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Crystal chemistry of natural layered double hydroxides. 3. The crystal structure of Mg,Al-disordered quintinite-2H

Published online by Cambridge University Press:  05 July 2018

E. S. Zhitova
Affiliation:
Department of Crystallography, Faculty of Geology, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia
V. N. Yakovenchuk
Affiliation:
Geological Institute, Kola Science Center, Russian Academy of Sciences, Apatity, Russia Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Russia
S. V. Krivovichev*
Affiliation:
Department of Crystallography, Faculty of Geology, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Russia
A. A. Zolotarev
Affiliation:
Department of Crystallography, Faculty of Geology, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia
Y. A. Pakhomovsky
Affiliation:
Geological Institute, Kola Science Center, Russian Academy of Sciences, Apatity, Russia Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Russia
G. Yu. Ivanyuk
Affiliation:
Geological Institute, Kola Science Center, Russian Academy of Sciences, Apatity, Russia Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Russia
*

Abstract

Two crystals of Mg, Al-disordered quintinite-2H (Q1 and Q2), [Mg4Al2(OH)12](CO3)(H2O)3, from the Kovdor alkaline massif, Kola peninsula, Russia, have been characterized chemically and structurally. Both crystals have hexagonal symmetry, P63/mcm, a = 3.0455(10)/3.0446(9), c = 15.125(7)/15.178(5) Å, V = 121.49(8)/121.84(6) Å3. The structures of the two crystals have been solved by direct methods and refined to R1 = 0.046 and 0.035 on the basis of 76 and 82 unique observed reflections for Q1 and Q2, respectively. Diffraction patterns obtained using an image-plate area detector showed the almost complete absence of superstructure reflections which would be indicative of the Mg-Al ordering in metal hydroxide layers, as has been observed recently for other quintinite polytypes. The crystal structures are based on double hydroxide layers [M(OH)2] with an average disordered distribution of Mg2+ and Al3+ cations. Average <M–OH> bond lengths for the metal site are 2.017 and 2.020 Åfor Q1 and Q2, respectively, and are consistent with a highly Mg-Al disordered, average occupancy. The layer stacking sequence can be expressed as …=AC=CA=…, corresponding to a Mg-Al-disordered 2H polytype of quintinite. The observed disorder is probably the result of a relatively high temperature of formation for the Q1 and Q2 crystals compared to ordered polytypes. This suggestion is in general agreement with the previous observations which demonstrated, for the Mg-Al system, a higher-temperature regime of formation of the hexagonal (or pseudo-hexagonal in the case of quintinite-2H-3c) 2H polytype in comparison to the rhombohedral (or pseudo-rhombohedral in the case of quintinite-1M) 3R polytype.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2010

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References

Allmann, R. (1968) The crystal structure of pyroaurite. Acta Crystallographica B24, 972979.CrossRefGoogle Scholar
Allmann, R. and Jepsen, H.P. (1969) Die struktur des Hydrotalkits. Neues Jahrbuch für Mineralogie, Monatshefte, 1969, 544551.Google Scholar
Arakcheeva, A.V., Pushcharovskii, D.Yu., Atencio, D. and Lubman, G.U. (1996) Crystal structure and comparative crystal chemistry of Al2Mg4(OH)12(CO3)-3H2O, a new mineral from the hydrotalcite-manasseite group. Crystallography Reports, 41, 972981.Google Scholar
Bellotto, M., Rebours, B., Clause, O., Lynch, L., Bazin, D. and Elkaim, E. (1996) A reexamination of hydrotalcite crystal chemistry. Journal of Physical Chemistry, 100, 85278534.CrossRefGoogle Scholar
Bonaccorsi, E., Merlino, S. and Orlandi, P. (2007) Zincalstibite, a new mineral, and cualstibite: crystal chemical and structural relationships. American Mineralogist, 92, 198203.CrossRefGoogle Scholar
Chao, G.Y. and Gault, R.A. (1997) Quintinite-2H, quintinite-3T, charmarite-2H, charmarite-3T and caresite-3T, a new group of carbonate minerals related to the hydrotalcite/manasseite group. The Canadian Mineralogist, 35, 15411549.Google Scholar
Cooper, M.A. and Hawthorne, F.C. (1996) The crystal structure of shigaite, (SO4)2Na(H2O)6{H2O}6, hydrotalcite-group mineral. The Canadian Mineralogist, 34, 9197.Google Scholar
Drits, V.A., Sokolova, T.N., Sokolova, G.V. and Cherkashin, V.I. (1987) New members of the hydrotalcite-manasseite group. Clays and Clay Minerals, 35,401417.CrossRefGoogle Scholar
Evans, D.G. and Slade, R.C.T. (2006) Structural aspects of layered double hydroxides. Pp. 187 in: Layered Double Hydroxides (Duan, X. and Evans, D.G., editors). Springer, Berlin.Google ScholarPubMed
Huminicki, D.M.C. and Hawthorne, F.C. (2003) The crystal structure of nikischerite, (SO4)2(OH)18(H2O)12, a mineral of the shigaite group. The Canadian Mineralogist 41, 7982.CrossRefGoogle Scholar
Kim, D., Huang, C., Lee, H., Han, I., Kang, S., Kwon, S., Lee, I., Han, Y. and Kim, H. (2003) Hydrotalcite-type catalysts for narrow-range oxyethylation of 1-dodecanol using ethyleneoxide. Applied Catalysis A: General, 249, 229240.CrossRefGoogle Scholar
Krivovichev, S.V., Yakovenchuk, V.N., Zhitova, E.S., Zolotarev, A.A., Pakhomovsky, Ya.A. and Ivanyuk, G.Yu. (2010 a) Crystal chemistry of natural layered double hydroxides. 1. Quintinite-2H-3c from Kovdor alkaline massif, Kola peninsula, Russia. Mineralogical Magazine, 74, 821832.CrossRefGoogle Scholar
Krivovichev, S.V., Yakovenchuk, V.N., Zhitova, E.S., Zolotarev, A.A., Pakhomovsky, Ya.A., Ivanyuk, G.Yu. (2010 b) Crystal chemistry of natural layered double hydroxides. 2. Quintinite-IM: first evidence of monoclinic polytype in M 2+-M 3+ layered double hydroxides. Mineralogical Magazine, 74, 833840.CrossRefGoogle Scholar
Merlino, S. and Orlandi, P. (2001) Carraraite and zaccagnaite, two new minerals from the Carrara marble quarries: their chemical compositions, physical properties, and structural features. American Mineralogist 86, 12931301.CrossRefGoogle Scholar
Pausch, I., Lohse, H.-H., Schurmann, K. and Allmann, R. (1986) Synthesis of disordered and Al-rich hydrotalcite-like compounds. Clays and Clay Minerals, 34, 507510.CrossRefGoogle Scholar
Richardson, M.C. and Braterman, P.S. (2007) Infrared spectra of oriented and nonoriented layered double hydroxides in the range from 4000 to 250 cm–1, with evidence for regular short-range order in a synthetic magnesium-aluminum LDH with Mg:Al = 2:1 but not with Mg:Al = 3:1. Journal of Physical Chemistry Clll, 42094215.Google Scholar
Rius, J. and Allmann, R. (1984) The superstructure of the double layer mineral wermlandite [Mg7(Al0.57 . Zeitschrift für Kristallographie, 168, 133144.CrossRefGoogle Scholar
Rius, J. and Plana, F. (1986) Contribution to the superstructure resolution of the double layer mineral motukoreaite. Neues Jahrbuch für Mineralogie, 6, 263272.Google Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica A64, 112122.CrossRefGoogle Scholar
Sideris, P.J., Nielsen, U.G., Gan, Z.H. and Grey, C.P. (2008) Mg/Al ordering in layered double hydroxides revealed by multinuclear NMR spectroscopy. Science, 321, 113117.CrossRefGoogle ScholarPubMed
Steeds, J.W. and Morniroli, J.P. (1992) Selected area electron diffraction (SAED) and convergent beam electron diffraction (CBED). Pp. 3784 in: Minerals and Reactions at the Atomic Scale (Buseck, P.R., editor). Reviews in Mineralogy, 27, Mineralogical Society of America, Washington D.C. CrossRefGoogle Scholar