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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

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

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