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Structure Determination of Trimethylsulfoxonium-Exchanged Vermiculite

Published online by Cambridge University Press:  01 January 2024

Candice A. Johns ,
Rubén Martos-Villa ,
Stephen Guggenheim  and
C. Ignacio Sainz-Díaz
Candice A. Johns
Affiliation:
Department of Earth and Environmental Sciences, University of Illinois at Chicago, 845 W. Taylor St., mc 186, Chicago, Illinois 60607, USA
Rubén Martos-Villa
Affiliation:
Facultad de Ciencias del Mar y Ambientales, Universidad de Cádiz, Av. República Saharaui s/n, 11510, Puerto Real, Spain
Stephen Guggenheim*
Affiliation:
Department of Earth and Environmental Sciences, University of Illinois at Chicago, 845 W. Taylor St., mc 186, Chicago, Illinois 60607, USA
C. Ignacio Sainz-Díaz
Affiliation:
Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. De las Palmeras, 4, 18100, Armilla, Granada, Spain
*
*E-mail address of corresponding author: [email protected]
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Abstract

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The structure of trimethylsulfoxonium-exchanged vermiculite has been examined to compare it with other onium-exchanged structures, such as tetramethylammonium- and tetramethylphosphonium-exchanged vermiculite. The three organic cations are tetrahedral in shape, but trimethylsulfoxonium [(CH3)3SO+] has an oxygen atom replacing a methyl group at one apex. This study describes the effect this substitution and the larger S atom have on the site location in the interlayer and the effect on the vermiculite 2:1 layer. These clay minerals may be commercially useful as adsorbents.

Na-exchanged crystals of vermiculite from Santa Olalla, Spain, were intercalated with trimethylsulfoxonium [Me3SO+ = (CH3)3SO+] molecules by refluxing in an aqueous 0.25 M trimethylsulfoxonium iodide solution at 80°C for 14 days. The resulting Me3SO+-exchanged vermiculite crystals were studied by single-crystal, X-ray diffraction methods and by computer modeling (density functional theory). Cell parameters are a = 5.349(2), b = 9.270(3), c = 13.825(8) Å, and β = 97.40(4)°, the space group is C2/m, and the polytype is 1M. Refinement results (R = 0.073, wR = 0.080) show that in the average structure of C2/m, the S atoms of the Me3SO+ molecules form two partially occupied planes [2.066(2) Å from each basal oxygen plane] between the 2:1 layers, and the S atoms show considerable positional disorder. The O atom of the Me3SO+ molecule occurs in the central plane of the interlayer, as far away from each 2:1 layer as possible. In projection down the c* axis, the Me3SO+ molecule resides within the center of the silicate rings from each adjacent 2:1 layer. In the ideal (static) model of the Me3SO+-exchanged vermiculite structure, the Me3SO+ molecule is oriented such that two methyl groups point toward charge-deficient bridging oxygen atoms of the basal plane; thus, the organic pillars charge compensate the bridging oxygen atoms of the 2:1 layer that are charge deficient. In projection, the oxygen atom of the Me3SO+ molecule projects over a tetrahedron containing Si. Computer modeling showed that if H2O is not included in the model, the Me3SO+ molecule (S and O atoms) is in the center of the interlayer, but with the addition of randomly placed H2O, two partially occupied planes similar to the X-ray derived model are formed.

Keywords

Computational ModelingOrganoclayTrimethylsulfoxonium-exchanged VermiculiteVermiculiteX-ray Structure Determination
Type
Research Article
Information
Clays and Clay Minerals , Volume 61 , Issue 3 , June 2013 , pp. 218 - 230
Copyright
Copyright © The Clay Minerals Society 2013

References

Barrer, R.M., 1984 Sorption and molecular sieve properties of clays and their importance as catalysts Philosophical Transactions of the Royal Society of London A311 333–352.Google Scholar
Barrer, R.M., 1989 Shape selective sorbents based on clay minerals: A review Clays and Clay Minerals 37 385–395.CrossRefGoogle Scholar
Barrer, R.M. and Millington, A.D., 1967 Sorption and intracrystalline porosity in organo-clays Journal of Colloid Interface Science 25 359–372.CrossRefGoogle Scholar
Barrer, R.M. and Perry, G.S., 1961 Sorption of mixtures, and selectivity in alkylammonium montmorillonites Journal of the Chemical Society 842–858.CrossRefGoogle Scholar
Frisch, M.J. Trucks, G.W. Schlegel, H.B. Scuseria, G.E. Robb, M.A. Chesseman, J.R. Zarzewki, V.G. Montgomery, J.A. Stratmann, R.E. Burant, J.C. Dapprich, S. Millam, J.M. Daniels, A.D. Kudin, K.N. Strain, M.C. Farkas, O. Tomasi, J. Barone, V. Cossi, M. Cammi, R. Mennucci, B. Pomelli, C. Adamo, C. Clifford, S. Ochterski, J. Petersson, G.A. Ayala, P.Y. Cui, Q. Morokuma, K. Malick, D.K. Rabuck, A.D. Raghavachari, K. Foresman, J.B. Cioslowski, J. Ortiz, J.V. Stefanov, B.B. Liu, G. Liashenko, A. Piskorz, P. Komaromi, I. Gomperts, R. Martin, R.L. Fox, D.J. Keith, T.A. Al-Laham, M.A. Peng, C.Y. Nanayakkara, A. Gonzalez, C. Challacombe, M. Gill, P.M.W. Johnson, B.G. Chen, W. Wong, M.W. Andres, J.L. Head-Gordon, M. Replogle, E.S. and Pople, J.A., 2004 Gaussian 03 Revision A.1 Pittsburgh, Pennsylvania, USA Gaussian, Inc..Google Scholar
Guggenheim, S. (2013) Glossary for clay science. Updated annually and can be down loaded at: .Google Scholar
Hernández-Laguna, A. Escamilla-Roa, E. Timón, V. Dove, M.T. and Sainz-Díaz, C.I., 2006 DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2:1 phyllosilicates Physics and Chemistry of Minerals 33 655–666.CrossRefGoogle Scholar
International Tables for X-ray Crystallography (Volume 4: Revised and Supplementary Tables to Volumes 2 and 3) (1974) Ibers, J.A. and Hamilton, W.C., editors. The Kynoch Press, Birmingham, England, pp. 71–147.Google Scholar
Knop, O. Cameron, S. Bakshi, P.K. Linden, A. and Roe, S.P., 1994 Crystal chemistry of tetraradial species. Part 5. Interaction between cation lone pairs and phenyl groups in tetraphenylborates: Crystal structures of Me3S+, Et3 S+, Me 3SO1,2+, Ph2I+, and 1-azoniapropellane tetraphenylborates Canadian Journal of Chemistry 72 1870–1881.CrossRefGoogle Scholar
Kolinsky, C. Puget, R. de Braver, C. and Jannin, M., 1994 Structures of trimethyloxosulfonium salts VIII. New refinement of the perchlorate (CH3)3SO+.ClO--4 Acta Crystallographica, Section C 1514–1516.CrossRefGoogle Scholar
Lee, J. Mortland, M.M. Chiou, C.T. Kile, D.E. and Boyd, S.A., 1990 Adsorption of benzene, toluene, and xylene by two tetramethylammonium-smectites having different charge densities Clays and Clay Minerals 38 113–120.CrossRefGoogle Scholar
Loewenstein, W., 1954 The distribution of aluminum in the tetrahedra of silicates and aluminates American Mineralogist 39 92–96.Google Scholar
Loudon, G.M., 1995 Organic Chemistry third edition California, USA The Benjamin/Cummings Publishing Company, Inc..Google Scholar
Martos-Villa, R. Guggenheim, S. and Sainz-Diaz, C. I., 2013 Interlayer water molecules in organocation-exchanged vermiculite and montmorillonite: A case study of tetramethylammonium American Mineralogist 98 8-9 1535–1542.CrossRefGoogle Scholar
Norrish, K., Serratosa, J.M., 1973 Factors in the weathering of mica to vermiculite Proceedings Of The International Clay Conference 1972 Madrid Division de Ciencias, CSIC 417–432.Google Scholar
Perdew, J.P. Ruzsinszky, A. Csonka, G.I. Vydrov, O.A. Scuseria, G.E. Constantin, L. Zhou, X. and Burke, K., 2008 Restoring the density-gradient expansion for exchange in solids and surfaces Physical Review Letters 100 136406.CrossRefGoogle ScholarPubMed
Ruiz-Conde, A. Ruiz-Amil, A. Perez-Rodriguez, J.L. Sanchez-Soto, P.J. and Aragan de la Cruz, F., 1997 Interaction of vermiculite with aliphatic amides (formamide, acetamide and propionamide): Formation and study of interstratified phases in the transformation of Mg- to NH4-vermiculite Clays and Clay Minerals 45 311–326.CrossRefGoogle Scholar
Sainz-Diaz, C.I. Palin, E.J. Hernández-Laguna, A. and Dove, M.T., 2003 Octahedral cation ordering of illite and smectite. Theoretical exchange potential determination and Monte Carlo simulations Physics and Chemistry of Minerals 30 382–392.CrossRefGoogle Scholar
Sainz-Díaz, C.I. Escamilla, E. and Hernández-Laguna, A., 2005 Quantum mechanical calculations of trans-vacant and cis-vacant polymorphism in dioctahedral 2:1 phyllosilicates American Mineralogist 90 1827–1834.CrossRefGoogle Scholar
Seidl, W. and Breu, J., 2005 Single crystal refinement of tetramethylammonium-hectorite Zeitschrift für Kristographie 220 169–176.Google Scholar
Soler, J.M. Artacho, E. Gale, J.D. García, A. Junquera, J. Ordejón, P. and Sánchez-Portal, D., 2002 The SIESTA method for ab-initio order-N materials simulation Journal of Physics: Condensed Matter 14 2745–2779.Google Scholar
Stout, G.H. and Jensen, L.H., 1968 X-ray Structure Determination: A Practical Guide New Jersey, USA John Wiley and Sons, Inc..Google Scholar
Troullier, N. and Martins, J.L., 1991 Efficient pseudopotentials for plane-wave calculations Physical Reviews B 43 1993–2006.CrossRefGoogle ScholarPubMed
Vahedi-Faridi, A. and Guggenheim, S., 1997 Crystal structure of tetramethylammonium-exchanged vermiculite Clays and Clay Minerals 45 859–866.CrossRefGoogle Scholar
Vahedi-Faridi, A. and Guggenheim, S., 1999 Structural study of tetramethylphosphonium-exchanged vermiculite Clays and Clay Minerals 47 219–225.CrossRefGoogle Scholar
Vahedi-Faridi, A. and Guggenheim, S., 1999 Structural study of monomethylammonium and dimethylammonium-exchanged vermiculites Clays and Clay Minerals 47 338–347.CrossRefGoogle Scholar