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Crystal Structure of a Vermiculite-Anilinium Intercalate

Published online by Cambridge University Press:  02 April 2024

P. G. Slade ,
C. Dean ,
P. K. Schultz  and
P. G. Self
P. G. Slade
Affiliation:
CSIRO, Division of Soils, Glen Osmond, South Australia 5064, Australia
C. Dean
Affiliation:
Physical and Inorganic Chemistry Department, University of Adelaide, Box 498 GPO, Adelaide 5001, Australia
P. K. Schultz
Affiliation:
Physical and Inorganic Chemistry Department, University of Adelaide, Box 498 GPO, Adelaide 5001, Australia
P. G. Self
Affiliation:
CSIRO, Division of Soils, Glen Osmond, South Australia 5064, Australia
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Abstract

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If anilinium ions are intercalated into Llano vermiculite, the stacking order of adjacent silicate layers is increased, resulting in a relatively sharp single crystal X-ray diffraction (XRD) pattern. The packing of intercalated organic members forms a superstructure and produces bonding from layer to layer which favors the stacking order. Superlattice reflections occur which, although sharp in the a*b* plane, are streaked along c*. Apparently there is little coherence between adjacent layers of ordered organic units.

A three-dimensional set of XRD reflections for a triclinic sub-cell having the following lattice parameters was measured: a = 5.326(3), b = 9.264(4), c = 14.82(5) Å, α = 90.31(7), β = 96.70(6), and γ = 89.55(5)°. In this unit cell (symmetry Cl), ditrigonal cavities in adjacent silicate layers are approximately opposite. Differential Fourier analyses and least-squares refinements showed that the principal axes of the anilinium ions, i.e., N-C(1)-C(4), are nearly perpendicular to the silicate layers. The planes of the aromatic rings, however, are about ±30° to X, neither parallel nor perpendicular to that direction, as indicated by earlier studies.

Inorganic cations and water molecules are also present in the interlayer; the former and some of the latter occupy sites near the middle of the layer. Anilinium-rich and anilinium-poor domains coexist. In the latter, the cation-water system predominates and apparently conforms to the superstructure. Although the cation-water structure could not be uniquely established from the reflections produced by the sub-cell, possible positional coordinates were obtained. From structural data for the silicate layers, no evidence was found for long-range Si/Al ordering in the tetrahedral sites.

Keywords

Anilinium ionCrystal structureIntercalateOrderingVermiculite
Type
Research Article
Information
Clays and Clay Minerals , Volume 35 , Issue 3 , June 1987 , pp. 177 - 188
Copyright
Copyright © 1987, The Clay Minerals Society

References

Brown, C. J., 1949 The crystal structure of aniline hydrochloride Acta Crystallogr. 2 228 – 232.CrossRefGoogle Scholar
Busing, W. R., Martin, K. O. and Levy, H. A. (1962) ORFLS, a Fortran crystallographic least-squares program: Oak Ridge Natl. Lab. Tech. Mem. 305, Oak Ridge National Laboratory, Tennessee, 75 pp.Google Scholar
de la Calle, C., Suquet, H. and Pezerat, H., 1985 Vermiculites hydratées à une couche Clay Miner. 20 221 – 230.CrossRefGoogle Scholar
Guss, J. M., Nockolds, C. E. and Wood, A. M., 1970 User manual for a computer-controlled BUERGER-SUPPER equi-inclination X-ray diffractometer Australia Crystal Structure Laboratory, School of Chemistry, Univ. Sydney, Sydney 34 – 35.Google Scholar
Hazen, R. M. and Burnham, C. W., 1973 The crystal structures of one-layer phlogopite and annite Amer. Mineral. 58 889 – 900.Google Scholar
International Tables for X-ray Crystallography, 1974 Vol. IV United Kingdom Kynoch Press, Birmingham 72 – 78.Google Scholar
Mathieson, A McL and Walker, G. F., 1954 Crystal structure of magnesium-vermiculite Amer. Mineral. 39 231 – 255.Google Scholar
Motherwell, W. D. S., 1978 PLUT078. A plotting program for Cambridge crystallographic data United Kingdom Chemical Laboratory, Cambridge Univ., Cambridge.Google Scholar
Nitta, I., Watanabe, T. and Taguchi, I., 1948 The crystal structure of aniline hydrobromide X-Sen 5 31 – 36.Google Scholar
Raupach, M., Slade, P. G., Janik, L. and Radoslovich, E. W., 1975 A polarized infrared and X-ray study of lysinevermiculite Clays & Clay Minerals 23 181 – 186.CrossRefGoogle Scholar
Sheldrick, G. M., 1976 SHELX. Program for crystal structure determination United Kingdom Cambridge Univ., Cambridge.Google Scholar
Shirozu, J. and Bailey, S. W., 1966 Crystal structure of a two layer Mg-vermiculite Amer. Mineral. 52 1124 – 1143.Google Scholar
Slade, P. G. and Raupach, M., 1982 Structural model for benzidine-vermiculite Clays & Clay Minerals 30 297 – 305.CrossRefGoogle Scholar
Slade, P. G., Raupach, M. and Emerson, W. W., 1978 The ordering of cetylpyridinium bromide on vermiculite Clays & Clay Minerals 26 125 – 134.CrossRefGoogle Scholar
Slade, P. G. and Stone, P. A., 1983 Structure of a vermiculite-aniline intercalate Clays & Clay Minerals 31 200 – 206.CrossRefGoogle Scholar
Slade, P. G. and Stone, P. A., 1984 Three-dimensional order and the structure of aniline-vermiculite Clays & Clay Minerals 32 223 – 226.CrossRefGoogle Scholar
Slade, P. G., Stone, P. A. and Radoslovich, E. W., 1985 Interlayer structures of the two-layer hydrates of Na- and Ca-vermiculites Clays & Clay Minerals 33 51 – 61.CrossRefGoogle Scholar
Thompson, J. G., 1984 29Si and 27Al nuclear magnetic resonance spectroscopy of 2:1 clay minerals Clay Miner. 19 229 – 236.CrossRefGoogle Scholar
Tokonami, M., 1965 Atomic scattering factor for O2− Acta Crystallogr. 19 486.CrossRefGoogle Scholar
Ware, N. G., 1981 Computer programs and calibration with the PIBS technique for quantitative electron probe analysis using a lithium-drifted silicon detector Computers and Geosciences 7 167 – 184.CrossRefGoogle Scholar