Hostname: page-component-848d4c4894-4hhp2 Total loading time: 0 Render date: 2024-05-10T07:55:07.643Z Has data issue: false hasContentIssue false
  • English
  • Français

Crystal chemistry of natural layered double hydroxides. I. Quintinite-2H-3c from the Kovdor alkaline massif, Kola peninsula, Russia

Published online by Cambridge University Press:  05 July 2018

S. V. Krivovichev ,
V. N. Yakovenchuk ,
E. S. Zhitova ,
A. A. Zolotarev ,
Y. A. Pakhomovsky  and
G. Yu. Ivanyuk
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
V. N. Yakovenchuk
Affiliation:
Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Russia Geological Institute, Kola Science Center, Russian Academy of Sciences, Apatity, Russia
E. S. Zhitova
Affiliation:
Department of Crystallography, Faculty of Geology, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, 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:
Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Russia Geological Institute, Kola Science Center, Russian Academy of Sciences, Apatity, Russia
G. Yu. Ivanyuk
Affiliation:
Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Russia Geological Institute, Kola Science Center, Russian Academy of Sciences, Apatity, Russia
Get access Rights & Permissions [Opens in a new window]

Abstract

The crystal structure of quintinite-2H-3c, [Mg4Al2(OH)12](CO3)(H2O)3, from the Kovdor alkaline massif, Kola peninsula, Russia, was solved by direct methods and refined to an agreement index (R1) of 0.055 for 484 unique reflections with |Fo| ≥ 4σF. The mineral is rhombohedral, R32, a = 5.2745(7), c = 45.36(1) Å. The diffraction pattern of the crystal has strong and sharp Bragg reflections having h–k = 3n and l = 3n and lines of weak superstructure reflections extended parallel to c* and centred at h–k ≠ 3n. The structure contains six layers within the unit cell with the layer stacking sequence of …AC=CA=AC=CA=AC=CA… The Mg and Al atoms are ordered in metal hydroxide layers to form a honeycomb superstructure. The full superstructure is formed by the combination of two-layer stacking sequence and Mg-Al ordering. This is the first time that a long-range superstructure in carbonate-bearing layered double hydroxide (LDH) has been observed. Taking into account Mg-Al ordering, the unique layer sequence can be written as …=Ab1C=Cb1A=Ab2C=Cb2A=Ab3C=Cb3A=… The use of an additional suffix is proposed in order to distinguish between LDH polytypes having the same general stacking sequence but with different c parameters compared with the ‘standard’ polytype. According to this notation, the quintinite studied here can be described as quintinite-2H-3c or quintinite-2H-3c[6R], indicating the real symmetry.

Keywords

layered double hydroxidesquintinitecrystal structurecation orderingpolytypism
Type
Research Article
Information
Mineralogical Magazine , Volume 74 , Issue 5 , October 2010 , pp. 821 - 832
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2010

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Allmann, R. (1968) The crystal structure of pyroaurite. Acta Crystallographica B24, 972–977.CrossRefGoogle Scholar
Allmann, R. and Donnay, J.D.H. (1969) About the structure of iowaite. American Mineralogist, 54, 296–299.Google Scholar
Allmann, R. and Jepsen, H.P. (1969) Die struktur des Hydrotalkits. Neues Jahrbuch für Mineralogie, Monatshefte, 1969, 544–551.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 hydro-talcite-manasseite group. Crystallography Reports, 41, 972–981.Google Scholar
Arrhenius, G.O. (2003) Crystals and Life. Helvetica Chimica Acta, 86, 1569–1586.CrossRefGoogle Scholar
Bellotto, M., Rebours, B., Clause, O., Lynch, I., Bazin, D. and Elkaim, E. (1996) A reexamination of hydrotalcite crystal chemistry. Journal of Physical Chemistry, 100, 8527–8534.CrossRefGoogle Scholar
Bookin, A.S. and Drits, V.A. (1993) Polytype diversity of the hydrotalcite-like minerals. I. Possible poly-types and their diffraction patterns. Clays and Clay Minerals, 41, 551–557.CrossRefGoogle Scholar
Bookin, A.S., Cherkashin, V.I. and Drits, V.A. (1993) Polytype diversity of the hydrotalcite-group minerals. II. Determination of the polytypes of experimentally studied varieties. Clays and Clay Minerals, 41, 558–564.CrossRefGoogle Scholar
Braithwaite, R.S.W., Dunn, P.J., Pritchard, R.G. and Paar, W.H. (1994) Iowaite, a re-investigation. Mineralogical Magazine, 58, 79–85.CrossRefGoogle Scholar
Britto, S. and Kamath, P.V. (2009) Structure of bayerite-based lithium-aluminum layered double hydroxides (LDHs): observation of monoclinic symmetry. Inorganic Chemistry, 48, 11646–11654.CrossRefGoogle ScholarPubMed
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, 1541–1549.Google Scholar
Choy, J.-H., Kwak, S.-Y., Park, J.-S., Jeong, Y.-J. and Portier, J. (1999) Intercalative nanohybrids of nucleoside monophosphates and DNA in layered metal hydroxide. Journal of the American Chemical Society, 121, 1399–1400.CrossRefGoogle Scholar
Christiansen, B.C., Balic-Zunic, T., Petit, P.O., Frandsen, C., Morup, S., Geckeis, H., Katerinopoulou, A. and Stipp, S.L.S. (2009) Composition and structure of an iron-bearing, layered double hydroxide (LDH) – Green rust sodium sulphate. Geochimica et Cosmochimica Acta, 73, 3579–3592.CrossRefGoogle Scholar
Cooper, M.A. and Hawthorne, F.C. (1996) The crystal structure of shigaite, Na(H2O)6{H2O}6, hydrotalcite-group mineral. The Canadian Mineralogist, 34, 91–97.Google Scholar
Drits, V.A. and Bookin, A.S. (2001) Crystal structure and X-ray identification of layered double hydroxides. Pp. 39–92 in: Layered Double Hydroxides: Present and Future (Rives, V., editor). Nova Science Publishers Inc., New York.Google Scholar
Duan, X. and Evans, D.G., editors (2006) Layered Double Hydroxides. Structure and Bonding, Vol. 119, Springer, Berlin.CrossRefGoogle Scholar
Evans, D.G. and Slade, R.C.T. (2006) Structural aspects of layered double hydroxides. Pp. 1–87 in: Layered Double Hydroxides (X. Duan and D.G. Evans, editors). Springer, Berlin.Google Scholar
Francois, M., Renaudin, G. and Evrard, O. (1998) A cementitious compound with composition 3CaOAl2O3CaCO311H2O. Acta Crystallographies C54, 1214–1217.Google Scholar
Frost, R.L. and Dickfos, M. (2007) Hydrated double carbonates – a Raman and infrared spectroscopic study. Polyhedron, 26, 4503–4508.CrossRefGoogle Scholar
Génin, J.-M.R., Ruby, C. and Upadhyay, C. (2006) Structure and thermodynamics of ferrous, stoichiometric and ferric oxyhydroxycarbonate green rusts; redox exibility and fougerite mineral. Solid State Sciences, 8, 1330–1343.CrossRefGoogle Scholar
Greenwell, H.C. and Coveney, P.V. (2006) Layered double hydroxide minerals as possible prebiotic information storage and transfer compounds. Origins of Life and Evolution of the Biosphere, 36, 13–37.CrossRefGoogle ScholarPubMed
Hansen, H.C.B. (2001) Environmental chemistry of iron(II)-iron(III) LDHs (Green Rusts). Pp. 413–434 in: Layered Double Hydroxides: Present and Future (Rives, V., editor). Nova Science Publishers Inc., New York.Google Scholar
Hofmeister, W. and von Platen, H. (1992) Crystal chemistry and atomic order in brucite-related double-layer structures. Crystallography Reviews, 3, 3–26.CrossRefGoogle Scholar
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, 79–82.CrossRefGoogle Scholar
Ingram, L. and Taylor, H.F.W. (1967) The crystal structures of sjögrenite and pyroaurite. Mineralogical Magazine, 36, 465–479.CrossRefGoogle Scholar
Ivanyuk, G.Yu. and Yakovenchuk, V.N. (1997) Minerals of the Kovdor Massif. Apatity, RAS Kola Science Center publishing, Russia, 116 pp. (in Russian).Google Scholar
Johnsen, R.E. and Norby, P. (2009) A structural study of stacking disorder in the decomposition oxide of MgAl layered double hydroxide: a DIFFaX plus analysis. Journal of Physical Chemistry C113, 19061–19066.Google Scholar
Khan, A.I. and O'Hare, D. (2002) Intercalation chemistry of layered double hydroxides: recent developments and applications. Journal of Materials Chemistry, 12, 3191–3198.CrossRefGoogle Scholar
Kirkpatrick, R.J., Kalinichev, A.G., Wang, J., Hou, X. and Amonette, J.E. (2005) Molecular modeling of the vibrational spectra of interlayer and surface species of layered double hydroxides. Pp. 239–285 in: The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides (Kloprogge, J.T., editor). The Clay Minerals Society, Aurora, Colorado, USA.Google Scholar
Kloprogge, J.T., Wharton, D., Hickey, L. and Frost, R.L. (2002) Infrared and Raman study of interlayer anions in Mg/Al hydrotalcite. American Mineralogist, 87, 623–629.CrossRefGoogle Scholar
Koch, B.C. and Morup, S. (1991) Identification of green rust in an ochre sludge. Clay Minerals, 26, 577–582.CrossRefGoogle Scholar
Kumar, P.P., Kalinichev, A.G. and Kirkpatrick, R.J. (2006) Hydration, swelling, interlayer structure, and hydrogen bonding in organolayered double hydroxides: insights from molecular dynamics simulation of citrate-intercalated hydrotalcite. Journal of Physical Chemistry B110, 3841–3844.CrossRefGoogle Scholar
Menezes, L.A.D. and Martins, J.M. (1984) The Jacupiranga mine, São Paulo, Brazil. Mineralogical Record, 15, 261–270.Google 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, 4209–4215.Google Scholar
Rius, J. and Allmann, R. (1984) The superstructure of the double layer mineral wermlandite (H2O)12]2- . Zeitschrift für Kristallographie, 168, 133–144.CrossRefGoogle Scholar
Rives, V., editor (2001) Layered Double Hydroxides: Present and Future. Nova Science Publishers Inc., New York.Google Scholar
Ruby, C., Abdelmoula, M., Aissa, R., Medjahdi, G., Brunelli, M. and François, M. (2008) Aluminium substitution in iron(II–III)-layered double hydroxides: formation and cationic order. Journal of Solid State Chemistry, 181, 2285–2291.CrossRefGoogle Scholar
Sheldrick, G.M. (2008) A short history of SHELX. Acta Crystallographica, A64, 112–122.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, ill, 113–117.CrossRefGoogle Scholar
Speck, A. (2003) Single-crystal structure validation with the program PLATON . Journal of Applied Crystallography, 36, 7–13.CrossRefGoogle Scholar
Stampfl, P.P. (1969) Ein basisches Eisen-II-III-Karbonat. Corrosion Science, 9, 185–187.CrossRefGoogle Scholar
Stanimirova, T., Piperov, N., Petrova, N. and Kirov, G. (2004) Thermal evolution of Mg-Al-CO3 hydro-talcites. Clay Minerals, 39, 177–191.CrossRefGoogle Scholar
Taylor, H.F.W. (1973) Crystal structures of some double hydroxide minerals. Mineralogical Magazine, 39, 377–389.CrossRefGoogle Scholar
Terzis, A., Filippakis, S., Kuzel, H.-J. and Burzlaff, H. (1987) The crystal structure of Ca2Al(OH)6Cl-2H2O. Zeitschrift für Kristallographie 181, 29–34.CrossRefGoogle Scholar
Thyveetil, M.-A., Coveney, P.V., Greenwell, H.C. and Suter J.L. (2008) Computer simulation study of the structural stability and materials properties of DNA-intercalated layered double hydroxides. Journal of the American Chemical Society 130, 4742–4756.CrossRefGoogle ScholarPubMed
Trolard, F. (2006) Fougerite: from field experiment to the homologation of the mineral. Comptes Rendus Geoscience, 338, 1158–1166.CrossRefGoogle Scholar
Wang, J., Kalinichev, A.G., Kirkpatrick, R.J. and Hou, X. (2001) Molecular modeling of the structure and energetics of hydrotalcite hydration. Chemistry of Materials, 13, 145–150.CrossRefGoogle Scholar
Wang, J., Kalinichev, A.G., Amonette, J. and Kirkpatrick, R.J. (2003) Interlayer structure and dynamics of Cl-bearing hydrotalcite: far infrared spectroscopy and molecular dynamics modeling. American Mineralogist, 88, 398–409.CrossRefGoogle Scholar