Short Papers

The framework topo Iogy of Z S M - 2 3 :

A high silica zeolite
A. C. Rohrman, Jr., R. B. LaPierre, J. L.
S c h l e n k e r , J . D. Wood, E. W. Valyocsik, M. K .
Rubin, J. B. Higgins and W. J. Rohrbaugh*
Mobil Research and Development Corporation, Research
Department, Paulsboro, New Jersey 08066, USA

Z S M - 2 3 , a high-silica zeolite, is orthorhombic, space group,

Proton, with lattice parameters of: a=5.01+O.O21k, b
= 2 1 . 5 2 + 0 . 0 4 •, and c =11.13+0.03 A. The crystal structures
of Z S M - 2 2 and Z S M - 2 3 are closely related in that both
zeolites contain structurally identical subunits which generate
noninterpenetrating, one-dimensional channels defined by
lO-rings which are parallel to the short 5 A axis. The lO-ring
channel dimensions in Z S M - 2 2 and Z S M - 2 3 are essentially
the same, though subtle differences exist in the shapes of the
openings.

Keywords: ZSM-23; framework topology; high silica zeolites

INTRODUCTION
Z S M - 2 3 is a Mobil proprietary zeolite first synthesized
by Plank, Rosinski and Rubin 1. In a preferred
synthesis, sources of silica, alumina, caustic soda and Figure 1 Electron diffraction pattern of hkO-reciprocal lattice
pyrrolidine are reacted at 150 ° . 160°C until a crystalline layer. Note the extinction h + / = 2n due to the n-glide
product is formed. The crystals used were prepared by
M. E. Landis and have a disc-like habit. The pre- atomic coordinates for this structure are listed in Table 1.
parative procedure was that described in US Pat. 4 Comparison of the X-ray powder pattern of Z S M - 23
490 342 using N,N,N,N;N;N'-hexamethylheptanedi- with the X-ray powder diffraction pattern and data
ammonium dibromide ~. The Si/A1 ratio was 166. given for zeolite I S I - 4 by Takatsu and Kawata 7 and
with the X-ray powder pattern and data given by Parker
and Bibby for K Z - 1 8 , indicates that both these
EXPERIMENTAL
materials possess the framework topology of Z S M - 2 3 .
X-ray powder and electron diffraction data were
obtained for the hydrogen form of Z S M - 2 3 . Based on
electron diffraction results, the X-ray powder peak
(Figure 2a) at 35.81 ° 20 was assigned an index of (200),
and the 24 remaining best resolved peaks were input to Table 1 DLS - Atomic Coordinates of (xlO 4) of Z S M - 2 3 origin
an indexing algorithm, which returned an at mmn
orthorhombic cell with a de Wolff index of 27.4 ~,4.
Electron diffraction patterns indicated Pmmn symmetry Atom x y z
(Figure 1). Extensive tabulations of X-ray powder
diffraction data for Z S M - 2 3 are contained in US Pat. 4 T1 O000 2076 -0060
076 842 I. T2 0000 1700 -2696
Hypothetical frameworks consistent with the T3 0000 1353 2379
T4 0000 0000 2936
symmetry and cell parameters of Z S M - 2 3 were T5 5000 0000 4642
constructed, their structures refined using DLS 5, and 7-6 5000 1921 3638
the resulting coordinates used to compute Smith plots 6. 7-7 5000 1273 6030
The Smith plot of one of these models (Figure 2c) is O1 2500 2500 0000
02 0000 1671 -1261
compared with experimental powder patterns of 03 0000 1647 1085
Z S M - 2 3 in the as-synthesized (Figure 2a) and hydrogen 04 0000 2375 -3243
forms (Figure 2b) in Figure 2. T h e excellent agreement 05 2498 1296 -3101
leaves no doubt that this hypothetical model, shown in 06 0000 0611 2125
Figures3a and 3b, is the structure of Z S M - 2 3 . T h e DLS- 07 2507 1540 3151
08 2502 0000 3783
09 5000 0612 5418
O10 5000 1838 5085
* Author to whom correspondence should be directed

0 1 4 4 - 2 4 4 9 1 8 5 1 0 6 0 3 5 2 - 0 3 $03.00
© 1985 Butterworth & Co. (Publishers) Ltd.
352 ZEOLITES, 1985, Vo/ 5, November
 Short Papers

D E S C R I P T I O N OF T H E S T R U C T U R E
The Z S M - 2 3 framework is composed of 5; 6- and
10-rings of T-atoms. No 4-rings are present. Sinusoidal
chains of 5-rings traverse the length of the crystal in the
b-direction (Figure 3a) producing a unique bc-projection
with teardrop-shaped 10-membered ring openings with
dimensions of 4 . 5 x 5 . 6 /~. This linear noninter-
penetrating channel system parallels the a-axis. The
crystal structure of Z S M - 2 3 closely resembles
Z S M - 2 2 9 and a structural unit common to both
materials is denoted by heavy lines in Figure 4a
(projection) and 4b (rotated 12 degrees). When linked as
in Figure 4a and 4b, this unit produces Z S M - 2 2 . An
alternate linkage is shown in Figure 4c (projection) and
4d. Both linkages are present in Z S M - 2 3 . Exclusive
uses of the linkage in Figure 4c and 4d results in an

IO 80 Bo =o ,¢

70 70

(a) Experimental X-ray Powder [Sattem '~

80 eO
of ZSM-23 (as Synthesized)
eo 6o o¢

~O ~O
5o 5o K

• o o
• o 4o 4o

3o =o 3o

I I I I

~o
(b) Experimental )(-ray Powder Pattern
of ZSM-23 (Calcined)
6o eo

=o so

4o ~o

I
i I I

(c) Smith Plot of ZSM-23 Framework

,i

lO
Figure 2 Comparison of experimental and computed (Smith Plot) powder patterns of ZSM-23

ZEOLITES, 1985, Vol 5, November 353

Short Papers
r"-'

_../

(a) (b)
Figure 3 Framework structure of Z S M - 2 3 (a) in projection (bc-face) (b) rotated twelve degrees. Note 5-ring chain

i
Figure4 (a) •uilding block (outlined) and linkage in Z S M - 2 2 and Z S M - 2 3 ; (b) building block and linkage in Z S M - 2 2 and ZSM•23 (rotated
twelve degrees); (c) linkage in Z S M - 2 3 ; (d) linkage in Z S M - 2 3 (rotated twelve degrees)

additional hypothetical tetragonal structure with REFERENCES

a=22.2 /k, c=5.0/k, I4/mmrn symmetry and parallel
12- and 8-membered noninterpenetrating channels.
The ZSM-23 structure has 24 T-atoms per unit cell
and a computed density (for assumed end-member
SiO2 composition) of 2.0 g cm -3. We propose the
designation M T T for the framework topology of this
zeolite.
ACKNOWLEDGEMENTS
We thank Professor W. M. Meier of the ETH Zfirich
and E. L. Wu of the MRDC Paulsboro Laboratory for
valuable discussions and M. E. Landis, also of MRDC
Paulsboro Laboratory, for providing the sample used in
this study.
1 Plank, C. J., Rosinski, E. J. and Rubin, M. K. US Pat. 4 0 7 6 842
(1978)
2 Valyocsik, E. W. US Pat. 4 4 9 0 342 (1984)
3 Taupin, D. J. J. Appl. Crystallogr. 1973, 6, 3 8 0
4 de Wolff, P. M. J. Appl. Crystallogr. 1968, 1, 108
5 Baerlocher, Ch., Hepp, A. and Meier, W. M. 'DLS-76, A
Program for the Simulation of Crystal Structures by Geometric
Refinement', Z(Jrich, Switzerland, 1979
6 Smith, D. K. 'A Revised Program for Calculating X-ray Powder
Diffraction Patterns', UCRL-502.64, Lawrence Radiation
Laboratories, 1967
7 Takatsu, K. and Kawata, N. Eur. Pat. Appl. No. EP A 102497
(1984)
8 Parker, L. M. and Bibby, B. M. Zeolites, 1983, 3, 8
9 Kokotailo, G. T., Schlenker, J. L., Dwyer, F. G. and Valyocsik, E.
W. Zeofites 1985, 5, 349
(Received 3 October1984," revised12July 1985)

354 ZEOLITES, 1985, Vol 5, November