this volume were produced electronically using the LATEX 2" typesetting system [Lamport (1994). A Document Preparation System. 2nd ed. Reading: Addison-Wesley], which has the following advantages:

(i) Headline, origin: hand-keyed. (ii) Generators: hand-keyed. (iii) General positions: created by a program from a set of generators. The algorithm uses the well known generating process for space groups based on their solvability property, cf. Section 8.3.5 of IT A. (iv) Maximal subgroups: hand-keyed. The data for the subgroup generators (or general-position representatives for the cases of translationengleiche subgroups and klassengleiche subgroups with ‘loss of centring translations’), for transformation matrices and for conjugacy relations between subgroups were checked by specially designed computer programs. (v) Minimal supergroups: created automatically from the data for maximal subgroups.

(1) correcting and modifying the layout and the data are easy; (2) correcting or updating these for further editions of this volume should also be simple; (3) the cost of production for the first edition and later editions should be kept low. A separate data file was created for every space group in each setting listed in the tables. These files contained only the information about the subgroups and supergroups, encoded using specially created LATEX 2" commands and macros. These macros were defined in a separate package file which essentially contained the algorithm for the layout. Keeping the formatting information separate from the content as much as possible allowed us to change the layout by redefining the macros without changing the data files. This was done several times during the production of the tables. The data files are relatively simple and only a minimal knowledge of LATEX 2" is required to create and revise them should it be necessary later. A template file was used to facilitate the initial data entry by filling blank spaces and copying pieces of text in a text editor. It was also possible to write computer programs to extract the information from the data files directly. Such programs were used for checking the data in the files that were used to typeset the volume. The data prepared for Part 2 were later converted into a more convenient, machine-readable format so that they could be used in the database of the Bilbao Crystallographic Server at http://www.cryst.ehu.es/. The final composition of all plane-group and space-group tables of maximal subgroups and minimal supergroups was done by a single computer job. References in the tables from one page to another were automatically computed. The run takes 1 to 2 minutes on a modern workstation. The result is a PostScript or pdf file which can be fed to most laser printers or other modern printing/typesetting equipment. The resulting files were also used for the preparation of the fifth edition of International Tables for Crystallography Volume A (2002) (abbreviated as IT A). Sections of the data files of Part 2 of the present volume were transferred directly to the data files for Parts 6 and 7 of IT A to provide the subgroup and supergroup information listed there. The formatting macros were rewritten to achieve the layout used in IT A.

The electronic preparation of the subgroup tables of Part 2 was carried out on various Unix- and Windows-based computers in Sofia, Bilbao, Stuttgart and Karlsruhe. The development of the computer programs and the layout macros in the package file was done in parallel by different members of the team. Th. Hahn (Aachen) contributed to the final arrangement of the data. The tables of Part 3 have a different layout, and a style file of their own was created for their production. Again, separate data files were prepared for every space group, containing only the information concerning the subgroups. The macros of the style file were developed by U. Mu¨ller, who also hand-keyed all files over the course of seven years. Most of the data of Part 2 were checked using computer programs developed by F. Ga¨hler (cf. Chapter 1.3) and A. Kirov. The relations of the Wyckoff positions (Part 3) were checked by G. Nolze (Berlin) with the aid of his computer program POWDER CELL [Nolze (1996). POWDER CELL. Computer program for the calculation of X-ray powder diagrams. Bundesanstalt fu¨r Materialforschung, Berlin]. In addition, all relations were cross-checked with the program WYCKSPLIT [Kroumova et al. (1998). J. Appl. Cryst. 31, 646; http://www. cryst.ehu.es/cryst/wpsplit.html], with the exception of the positions of high multiplicities of some cubic space groups with subgroup indices > 50, which could not be handled by the program.

xi

List of symbols and abbreviations used in this volume By Mois I. Aroyo, Ulrich Mu¨ller and Hans Wondratschek (1) Points and point space

(4) Groups

P, Q, R, X O An ; An ; Pn En ; En x; y; z; or xi x X~ x~ x~ i x0

G R H; U M M P; S; V; Z T ðGÞ; T ðRÞ A E

x0i

points origin n-dimensional affine space n-dimensional Euclidean point space point coordinates column of point coordinates image point column of coordinates of an image point coordinates of an image point column of coordinates in a new coordinate system (after basis transformation) coordinates in a new coordinate system

F I N O

(2) Vectors and vector space a, b, c; or ai r, x o a, b, c , , ; or j r ri (a)T Vn

NG ðHÞ NE ðHÞ NA ðHÞ PG ; PH SG ðXÞ; SH ðXÞ

basis vectors of the space vectors, position vectors zero vector (all coefficients zero) lattice lengths of basis vectors parameters angles between basis vectors column of vector coefficients vector coefficients row of basis vectors n-dimensional vector space

a; b ; g ; h; m; t e

2; 21 ; m; 1; . . . i or [i]

group; space group space group (Chapter 1.4) subgroups of G maximal subgroup of G (Chapter 1.4) Hermann’s group (Chapters 1.2, 1.7, 2.1) groups or sets of group elements, e.g. cosets group of all translations of G; R group of all affine mappings = affine group group of all isometries (motions) = Euclidean group factor group trivial group, consisting of the unit element e only normal subgroup group of all orthogonal mappings = orthogonal group normalizer of H in G Euclidean normalizer of H affine normalizer of H point groups of the space groups G, H site-symmetry groups of point X in the space groups G, H group elements unit element symmetry operations index of H in G

(5) Symbols used in the tables p n, n0 , n00 , n000 q, r, u, v, w a, b, c a0 , b0 , c 0 x, y, z t(1, 0, 0), t(0, 1, 0), . . .

(3) Mappings and their matrices and columns A, W (3  3) matrices T A matrix A transposed I (3  3) unit matrix Aik, Wik coefficients (A, a), (W, w) matrix–column pairs W augmented matrix x; x~ ; t augmented columns P, P transformation matrices A; I ; W mappings w column of the translation part of a mapping wi coefficients of the translation part of a mapping fundamental matrix and its coefficients G, Gik det( . . . ) determinant of a matrix tr( . . . ) trace of a matrix

prime number > 1 arbitrary positive integer numbers arbitrary integer numbers in the given range basis vectors of the space group basis vectors of the subgroup or supergroup point coordinates in the space group generating translations

(6) Abbreviations HM symbol IT A PCA k-subgroup t-subgroup

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Hermann–Mauguin symbol International Tables for Crystallography Volume A parent-clamping approximation klassengleiche subgroup translationengleiche subgroup

International Tables for Crystallography (2011). Vol. A1, Chapter 1.1, pp. 2–6.

1.1. Historical introduction By Mois I. Aroyo, Ulrich Mu¨ller and Hans Wondratschek

concepts of unit cell and of translation symmetry were thus introduced implicitly. The classification of the 14 underlying lattices of translations was completed by Auguste Bravais (1850). In the second half of the nineteenth century, interest turned to the derivation and classification of infinite regular systems of points or figures, in particular by Leonhard Sohncke and Evgraf Stepanovich Fedorov. Sohncke (1879), Fedorov (1891), Arthur Schoenflies (1891) and later William Barlow (1894) turned to the investigation of the underlying groups, the space groups and plane groups. The derivation and classification of these groups were completed in the early 1890s. It was a plausible hypothesis that the structures of crystals were related to combinations of regular systems of atoms (Haag, 1887) and that the symmetry of a crystal structure should be a space group, but both conjectures were speculations at that time with no experimental proof. This also applies to the atom packings described by Sohncke and Barlow, such as a model of the NaCl structure (which they did not assign to any substance).

1.1.1. The fundamental laws of crystallography The documentation concerning group-theoretical aspects of group–subgroup relations and the rising importance of these relations in three-dimensional crystallography is scattered widely in the literature. This short review, therefore, cannot be exhaustive and may even be unbalanced if the authors have missed essential sources. Not included here is the progress made in the general theory of crystallographic groups, e.g. in higher dimensions, which is connected with the names of the mathematicians and physicists Ascher, Brown, Janner, Janssen, Neubu¨ser, Plesken, Souvignier, Zassenhaus and others. This volume A1 of International Tables for Crystallography, abbreviated IT A1, is concerned with objects belonging to the ‘classical’ theory of crystallographic groups. For a long time, the objective of crystallography, as implied by the word itself, was the description of crystals which were found in nature or which grew from solutions of salts or from melts. Crystals often display more-or-less planar faces which are symmetrically equivalent or can be made so by parallel shifting of the faces along their normals such that they form a regular body. The existence of characteristic angles between crystal faces was observed by Niels Stensen in 1669. The importance of the shape of crystals and their regularity was supported by observations on the cleavage of crystals. It was in particular this regularity which attracted mineralogists, chemists, physicists and eventually mathematicians, and led to the establishment of the laws by which this regularity was governed. The law of symmetry and the law of rational indices were formulated by Rene´ Just Hau¨y around 1800. These studies were restricted to the shape of macroscopic crystals and their physical properties, because only these were accessible to measurements until the beginning of the twentieth century. Later in the nineteenth century, interest turned to ‘regular systems’ of points, for which the arrangement of points around every point is the same. These were studied by Wiener (1863) and Sohncke (1874). For such sets, there are isometric mappings of any point onto any other point which are such that they map the whole set onto itself. The primary aim was the classification and listing of such regular systems, while the groups of isometries behind these systems were of secondary importance. These regular systems were at first the sets of crystal faces, of face normals of crystal faces and of directions in crystals which are equivalent with respect to the physical properties or the symmetry of the external shape of the crystal. The listing and the classification of these finite sets was based on the law of rational indices and resulted in the derivation of the 32 crystal classes of point groups by Moritz Ludwig Frankenheim in 1826, Johann Friedrich Christian Hessel in 1830 and Axel V. Gadolin in 1867, cited by Burckhardt (1988). The list of this classification contained crystal classes that had not been observed in any crystal and included group–subgroup relations implicitly. Crystal cleavage led Hau¨y in 1784 to assume small parallelepipeds as building blocks of crystals. In 1824, Ludwig August Seeber explained certain physical properties of crystals by placing molecules at the vertices of the parallelepipeds. The Copyright © 2011 International Union of Crystallography

1.1.2. Symmetry and crystal-structure determination In 1895, Wilhelm Ro¨ntgen, then at the University of Wu¨rzburg, discovered what he called X-rays. Medical applications emerged the following year, but it was 17 years later that Max von Laue suggested at a scientific discussion in Munich that a crystal should be able to act as a diffraction grating for X-rays. Two young physicists, Walther Friedrich and Paul Knipping, successfully performed the experiment in May 1912 with a crystal of copper sulfate. In von Laue’s opinion, the experiment was so important that he later publicly donated one third of his 1914 Nobel prize to Friedrich and Knipping. The discovery immediately aroused the curiosity of father William Henry Bragg and son William Lawrence Bragg. The son’s experiments in Cambridge, initially with NaCl and KCl, led to the development of the Bragg equation and to the first crystal-structure determinations of diamond and simple inorganic materials. Since then, the determination of crystal structures has been an ever-growing enterprise. The diffraction of X-rays by crystals is partly determined by the space group and partly by the relative arrangement of the atoms, i.e. by the atomic coordinates and the lattice parameters. The presentations by Fedorov and Schoenflies of the 230 space groups were not yet appropriate for use in structure determinations with X-rays. The breakthrough came with the fundamental book of Paul Niggli (1919), who described the space groups geometrically by symmetry elements and point positions and provided the first tables of what are now called Wyckoff positions. Niggli emphasized the importance of the multiplicity and site symmetry of the positions and demonstrated with examples the meaning of the reflection conditions. Niggli’s book pointed the way. The publication of related tables by Ralph W. G. Wyckoff (1922) included diagrams of the unit cells with special positions and symmetry elements. Additional tables by Astbury & Yardley (1924) listed ‘abnormal

2

1.1. HISTORICAL INTRODUCTION spacings’ for the space groups, i.e. the reflection conditions. These tables made the concepts and the data of geometric crystallography widely available and were the basis for the series Internationale Tabellen zur Bestimmung von Kristallstrukturen (1935) (abbreviated as IT 35), International Tables for X-ray Crystallography, Vol. I (1952, 1965, 1969) (abbreviated as IT 52) and International Tables for Crystallography, Vol. A (1983 and subsequent editions 1987, 1992, 1995, 2002, 2005) (abbreviated as IT A). Group–subgroup relations were used in the original derivation of the space groups and plane groups. However, in the first decades of crystal-structure determinations, the derivation of geometric data (atomic coordinates) was of prime importance and the group-theoretical information in the publications was small, although implicitly present. With the growing number of crystal structures determined, however, it became essential to understand the rules and laws of crystal chemistry, to classify the incomprehensible set of structures into crystal-structure types, to develop methods for ordering the structure types in a systematic way, to show relations among them and to find common underlying principles. To this end, different approaches were presented over time. By 1926, the number of crystal structures was already large enough for Viktor Moritz Goldschmidt to formulate basic principles of packing of atoms and ions in inorganic solids (Goldschmidt, 1926). Shortly afterwards, Linus Pauling (1928, 1929) formulated his famous rules about ionic radii, valence bonds, coordination polyhedra and the joining of these polyhedra. Later, Wilhelm Biltz (1934) focused attention on the volume requirements of atoms. Many other important factors determining crystal structures, such as chemical bonding, molecular shape, valenceelectron concentration, electronic band structures, crystal-orbital overlap populations and others, have been the subject of subsequent studies. Each one of these aspects can serve as an ordering principle in crystal chemistry, giving insights from a different point of view. For the aspects mentioned above, symmetry considerations are only secondary tools or even unimportant, and group–subgroup relations hardly play a role. Although symmetry is indispensable for the description of a specific crystal structure, for a long time crystal symmetry and the group–subgroup relations involved did not attract much attention as possible tools for working out the relations between crystal structures. This has even been the case for most textbooks on solid-state chemistry and physics. The lack of symmetry considerations is almost a characteristic feature of many of these books. There is a reason for this astonishing fact: the necessary group-theoretical material only became available in a useful form in 1965, namely as a listing of the maximal subgroups of all space groups by Neubu¨ser & Wondratschek. However, for another 18 years this material was only distributed among interested scientists before it was finally included in the 1983 edition of IT A. And yet, even in the printing of 2005, the listing of the subgroups in Volume A is incomplete. It is this present Volume A1 which contains the complete listing.

(I) a nomenclature of the space-group types, a predecessor of the Hermann–Mauguin nomenclature; (II) a method for the derivation of the 230 space-group types which is related to the nomenclature in (I); (III) the derivation of the 75 types of rod groups and the 80 types of layer groups; and (IV) the subgroups of space groups. In paper (IV), Hermann introduced two distinct kinds of subgroups. The translationengleiche subgroups of a space group G have retained all translations of G but belong to a crystal class of lower symmetry than the crystal class of G (Hermann used the term zellengleiche instead of translationengleiche, see footnote 10 in Section 1.2.6). The klassengleiche subgroups are those which belong to the same crystal class as G, but have lost translations compared with G. General subgroups are those which have lost translations as well as crystal-class symmetry. Hermann proved the theorem, later called Hermann’s theorem, that any general subgroup is a klassengleiche subgroup of a uniquely determined translationengleiche subgroup M of G. In particular, this implies that a maximal subgroup of G is either a translationengleiche subgroup or a klassengleiche subgroup of G. Because of the strong relation (homomorphism) between a space group G and its point group P G, the set of translationengleiche subgroups of G is in a one-to-one correspondence with the set of subgroups of the point group P G. The crystallographic point groups are groups of maximal order 48 with well known group–subgroup relations and with not more than 96 subgroups. Thus, the maximal translationengleiche subgroups of any space group G can be obtained easily by comparison with the subgroups of its point group P G. The kind of derivation of the space-group types by H. Heesch (1930) also gives access to translationengleiche subgroups. In IT 35, the