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Crystal Structure of Kaolinite: Dimethylsulfoxide Intercalate

Published online by Cambridge University Press:  02 April 2024

J. G. Thompson*
Affiliation:
Geology Department, James Cook University of North Queensland, Townsville, Queensland 4811, Australia
C. Cuff
Affiliation:
Geology Department, James Cook University of North Queensland, Townsville, Queensland 4811, Australia
*
1Present address: Research School of Chemistry, Australian National University, GPO Box 4, Canberra ACT 2601, Australia.
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Abstract

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The crystal structure of the kaolinite: dimethylsulfoxide (DMSO) intercalate (P1, a = 5.187(2), b = 8.964(3), c = 11.838(4) Å, α = 91.53(1)°, β = 108.59(2), γ = 89.92(1)°) has been determined using spectroscopic and X-ray and neutron powder diffraction data. Both the X-ray and neutron powder diffraction patterns were refined. Solid-state 13C, 29Si, and 27Al nuclear magnetic resonance data and previously collected infrared spectroscopic data provided a useful starting model for structural refinement. Due to the extreme overlap of reflections of this low-symmetry unit cell, the Rietveld method proved inadequate, and quasi-single crystal methods were employed. Each DMSO molecule was found to be triply hydrogen bonded above the octahedral vacancy in the gibbsitic sheet of the kaolinite layer. One methyl group is keyed into the ditrigonal hole in the tetrahedral sheet with the other S-C bond parallel to the sheet. The DMSO molecules are accommodated by significant horizontal displacement of individual kaolinite layers to achieve almost perfect overlap of the octahedral vacancy by the adjacent ditrigonal hole.

Type
Research Article
Copyright
Copyright © 1985, The Clay Minerals Society

References

Adams, J. M., 1978 Unifying features relating to the 3D structures of some intercalates of kaolinite Clays & Clay Minerals 26 291295.CrossRefGoogle Scholar
Adams, J. M., 1979 The crystal structure of a dickite: iV-methylformamide intercalate [Al2Si2O5(OH)4-HCONHCHJ Acta Crystaliogr. B35 10841088.CrossRefGoogle Scholar
Adams, J. M., 1983 Hydrogen atom positions in kaolinite by neutron profile refinement Clays & Clay Minerals 31 352356.CrossRefGoogle Scholar
Adams, J. M. and Jefferson, D. A., 1976 The crystal structure of a dickite: formamide intercalate AkSi OjCOHV HCONH2 Acta Crystallogr. B32 11801183.CrossRefGoogle Scholar
Adams, J. M. and Wahl, G., 1980 Thermal decomposition of a kaolinite: dimethylsulfoxide intercalate Clays & Clay Minerals 28 130134.CrossRefGoogle Scholar
Barron, P. F., Frost, R. L., Skjemstad, J. O. and Koppi, A. J., 1983 Detection of two silicon environments in kaolins via solid state 29Si NMR Nature 302 4950.CrossRefGoogle Scholar
Brindley, G. W. and Robinson, K., 1946 The structure of kaolinite Mineral. Mag. 27 242253.Google Scholar
Calvert, G. S., 1984 Simplified, complete CsCl-hydrazine-dimethylsulfoxide intercalation of kaolinite Clays & Clay Minerals 32 125130.CrossRefGoogle Scholar
Chang, H. C. and Houng, K. H., 1984 DMSO intercalation as a method in the identification of kaolinite from chlorite in soil clay samples Bull. Inst. Chem. Acad. Sin. 31 3139.Google Scholar
Costanzo, P. M., Giese, R. F. Jr. and Clemency, C. V., 1984 Synthesis of a 10-Å hydrated kaolinite Clays & Clay Minerals 32 2935.CrossRefGoogle Scholar
Costanzo, P. M., Giese, R. F. Jr. and Lipsicas, M., 1984 Static and dynamic structure in hydrated kaolinites. I. The static structure Clays & Clay Minerals 32 419428.CrossRefGoogle Scholar
Hamilton, W. C., 1965 Significance tests on the crystal-lographic R factor Acta Crystallogr. 18 502510.CrossRefGoogle Scholar
Hinckley, D. N. and Swineford, A., 1963 Variability in “crystallinity” values among the kaolin deposits of the coastal plain of Georgia and South Carolina Clays and Clay Minerals, Proc. 11th Natl. Conf., Ottawa, Ontario, 1962 New York Pergamon Press 229235.Google Scholar
Jackson, M. L. and Abdel-Kader, F. H., 1978 Kaolinite intercalation procedure for all sizes and types with X-ray diffraction spacing distinctive from other phyllosilicates Clays & Clay Minerals 26 8187.CrossRefGoogle Scholar
Jacobs, H., Sterckx, M. and Serratosa, J. M., 1970 A contribution to the study of the intercalation of dimethyl sulfoxide in the kaolinite lattice Proc. Reunion Hispano-Belge Miner. Arg., Madrid Madrid Cons. Super. Invest. Cient. 154160.Google Scholar
Lampe, F. V. v., Muller, D., Gessner, W., Grimmer, A.-R. and Scheler, G., 1982 27Al-NMR studies comparing the mineral zunyite and basic aluminium salts of tridecameric Al-oxo-hydroxo-aquo-cations Z. Anorg. Allg. Chem. 489 1622.Google Scholar
Lipsicas, M., 1984 Molecular motions and surface interactions in clay intercalates Phys. Chem. Porous Media 107 191202.Google Scholar
Nakamoto, K., Margoshes, M. and Rundle, R. E., 1955 Stretching frequencies as a function of distances in hydrogen bonds J. Amer. Chem. Soc. 11 64806486.CrossRefGoogle Scholar
Olejnik, S., Aylmore, L. A. G., Posner, A. M. and Quirk, J. P., 1968 Infrared spectra of kaolin mineral-dimethyl sulfoxide complexes J. Phys. Chem. 72 241249.CrossRefGoogle Scholar
Plançon, A. and Tchoubar, C., 1977 Determination of structural defects in phyllosilicates by X-ray powder diffraction—II. Nature and proportion of defects in natural kaolinites Clays & Clay Minerals 25 436450.CrossRefGoogle Scholar
Rietveld, H. M., 1967 Line profiles of neutron diffraction peaks for structure refinement Acta Crystallogr. 22 151152.CrossRefGoogle Scholar
Rietveld, H. M., 1969 A profile refinement method for nuclear and magnetic structures J. Appi. Cryst. 30 6567.CrossRefGoogle Scholar
Sanchez Camazano, M. and Gonzalez Garcia, S., 1970 Modification of the kaolinite crystal habit by dimethyl sulfoxide treatment An. Edafol. Agrobiol. 29 651655.Google Scholar
Sheldrick, G. M., 1976 A program for crystal structure determination: University Chemical Laboratory United Kingdom Cambridge.Google Scholar
Suitch, P. R. and Young, R. A., 1983 Atom positions in highly ordered kaolinite Clays & Clay Minerals 31 357366.CrossRefGoogle Scholar
Thomas, R., Shoemaker, C. B. and Klaas, E., 1966 The molecular and crystal structure of dimethyl sulfoxide, (H3C)2SO Acta Crystallogr. 21 1220.CrossRefGoogle Scholar
Thompson, J. G., 1985 Interpretation of solid state 13C and 29Si nuclear magnetic resonance spectra of kaolinite intercalates Clays & Clay Minerals 33 173180.CrossRefGoogle Scholar
Weiss, A., Thielepape, W. and Orth, H., 1966 Neue Kaoliniteinlagerungsverbindungen Proc. Int. Clay Conf., Jerusalem, 1966 1 277293.Google Scholar
Wiles, D. B. and Young, R. A., 1981 New computer program for Rietveld analysis of X-ray powder diffraction patterns J. Appi. Crystallogr. 14 149151.CrossRefGoogle Scholar
Young, R. A. and Wiles, D. B., 1981 Application of the Rietveld method for structure refinement with powder diffraction data Adv. X-ray Anal. 24 123.Google Scholar
Zvyagin, B. B., 1960 Electron diffraction determination of the structure of kaolinite Kristallografiya 5 3241.Google Scholar