`
`
`
`
`
`
`
`
`
`Exhibit 2033.001
`
`Exhibit 2033.001
`
`

`

`ATLAS
`
`OF ZEOLITE
`
`FRAMEWORK TYPES
`
`Exhibit 2033.002
`
`Exhibit 2033.002
`
`

`

`ATLAS
`
`OF ZEOLITE
`
`FRAMEWORK TYPES
`
`Sixth Revised Edition
`
`dedicated to
`
`Walter M. Meier
`
`co—author of the first edition of the Atlas and
`
`co-founder of the IZA Structure Commission
`
`on the occasion of his 80th birthday
`
`Christian Baerlocher and Lynne B. McCusker
`Laboratory of Crystallography
`ETH Zurich
`
`8093 Zurich, Switzerland
`
`David H. Olson
`
`Department of Chemistry and Chemical Biology
`Rutgers University
`Piscataway, NJ 08854, USA
`
`Published on behalf of the
`
`Structure Commission of the international Zeolite Association by
`
`
`
`Amsterdam — London - New York - Oxford - Paris — Shannon - Tokyo
`
`Exhibit 2033.003
`
`Exhibit 2033.003
`
`

`

`Elsevier
`Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands
`Liname House, Jordan Hill, Oxford OX2 8DP, UK
`
`First edition 1978, published by the Structure Commission of the International Zeolite Association
`Second revised edition, 1987, published by Butterworth—Heinemzmn
`Third revised edition, 1992, published by Butterwonh‘Heinemann
`Fourth revised edition. 1996, published by Elsevier Science
`Fifth revised edition, first impression, 2001, published by Elsevier Science
`Fifth revised edition, second impression 2001, published by Elsevier Science
`Sixth revised edition, first impression 2007
`
`Copyright © 2007 Elsevier B.Vi All rights reserved
`
`No pan of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means electronic, mechanical, pholocopying, recording or
`otherwtse without the prior written permission of the publisher
`Permissions may be sought directly from Elsevier’s Science 8; Technology Rights Department in Oxford, UK: phone (+44%) 10‘) l865 843830; fax H44) (0) 1365 853333:
`\1
`
`email: pcmnssionsttielsevier corn. Alternatiw y you can submit your request onlinc by Visiting the Elsevrer web Slic at hrtp'f/olsevier com/locate/pcrmissions, and selecting
`Obtaining permirrimz lo we Elsevier mammal
`Notice
`No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise. or from any use
`or operation (ii any methods, products. instructions or ideas contained in the material herein Because ot rapid advances in the medical sciences, in particular, independent
`Verification ofdiagnoses and drug dosages shouid be made
`
`Library of Congress Cataloging-invl’ublication Data
`A catalog record for this book is available from the Library of Congress
`
`British Library Cataloguing in Publication Data
`A catalogue record for this book is available from the British Library
`
`ISBN: 978—0—444—53064-6
`
`For information on all Elsevier publications
`
`visit our website at b00ks.elsevier.com
`
`Printed and bound in The Netherlands
`
`070809101110987654321
`
`
`Working together to grow
`libraries in developing countries
`wwwelseviencom [ W‘wbookaidrorg l wwwsabreorg
`Sabre Foundation
`ELSEVIER mama
`
`Exhibit 2033.004
`
`Exhibit 2033.004
`
`

`

`TABLE OF CONTENTS
`
`Preface
`
`Introduction and Explanatory Notes
`
`Framework Type Data Sheets (arranged by 3—lcttcr code in alphabetical order)
`
`1
`
`3
`
`13
`
`ABW
`ACO
`AEI
`AEL
`AEN
`AET
`AFG
`AFI
`
`AFN
`AFO
`AFR
`AFS
`AFT
`AFX
`AFY
`
`AHT
`ANA
`APC
`APD
`
`AST
`ASV
`ATN
`ATO
`ATS
`ATT
`ATV
`AWO
`AWW
`BCT
`*BEA
`BBC
`BIK
`BOG
`BPH
`BRE
`CAN
`CAS
`
`CDO
`CF]
`
`CGF
`CGS
`CHA
`
`-CHI
`-CLO
`CON
`CZP
`DAC
`DDR
`
`Li-A (Barrer and White)
`ACP-l
`AlPO-lS
`AlPO—l l
`AlPO-EN3
`AlPO—8
`Afghanite
`AlPO—S
`
`AlPO—l4
`AlPO—4l
`SAPO-40
`MAPSO—46
`AlPO—SZ
`SAPO-56
`CoAPO« SO
`
`AlPO~H2
`Analcime
`AlPO—C
`AlPO—D
`
`AlPO— l 6
`ASU—7
`MAPO—39
`AIPO-3l
`MAPO-36
`AlPO— l 2-TAMU
`AlPO—25
`AlPO-Zl
`AlPO—ZZ
`Mg—BCTT
`Beta
`FOS-S (Beta polymorph C)
`Bikitaite
`Boggsite
`Beryllophosphate—H
`Brewsterite
`Cancrlnite
`Cesium Aluminosilicate
`
`CDS-l
`CIT—5
`
`Co-Ga-Phosphate—S
`Co—Ga—Phosphate—6
`Chabazite
`
`Chiavennite
`Cloverite
`CIT—l
`Chiral Zincophosphate
`Dachiardite
`Deca-dodecasil 3R
`
`DFO
`DFT
`DOH
`DON
`EAB
`EDI
`EMT
`EON
`
`EPI
`ERI
`ESV
`ETR
`EUO
`EZT
`FAR
`
`FAU
`FER
`FRA
`GIS
`
`GIU
`GME
`GON
`GOO
`HEU
`IFR
`IHW
`IMF
`ISV
`ITE
`ITH
`ITW
`IWR
`IWV
`[WW
`J BW
`KFI
`LAU
`
`LEV
`L10
`
`-LIT
`LOS
`LOV
`
`LTA
`LTL
`LTN
`MAR
`MAZ
`MEI
`
`DAF—l
`DAF—Z
`Dodecasil 1H
`UTD—lF
`TMA—E (Aiello and Barrer)
`Edingtonite
`EMC-Z
`ECR—l
`
`Epistilbite
`Erionite
`HRS—7
`ECR—34
`EU— I
`EMM—3
`Famcseite
`
`Faujasite
`Ferrierite
`Franzinite
`Gismondine
`
`Giuseppettite
`Gmelinite
`GUS—l
`Goosecreekite
`Heulandite
`ITQ-4
`lTQ—32
`IM—5
`ITQ-7
`ITQ—3
`lTQ— l 3
`ITQ— 1'2
`ITQo24
`ITQ—27
`ITQ—ZZ
`Na—J (Barrer and White)
`ZK—S
`Laumontite
`
`Levyne
`Liottite
`
`Lithoslte
`Losod
`Lovdarite
`
`Linde Type A
`Linde Type L
`Linde Type N
`Marinellite
`Mazzite
`ZSM-lS
`
`Exhibit 2033.005
`
`Exhibit 2033.005
`
`

`

`Vi
`
`MEL
`
`MEP
`MER
`MFI
`MFS
`MON
`MOR
`MOZ
`MSE
`MSO
`MTF
`MTN
`
`MTT
`MTW
`MWW
`NAB
`NAT
`NES
`NON
`
`NPO
`NSI
`OBW
`OFF
`OSI
`080
`OWE
`-PAR
`
`PAU
`PHI
`PON
`RHO
`
`-RON
`RRO
`RSN
`RTE
`RTH
`RUT
`RWR
`
`RWY
`SAO
`
`ZSM-ll
`
`Melanophlogite
`Merlinoite
`ZSM—S
`ZSM<57
`Montesommaite
`Mordenite
`ZSM—lO
`MCM-68
`MCM-6l
`MCM-35
`ZSM-39
`
`ZSM-23
`ZSM—IZ
`MCM—22
`Nabesite
`Natrolite
`NU—87
`Nonasil
`
`Nitridophosphate—l
`Nu-6(2)
`OSB—Z
`Offretite
`UiO-6
`088—1
`UiO—28
`Partheite
`
`Paulingite
`Phillipsite
`IST-I
`Rho
`
`Roggianite
`RUB—41
`RUB -17
`RUB-3
`RUB - 13
`RUB- 10
`RUB-24
`
`UCR-ZO
`STA-l
`
`-
`
`SAS
`
`SAT
`SAV
`SBE
`SBS
`SBT
`SFE
`SFF
`SFG
`SFH
`SFN
`SFO
`
`SGT
`SIV
`SOD
`SOS
`SSY
`STF
`ST]
`
`STT
`SZR
`TER
`THO
`TOL
`TON
`TSC
`TUN
`
`UEI
`UFI
`UOZ
`USI
`
`UTL
`VET
`VFI
`VNI
`VSV
`WEI
`-WEN
`
`YUG
`ZON
`
`STA-6
`
`STA—2
`Mg-STA-7
`UCSB«8Co
`UCSB—6GaCo
`UCSB—lOGaZn
`$32—48
`SSZ—44
`$82—58
`SSZ—53
`SSZ—59
`SSZ—Sl
`
`Sigma—2
`SIZ—7
`Sodalite
`SU— 1 6
`SSZ—6O
`SSZ—35
`Stilbite
`
`S SZ—23
`SUZ—4
`Terranovaite
`Thomsonite
`ordered Tounkite
`Theta~l
`Tsehortnerite
`TNU-9
`
`Mu-l 8
`UZM-S
`IM- 10
`IM—6
`
`IM-12
`VPI-8
`VPI—S
`VPI—9
`VPI-7
`Weinebeneite
`Wenkite
`
`Yugawaralite
`ZAPO—Ml
`
`Appendices
`A. Additional information for the data sheets of
`
`CHA, GIS, IMF, IWW, MFI, PAU, TUN, UTL
`
`B, Rules for Framework Type Assignment
`
`C.
`
`Secondary Building Units
`
`D. Composite Building Units
`E. Channel Dimensions
`
`F. Topological Densities
`
`G. Origin of 3—Letter Codes and Type Material Names
`
`Isotypie Material Index
`
`367
`
`371
`
`373
`
`375
`381
`
`387
`
`389
`
`393
`
`Exhibit 2033.006
`
`Exhibit 2033.006
`
`

`

`PREFACE
`
`In this sixth edition of the Atlas of Zeolite Framework Types, data are presented for each of the 176
`
`unique zeolite Framework Types that had been approved and assigned a 3—letter code by the Structure
`Commission of the IZA (IZA—SC) by February 2007. Six years ago, this number was 133. The
`
`number of new verified Framework Types reflects the vibrant activity that persists within the zeolite
`
`community.
`
`In 1970, the paper that can be considered to be the forerunner of the first edition of the
`
`Atlas was published“) and it described the 27 zeolite framework structures known at the time. With
`each edition of the Atlas, this number has grown and the exponential trend continues.
`In that initial
`
`paper, the foundation for a systematic description of zeolite framework structures was laid, and we are
`still using these basic concepts.
`It is with pleasure and gratitude for this pioneering work that we
`dedicate this edition of the Atlas to Walter M. Meier, coauthor of that first Atlas and co—founder of the
`
`Structure Commission of the IZA, on the occasion of his 80th birthday.
`
`Each of the zeolite Framework Types included in this book has been examined by the members of
`
`the IZA—SC to verify that it conforms to the IZA—SC definition of a zeolite, that it is unique, and that
`the structure has been satisfactorily proven. The three-letter code that is then assigned is officially
`
`recognized by IUPAC, and is used in the nomenclature recommended by IUPAC for these materials“)
`The rules used by the IZA-SC are given in Appendix B.
`
`As a frequently quoted work of reference, the Atlas must be updated on a regular basis to be of full
`
`use. Not only must new Framework Types be added, but corrections and new information on existing
`
`entries must also be disseminated. To do this, the IZA-SC maintains a freely available searchable
`
`database on the intemet at http://www.iza—structure.org/databases/. Although all the information in
`
`this book (and more) is available at that website, even the most technologically—minded individuals
`
`will admit that it is sometimes easier to access the desired information in a book. This is why we
`continue to publish a hard copy of the most used data on a periodic basis.
`
`In this edition we have prepared new stereo drawings of all Framework Types, added over 250
`
`references, and for the first time, included some composite building units that are common to more
`
`than one Framework Type. To make room for the latter, we have removed the loop configurations
`
`(still available on the web), reasoning that the vertex symbols provide very similar information. To
`
`minimize errors, the data sheets have all been generated directly from the zeolite database that is used
`for the online version of the Atlas.
`
`We wish to acknowledge the assistance and collaboration of many fellow scientists. who have
`
`provided us with information and suggested improvements. We are particularly indebted to Henk van
`
`Koningsveld, who determined the secondary building units for all
`
`the new frameworks, and the
`
`members of the IZA Structure Commission, who provided additional
`
`information and proofread
`
`tirelessly.
`
`It does not seem to be possible to assemble such a compilation without mistakes or
`
`oversights, so We will be grateful for any corrections and/or additions that you communicate to us.
`
`February 2007
`
`Christian Baerlocher
`
`Lynne B. McCusker
`
`David H. Olson
`
`Exhibit 2033.007
`
`Exhibit 2033.007
`
`

`

`2 S
`
`tructure Commission of the International Zeolite Association
`
`Christian Baerlocher
`
`Allen W. Burton
`
`Werner H. Baur
`
`Robert W. Broach
`
`Douglas L. Dorset
`Reinhard X. Fischer
`
`Hermann Gies
`
`Richard M. Kirchner
`
`Raul F. Lobe
`
`Lynne B. McCusker
`Walter M. Meier***
`
`Russell E. Morris
`
`Wilfried J. Mortier
`
`Michael O'Keeffe
`
`David H. Olson***
`
`Michael MJ. Treacy*
`
`Henk van Koningsveld**
`Osamu Terasaki
`
`* Chairperson
`
`** C0—Chairperson
`
`*** Honorary Life Member
`
`Previous IZA Special Publications:
`
`W.M. Meier and DH. Olson, Atlas oneolite Structure Types (1978)
`
`W.M. Meier and DH. Olson, Atlas oneolite Structure Types, 2nd ed. (1987)
`
`W.M. Meier and DH. Olson, Atlas oneolite Structure Types, 3rd ed. (1992)
`
`W.M. Meier, D.H. Olson and Ch. Baerlocher, Atlas oneolite Structure Types, 4th ed. (1996)
`
`Ch. Baerlocher, W.M. Meier and DH. Olson, Atlas oneo/ite Framework Types, 5th ed. (2001)
`
`W.J. Monier, Compilation ofExtra Framework Sites in Zeolites (1982)
`
`R. von Ballmoos, Collection ofSimulated XRD Powder Patternsfor Zeolites (1984)
`
`R. von Ballmoos and J.B. Higgins, Collection of Simulated XRD Powder Patterns for Zeolites,
`2nd ed. (1990)
`
`M.M.J. Treacy, J‘B. Higgins and R. von Ballmoos, Collection of Simulated XRD Powder
`Patternsfor Zeolites, 3rd ed. (1996)
`
`M.M.J. Treacy and J.B. Higgins, Collection ofSimulated XRD Powder Patterns for Zeolites, 4th
`ed. (2001)
`
`H. Robson and KP. Lillerud, Verified Synthesis of Zeolitic Materials (1998)
`
`Exhibit 2033.008
`
`Exhibit 2033.008
`
`

`

`'43
`
`INTRODUCTION AND EXPLANATORY NOTES
`
`Zeolites and zeolite—like materials do not comprise an easily definable family of crystalline solids.
`
`A simple criterion for distinguishing zeolites and zeolite—like materials from denser tectosilicates is
`based on the framework density (FD),
`the number of tetrahedrally coordinated framework atoms
`(T-atorns) per 1000 A3.
`Figure I shows the distribution of these values for porous and dense
`frameworks, whose structures are well established”). A gap is clearly recognizable between zeolite—
`
`type and dense tetrahedral framework structures. The maximum FD for a zeolite ranges from 19 to
`over 21 Tvatoms per 1000 A3, depending on the type of smallest ring present, whereas the minimum
`for denser structures ranges from 20 to 22. Strictly speaking the boundaries defined in Figure 1 for the
`framework densities only apply to fully crosslinked frameworks, so interrupted frameworks have not
`been included.
`
`For each Framework Type Code (see below), two pages of data are included in this Atlas, The first
`
`page lists the information that characterizes the Framework Type. This includes crystallographic data
`
`(highest possible space group, cell constants of the idealized framework), coordination sequences,
`vertex symbols and composite building units. Taken together, the coordination sequences and the
`
`vertex symbols define the Framework Type. On the second page, data for the Type Material (ie the
`real material on which the idealized Framework Type is based) can be found. Although the channel
`
`the channel description also includes the
`dimensionality is a property of the Framework Type,
`observed ring dimensions, and must therefore refer to the Type Material. For each Framework Type, a
`
`list of isotypic materials with the corresponding references is also given. The different entries in the
`data sheets are described in more detail below.
`
`Framework Type Page
`
`Framework Type Code
`
`Following the rules set up by an IUPAC Commission on Zeolite Nomenclature in 1979““, designations
`consisting of three capital
`letters (in boldface type) have been used throughout. The codes are
`
`generally derived from the names of the Type Materials (see Appendix G) and do not include numbers
`and characters other than capital Roman letters. The assignment of Framework Type Codes is subject
`
`to review and clearance by the IZA Structure Commission according to a decision of the IZA Council
`(taken at the time of the 7th IZC in Tokyo, 1986). Codes are only assigned to established structures
`
`that satisfy the rules of the IZA Structure Commission (see Appendix B for a listing of these rules).
`
`For interrupted frameworks, the 3-letter code is preceded by a hyphen. These mnemonic codes should
`
`not be confused or equated with actual materials. They only describe and define the network of the
`
`corner sharing tetrahedrally coordinated framework atoms. Thus, designations such as NaFAU are
`
`untenable. However, a material can be described using the IUPAC crystal chemical formula”, as
`
`INasgl [Aleh34 03841-FAU or INaal [Al—Si‘01-FAU. Note that the chemical elements must be enclosed
`
`within the appropriate (boldface) brackets (i.e. l
`
`l for guest species and [
`
`] for the framework host)
`
`Exhibit 2033.009
`
`Exhibit 2033.009
`
`

`

`FD
`
`26
`
`24
`
`22
`
`mogkmzc
`
`mm:
`mrdien‘m
`
`banukite
`
`Seapolite
`mracekum, ,
`
`smlm’lrc
`
`qurLl
`
`crix‘uyhalil:
`Lridymtt:
`
`
`
`'
`,
`20 y'" f;
`_
`-
`
`:
`:0;
`
`'
`
`
`
`'
`"
`
`0W7?)
`"MAEN‘:
`
`“33
`
`L:
`
`I?"
`
`L
`
`.
`
`:CrM’l‘F‘,
`o
`
`.
`
`”
`
`' '
`
`O
`
`8
`I
`. o .
`O
`i x H. ..
`g
`° 5 . 0". '
`:
`,
`I
`O
`:1.
`... \MTN:'
`o
`.
`.
`
`|
`
`.
`
`’
`
`.
`
`8
`
`.
`
`(mu!
`. -
`:Wfl')
`‘
`
`,.
`
`e
`
`*
`
`9
`
`i
`
`I
`I
`.
`.
`
`5
`
`'
`
`.
`
`.
`. C
`
`°
`
`O
`.
`
`,-
`
`
`
`18
`
`16
`
`14
`
`12—1
`4
`
`10
`
`8 J
`
`Fig. 1.
`
`Framework density calculated for the idealized SiOZ framework vs. average size of the smallest ring in
`the Structure.
`
`Average Size of Smallest Ring
`
`Exhibit 2033.010
`
`Exhibit 2033.010
`
`

`

`and that the stoichiometry may, but does not have to be specified. Framework Types do not depend on
`
`composition, distribution of the T—atoms (Si, Al, P, Ga, Ge, B, Be, etc.), cell dimensions or symmetry.
`
`The Framework Types have been arranged in alphabetical order according to the Framework Type
`Code, because structural criteria alone do not provide an unambiguous classification scheme. This
`
`also facilitates later insertion of new codes and allows simple indexing. The Framework Type Code is
`
`given at the top of each page. On the first page this is supplemented with the maximum space group
`
`symmetry for the framework, and on the second page with the full name of the Type Material.
`
`In this
`
`edition, the new designation "8" in space groups with doubleglide planes has been used (e.g. Cmma is
`now Cmme).
`
`Framework drawing
`
`A stereographic drawing of the framework, generated using the program CrystalMakerm is
`presented for each Framework Type. Although the depth fading helps in viewing the drawings, the
`use of a stereo viewer is recommended (can be obtained from any electron microscopy supply house).
`
`The coordinates of the idealized, highest symmetry structures have been used for these drawings.
`
`Only the positions of the T—atoms are shown. The T—O-T bridges are represented by straight lines.
`This idealization makes it easier to visualize the topology and the basic features of these (often
`
`complex) framework structures. The unit cell is outlined and the orientation of the axes indicated. For
`most frameworks, more than a unit cell is shown, but for cases where the figures would have been too
`
`In these cases a projection along a major axis is
`complex, only a part of the unit cell is depicted.
`shown to help in visualizing the buildup of the complete framework.
`
`Idealized cell parameters
`
`The idealized cell parameters were obtained from a DLS—refinementm’ using the given (highest
`
`possible) symmetry of the Framework Type. The refinement was carried out assuming a (sometimes
`hypothetical) SiO2 composition and with the following prescribed interatomic distances: dg,,O = [bl/OX,
`doc : 2.629A and Dghg, = 3.0721 using the weights of 2.0, 0.61 and 0.23, respectively.
`0
`
`Coordination sequences (CS) and vertex symbols
`
`The concept of coordination sequences was originally introduced by Brunner and Lavesm and first
`applied to zeolite frameworks by Meier and Moeckm.
`In a typical zeolite framework, each T-atom is
`connected to N1 = 4 neighboring T—atoms through oxygen bridges. These neighboring T—atoms are
`then linked in the same manner to N2 T—atoms in the next shell. The latter are connected to N3
`
`In this way, a coordination sequence can be
`T—atoms etc. Each T—atom is counted only once.
`determined for each T-atom of the 4—connected net of T-atoms. It follows that
`
`310:1
`
`N.s4
`
`N2512
`
`N3536...
`
`Nks4-3k“
`
`CS's are listed from N, up to N10 for each topologically distinct T~atom in the framework structure
`
`along with the site multiplicity and the site symmetry (both in parenthesis).
`
`The vertex symbol was first used in connection with zeolite-type networks by M. O’Keefe and ST.
`
`Hyde”). This symbol indicates the size of the smallest ring associated with each of the 6 angles of a
`
`Exhibit 2033.011
`
`Exhibit 2033.011
`
`

`

`6 t
`
`etrahedron (T—atom). The symbols for opposite pairs of angles are grouped together. For FAU the
`
`vertex symbol reads 4-4-4-6-61‘2,
`
`indicating that one pair of opposing angles contains 4—rings, a
`
`second pair a 4—ring and a 6-ring, and the final pair a 6—ring and a lZ—ring.
`
`It is useful for determining
`
`In the case of DOH, for example, the vertex symbols for the four
`the smallest rings in a framework.
`T—atoms are 555556, 455656, 56-55-56 and 5555-55, so the smallest rings are 4— and 5—rings,
`
`(4.75 in Figure 1). Sometimes more than one ring of the same size is found for a single angle. This is
`indicated with a subscript like 63 or 82. An asterisk in the vertex symbol indicates that no ring is
`
`formed for that angle.
`
`The coordination sequence and the vertex symbol together appear to be unique for a particular
`
`framework topology. That
`
`is, they can be used to distinguish different zeolite Framework Types
`
`unambiguously.
`
`in this way, isotypic frameworks can be recognized easily.
`
`Secondary building units (SBU'S)
`
`Zeolite frameworks can be thought
`
`to consist of finite or infinite (i.e. chain- or layer—like)
`
`component units. The finite units which have been found to occur in at
`
`least
`
`two tetrahedral
`
`frameworks are shown in Appendix C. These secondary building units (primary building units are
`
`TO4 tetrahedra), which contain up to 16 T-atoms, are derived assuming that the entire framework is
`
`made up of one type of SBU only.
`
`It should be noted that SBU’s are invariably non—chiral (neither
`
`left~ nor right—handed) and a unit cell always contains an integral number of them. As far as
`
`practicable, all possible SBU‘s have been listed. The number of observed SBU’s has increased from
`20 in 2001 to 23.
`For Framework Types with an SBU that only occurs once or for which
`
`combinations of SBU’S are necessary, the reader is referred to the Compendium of Zeolile Framework
`
`Types. Building Schemes and Type Characteristics by H. van Koningsveld‘m’, where all SBU‘s are
`listed in detail. The symbols given below the drawings in Appendix C are used in the data sheets.
`If
`
`more than one SBU is possible for a given Framework Type. all are listed. The number given in
`
`parenthesis in Appendix C indicates the frequency of the occurrence of that SB U. The SBU’s are only
`
`theoretical topological building units and should not be considered to be or equated with species that
`
`may be in the solution/gel during the crystallization of a zeolitic material.
`
`Framework description
`
`For all 19 Framework Types belonging to the so—called ABC-6~family, the ABC stacking sequence
`
`is given. Some other structural relationships which are thought to be helpful are also listed.
`
`Composite Building Units (CBU’s)
`
`Some units (eg. double 6-ring, cancrinite cage, alpha cavity, double crankshaft chain) appear in
`
`several different
`
`framework structures, and can be useful
`
`in identifying relationships between
`
`Framework Types. Smith has compiled an exhaustive list of such units, not only for zeolite structures
`
`In his Compendiumm”, van Koningsveld
`but also for hypothetical 3—dimensional 4-connected nets‘”).
`has also included an extensive list of them. Here we have arbitrarily selected just 47 Composite
`
`Building Units and five chains (Appendix D) that are found in at least two different Framework Types.
`
`These are different from secondary building units in that they are not required to be achiral. and cannot
`
`Exhibit 2033.012
`
`Exhibit 2033.012
`
`

`

`7
`
`necessarily be used to build the entire framework. To facilitate communication, each unit has been
`
`assigned a lower case italic three»character designation. With the exception of the double 4', 6— and 8—
`
`rings (d4r, (Mr and (Br, respectively), a code corresponding to one of the Framework Types containing
`
`the CBU has been used for this purpose. A comparison of the notation used by Smith, van
`
`Koningsveld and here is also given in Appendix D.
`
`Materials with this Framework Type
`
`Under this heading, as—synthesized materials that have the same Framework Type but different
`
`chemical composition or have a different laboratory designation are listed. Materials obtained by
`
`postvsynthesis treatment (eg. ion exchange, dealumination, etc.) are generally not included. The Type
`Material (defined on the second page) is given first and marked with an asterisk. These materials are
`
`also listed in the Isotypic Material Index at the end of the book.
`
`References
`
`The list of references Cited is far from complete. As a general rule, references for the Type
`
`Material are to the work that first established the Framework Type and to subsequent work adding
`
`significant information regarding the framework topology. Thus papers on non—framework species
`have not been included. References for other materials with a specific framework type are limited to
`
`work in which sufficient data are provided to establish the framework type.
`
`For most of the codes from ABW to RHO, complete references, cell constant data, space groups,
`
`site symmetries, symmetry relationships, structural diagrams, positional coordinates and chemical
`
`compositions for all crystal structure determinations published up to April 2000 can be found in the
`
`Landolt~Bomstein Series on Microporous and other framework materials with zeolite—type structures
`edited by W.H. Baur and R.X. Fischer”).
`
`Type Material Page
`
`The Type Material is the species first used to establish the Framework Type. Detailed information
`about the material is given on this page.
`
`Crystal chemical data
`
`The chemical composition, expressed in terms of unit cell contents, has been idealized Where
`
`necessary for simplicity, The chemical formula is given according to IUPAC recommendations”). For
`
`In
`each Type Material, the space group and cell parameters listed are taken from the reference cited.
`many instances, further refinement of the structure taking into account ordering etc. would yield a
`
`lower symmetry. It should also be noted that the space group and other crystallographic data related to
`
`the Type Material structure do not necessarily apply to isotypes.
`
`In some cases. the space group setting of the Type Material differs from that of the Framework
`
`Type.
`
`In these cases,
`
`the relationship between the two unit cells is given. This relationship is
`
`important when comparing the orientation of the channel direction and the Viewing direction of ring
`
`Exhibit 2033.013
`
`Exhibit 2033.013
`
`

`

`8 d
`
`rawings (both are given for the axis orientation of the Type Material) with that of the framework
`
`drawing.
`
`Framework density (FD)
`
`The framework density is defined as the number of T—atoms per 1000 A3. The number given refers
`to the Type Material. For non-zeolitic framework structures, these values tend to be at least 20 to 21
`T/ 1000 A3, while for zeolites with fully crosslinked frameworks, the observed values range from
`~12.l, for structures with the largest pore volume, to ~20.6. To date, FD‘s of less than 12 have only
`
`been encountered for the interrupted framework cloverite (-CLO)”3’, for the sulfide UCR—ZOM’
`. The PD is obviously related to the pore volume but does
`(RWY), and for hypothetical networks/“5)
`not reflect the size of the pore openings. For some of the more flexible zeolite structures, the FD
`
`values can vary appreciably.
`
`In these cases (eg. gismondine) values are given for the Type Material
`
`and for the framework in its most expanded state. The flexibility of a framework structure is, to some
`
`extent,
`
`revealed by the possible variation in FD.
`
`FD values may also depend on chemical
`
`composition.
`
`Channels
`
`A shorthand notation has been adopted for the description of the channels in the various
`
`frameworks. Each system of equivalent channels has been characterized by
`
`-
`
`-
`
`-
`
`the channel direction (relative to the axes of the Type Material structure),
`
`the number of T—atoms (in bold type) forming the rings controlling diffusion through the
`channels, and
`
`the crystallographic free diameters of the channels in Angstrom units.
`
`The number of asterisks in the notation indicates whether the channel system is one—, two or three—
`
`dimensional.
`
`In most cases,
`
`the smaller openings simply form windows (rather than channels)
`
`Interconnecting channel systems are separated by a double arrow (4—9). A
`connecting larger cavities.
`vertical bar (I) means that there is no direct access from one channel system to the other. The
`
`examples below have been selected to illustrate the use of this notation.
`Cancrinite
`[001] 12 5.9 x 59*
`
`Offretite
`
`Mordenite
`Zeolite Rho
`
`[001] 12 6.7x6.8* H _L[001] 8 3.6x4.9**
`
`[001] 12 6.5X7.0* (—> {[010] 8 3.4x4.8 <—>[001] 8 2.6x5.7}*
`<100> 8 3.6x3.6*** l <100> 8 3.6x3,6***
`
`Gismondine
`
`{[100] 8 3.1x4.5 <—> [010] 8 2.8 x4.8}***
`
`Cancrinite is characterized by a l—dimensional system of channels parallel to [001] (or c) with circular
`
`lZ—ring apertures.
`
`In offretite, the main channels are similar but they are interconnected at right angles
`
`by a 2-dimensional system of 8—ring channels, and thus form a 3—dimensional channel system, The
`
`channel system in mordenite is essentially 2—dimensional with somewhat elliptical 12—ring apertures.
`
`The 8—ring limiting diffusion in the [001] direction is an example of a highly puckered aperture.
`
`Zeolite rho is an example of a Framework Type containing two non—interconnecting 3—dimensional
`
`channel systems which are displaced with respect to one another (<100> means there are channels
`
`Exhibit 2033.014
`
`Exhibit 2033.014
`
`

`

`9
`
`parallel to all crystallographically equivalent axes of the cubic structure, i.e., along [100], [010] and
`
`[OOl D.
`
`In gismondine, the channels parallel to [100] together with those parallel to {010} give rise to a
`
`3-dimensional channel system which can be pictured as an array of partially overlapping tubes.
`
`A summary of the channel systems, ordered by decreasing number of T—atoms in the largest ring, is
`
`given in Appendix E. The free diameter values (effective pore width) given in the channel description
`and on the ring drawings are based upon the atomic coordinates of the Type Material and an oxygen
`radius of 1.3513” Both minimum and maximum values are given for non-circular apertures.
`In some
`instances, the corresponding interatomic distance vectors are only approximately coplanar, in other
`
`cases the plane of the ring is not normal to the direction of the channel. Close inspection of the
`framework and ring drawings should provide qualitative evidence of these factors.
`Some ring
`
`openings are defined by a very complex arrangement of oxygen atoms, so in these cases other short
`
`interatomic distances that are not listed may also be observed.
`
`It should be noted that crystallographic
`
`free diameters may depend upon the hydration state of the zeolite, particularly for the more flexible
`frameworks.
`It should also be borne in mind that effective free diameters can be affected by non—
`
`framework cations and may also be temperature dependent.
`
`Note that
`
`the channel direction is given for the axis orientation of the Type Material. This
`
`orientation may be different from the orientation given in the framework drawing (see the cell
`
`relationship given under "crystal chemical data" for these cases).
`
`Stability
`
`In some cases, the Type Material is not stable to heating and/or removal of the template. This has
`been indicated, if the information was available.
`
`Ring drawings
`
`Stereographic drawings of the limiting channel windows are presented for all Framework Types.
`In contrast to the framework drawings, all atoms are shown in the ring drawings. Their positions are
`
`based on the crystal structure of the Type Material, and therefore the ring dimensions and the viewing
`
`direction are also those of the Type Material. As explained in the crystal chemical data section, for a
`
`few Type Materials, the orientation of the crystallographic axes is different from that given for the
`
`Framework Type.
`
`In these cases, the relationship given in the "crystal chemical data" section must be
`
`applied when comparing the viewing direction of the ring drawings with that of the framework
`
`drawing.
`
`Exhibit 2033.015
`
`Exhibit 2033.015
`
`

`

`10
`
`Topological densities
`
`Supplementary Information
`
`‘ The coordination sequences (CS) can be used to calculate a topological density (TD). As might be
`
`expected,
`
`the CS is a periodic function. This has been established for all observed framework
`
`topologies by GrossewKunstleve, Brunner and Sloanel'f”. They showed that the CS of any T—atom can
`be described exactly by a set of p quadratic equations
`
`Nk=a3k2+bik+q
`
`n=0,1,2,...and i=1,2,3,...p
`for k=i+np,
`
`For example, the CS of ABW (N124 biz-10 N3-21 N4-36 N5-54 N6-78 N7-106, etc.) is exactly
`described by a set of three quadratic equations (p=3). namely
`
`N1, = 19/91c2 + 1/9k+ 16/9
`
`for k :1 +311,
`
`1120.13,...
`
`Nk = 19/9 k2 —1/9k+ 16/9
`
`for k=2+3n,
`
`n=0,l,2,...
`
`Nk = 19/9 k2 — Ok+2
`
`for k=3 +3n,
`
`n=0,1,2,...
`
`The number of equations p necessary to calculate all members of a particular coordination
`
`sequence varies from p=1 for SOD and p242 for FAU to p=l40,900,760 for EUO.
`
`With growing index k (the shell number of the CS), the linear and constant coefficients, b, and Ci,
`
`respectively, become less and less important. Therefore we can define the exact topological density
`
`TD as the mean of all a, divided by the dimensionality of the topology (i.e. 3 for zeolites)
`
`_. <ai> _
`1
`1,
`TD ——-3——— 3-5.:‘11
`
`This TD is the same for all T atoms in a given structure. For some frameworks, this calculation can
`
`take quite a long time, so an approximation valid to $0.001 has been used to calculate the values given
`
`in Appendix F for each of the Framework Types. The value for <a,> has been approximated as the
`mean of ai for the last 100 terms of a CS with 1000 terms (TD1000: 100), weighted with the
`
`multiplicity of the atom position, and divided by three (dimensionality). The value for TDm (sum of
`the CS values for NO to NO), which was listed in the first four editions of the Atlas, is also given for
`
`comparison. There is a simple relationship between TD and TD“): TDIO ~ TD *1155. Since TDIO is
`an approximation, i.e. it is ’arbitarily‘ terminated at N“), the values obtained by this formula deviate by
`11% for ——CLO and 5% for FAU but the differences are generally below 3%.
`It seems that for very
`
`open structures, 10 steps are not sufficient for a satifactory convergence. The correlation factor
`
`between the exact topological density TD and the framework density PD is 0.82.
`
`Origin of 3—letter codes and Type Material names
`
`The derivation of the 3-1etter codes for the zeolite minerals is fairly obvious, because the c