Hostname: page-component-586b7cd67f-gb8f7 Total loading time: 0 Render date: 2024-11-25T09:10:30.025Z Has data issue: false hasContentIssue false
  • English
  • Français

Structure of a 1,4-Diazabicyclo[2,2,2]Octane-Vermiculite Intercalate

Published online by Cambridge University Press:  02 April 2024

P. G. Slade ,
P. K. Schultz  and
E. R. T. Tiekink
P. G. Slade
Affiliation:
CSIRO, Division of Soils, Glen Osmond, South Australia 5064, Australia
P. K. Schultz
Affiliation:
Department of Physical and Inorganic Chemistry, University of Adelaide, Box 498 GPO, Adelaide 5001, Australia
E. R. T. Tiekink
Affiliation:
Department of Physical and Inorganic Chemistry, University of Adelaide, Box 498 GPO, Adelaide 5001, Australia
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

1-4-diazabicyclo[2,2,2]octane dihydrochloride (DABCO·2HC1) was reacted with two vermic-ulite samples to produce intercalates which, at room temperature, had relatively sharp, single crystal X-ray diffraction patterns. At higher temperatures (250°C) the stacking order decreased, and consequently the 0kl reflections with k ≠ 3n became increasingly diffuse. The stacking order of previously heated samples returned when they were cooled. A superstructure was present in which DABCO cations occupied the corners and center of a cell 3a × b, compared with the standard vermiculite cell.

DABCO-intercalated Nyasaland vermiculite had the following monoclinic subcell (symmetry C1) parameters under ambient conditions: a = 5.341(2), b = 9.249(3), c = 14.50(1) Å, and ß = 96.98(5)°. Differential Fourier analyses and least-squares refinement led to a final R value of 12.6% for 1814 reflections. The crystal structure analysis showed that individual DABCO ions were not symmetrically positioned between the silicate layers. A network of inorganic cations and water molecules was also present and governed the interlayer separation. At 250°C the d value was 13.7 Å, consistent with a dehydrated structure, in which each organic pillar has one amino group keyed into a ditrigonal cavity and the other amino group riding on the basal oxygens of an opposite tetrahedron.

Keywords

Crystal structureDABCOIntercalateStacking orderingVermiculite
Type
Research Article
Information
Clays and Clay Minerals , Volume 37 , Issue 1 , February 1989 , pp. 81 - 88
Copyright
Copyright © 1989, The Clay Minerals Society

References

Alcover, J. F., Gatineau, L. and Méring, J., 1973 Exchangeable cation distribution in nickel and magnesium vermiculite Clays & Clay Minerals 21 131 – 136.CrossRefGoogle Scholar
de la Calle, C., 1977 Structures des vermiculites. Facteurs conditionnant les mouvements de feuillets: Thésis Paris Université P. et M. Curie.Google Scholar
de la Calle, C., Dubernat, J., Suquet, H., Pezerat, H., Gaultier, J., Mamy, J. and Bailey, S. W., 1976 Crystal structure of two-layer Mg-vermiculite and Na, Cavermiculites Proc. Int. Clay Conf, Mexico City, 1975 Illinois Applied Publishing, Wilmette 201 – 209.Google Scholar
International Tables for X-ray Crystallography, 1974 Kynoch Press, Birmingham, United Kingdom 99 – 101.Google Scholar
Kennedy, S. W., Schultz, P. K., Slade, P. G. and Tiekink, E. R. T., 1987 Crystal structure of triethylenediamine di-hydrochloride: Z Kristallogr. 180 211 – 217.CrossRefGoogle Scholar
MacEwan, D. M. C. Wilson, M. J., Brindley, G. W. and Brown, G., 1980 Interlayer and intercalation complexes of clay minerals Crystal Structures of Clay Minerals and their X-ray Identification London Mineralogical Society 203.Google Scholar
Motherwell, W. D. S., 1978 PLUTO 78. A plotting program for Cambridge crystallographic data: Chemical Laboratory, Cambridge Univ. United Kingdom Cambridge.Google Scholar
Shabtai, J., Frydman, N., Lazar, R., Bond, G. C., Wells, P. B. and Tompkins, F. C., 1977 Synthesis and catalytic properties of a 1,4-diazabicyclo(2,2,2) octane-montmorillonite system—A novel type of molecular sieve Proc. Int. Cong. Catal, London, 1976 660 – 667.Google Scholar
Sheldrick, G. M., 1976 SHELX 76. Program for crystal structure determination: Cambridge Univ. United Kingdom 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., Dean, C., Schultz, P. K. and Self, P. G., 1987 Crystal structure of a vermiculite-anilinium intercalate Clays & Clay Minerals is 177 – 188.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 Raupach, M. (1982) Structural model for benzidine-vermiculite: Clays & Clay Minerals 30, 297–305.CrossRefGoogle Scholar
Slade, P. G. and Stone, P. A., 1983 Structure of a vermic-ulite-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
Terrin, D. D., 1965 Dissociation Constants of Organic Bases in Aqueous Solutions London Butterworths 285.Google Scholar
Thompson, J. G., 1984 29Si and27Al nuclear magnetic resonance spectroscopy of 2:1 clay minerals Clay Miner. 19 229 – 236.CrossRefGoogle Scholar
Tokonami, M., 1965 Atomic scattering factor for O 7 Acta Crystallogr. 19 486.CrossRefGoogle Scholar