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Crystal chemistry of halurgite, Mg4[B8O13(OH)2]2·7H2O, a microporous heterophylloborate mineral

  • Igor V. Pekov (a1), Natalia V. Zubkova (a1), Dmitry A. Ksenofontov (a1), Nikita V. Chukanov (a2), Oksana V. Korotchenkova (a3), Ilya I. Chaikovskiy (a3), Vasiliy O. Yapaskurt (a1), Sergey N. Britvin (a4) and Dmitry Yu. Pushcharovsky (a1)...

Abstract

Three samples of halurgite were re-examined: two from the Chelkar salt dome in the North Caspian Region, Western Kazakhstan (the type locality and including the type specimen), and one from a new locality in the Satimola salt dome located in the same region. The crystal structure of halurgite has been solved for the first time on the specimen from Chelkar with the empirical formula Mg3.94[B8.03O13.03(OH)1.97]2·7.16H2O; refinement began with single-crystal X-ray diffraction data and was subsequently refined on a powder sample using the Rietveld method (Rp = 0.0232, Rwp = 0.0354 and Robs = 0.0558). The idealised crystal chemical formula of halurgite is Mg4[B8O13(OH)2]2·7H2O. The mineral is monoclinic, P2/c, a = 13.201(2), b = 7.5622(10), c = 13.185(2) Å, β = 91.834(14)°, V = 1315.6(4) Å3 and Z = 2. The crystal structure is unique. Eight B polyhedra form a fundamental building block [B8O16(OH)2], which is a six-membered borate ring (built by two pairs of B tetrahedra and two B triangles) with two additional triangular BO2(OH) groups. Each [B8O16(OH)2] ring is linked to six adjacent analogous rings to form a [B8O13(OH)2] layer. These layers are connected via MgO6 and Mg(OH)2(H2O)4 octahedra into a microporous heteropolyhedral pseudo-framework. The crystal structure of halurgite can also be described in terms of an approach developed for heterophyllosilicates containing three-layer HOH modules, where HOH refers to an octahedral layer O sandwiched between two heteropolyhedral layers H. In halurgite the HOH module consists of two heteropolyhedral (BO3 triangles + BO4 tetrahedra) borate H layers [B8O13(OH)2] and a central interrupted O layer composed of MgO6 octahedra, whereas a more voluminous Mg(OH)2(H2O)4 octahedral complex and additional H2O molecules are located between HOH modules. Halurgite and four related synthetic H-free borates M2Cd3B16O28 and M2Ca3B16O28 (M = Rb or Cs) can be considered microporous heterophylloborates.

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*Author for correspondence: Igor V. Pekov, Email: igorpekov@mail.ru

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Associate Editor: Charles A Geiger

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Agilent Technologies (2014) CrysAlisPro Software system, version 1.171.37.34, Agilent Technologies UK Ltd, Oxford, UK.
Avrova, N.P., Bocharov, V.M., Khalturina, I.I., and Yunusova, Z.R. (1968) Mineralogy of borates in halogenic deposits. Pp. 169173 in: Geologiya i Razvedka Mestorozhdenii Tverdykh Poleznykh Iskopaemykh Kazakhstana (= Geology and Prospecting of Solid Mineral Resources of Kazakhstan). Nauka Publishing, Alma-Ata [in Russian].
Bermanec, V., Furić, K., Rajić, M. and Kniewald, G. (2003) Thermal stability and vibrational spectra of the sheet borate tuzlaite, NaCa[B5O8(OH)2]·3H2O. American Mineralogist, 88, 271276.
Britvin, S.N., Dolivo-Dobrovolsky, D.V. and Krzhizhanovskaya, M.G. (2017) Software for processing the X-ray powder diffraction data obtained from the curved image plate detector of Rigaku RAXIS Rapid II diffractometer. Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 146, 104107 [in Russian].
Burns, P.C., Grice, J.D. and Hawthorne, F.C. (1995) Borate minerals. I. Polyhedral clusters and fundamental building blocks. The Canadian Mineralogist, 33, 11311151.
Cámara, F., Sokolova, E., Abdu, Y.A. and Pautov, L.A. (2016) From structure topology to chemical composition. XIX. Titanium silicates: revision of the crystal structure and chemical formula of bafertisite, Ba2Fe2+4Ti2(Si2O7)2O2(OH)2F2, a group-II TS-block mineral. The Canadian Mineralogist, 54, 4963.
Chukanov, N.V. (2014) Infrared Spectra of Mineral Species: Extended Library. Springer–Verlag, Dordrecht, The Netherlands, 1716 pp.
Chukanov, N.V. and Chervonnyi, A.D. (2016) Infrared Spectroscopy of Minerals and Related Compounds. Springer-Verlag, Cham, Switzerland, 1109 pp.
Dong, X., Shi, Y., Zhou, Z., Pan, S., Yang, Z., Zhang, B., Yang, Y., Chen, Z. and Huang, Z. (2013) M2Cd3B16O28 (M = Rb, Cs): two isostructural alkali cadmium borates with a new type of borate layer. European Journal of Inorganic Chemistry, 2, 203207.
Ferraris, G. and Gula, A. (2005) Polysomatic aspects of microporous minerals – heterophyllosilicates, palysepioles and rhodesite-related structures. Pp. 69104 in: Micro- and Mesoporous Mineral Phases (Ferraris, G. and Merlino, S., editors) Reviews in Mineralogy & Geochemistry, 57. Mineralogical Society of America and the Geochemical Society, Chantilly, Virginia, USA.
Ferraris, G., Ivaldi, G., Pushcharovsky, D.Y., Zubkova, N.V. and Pekov, I.V. (2001) The crystal structure of delindeite, Ba2{(Na,K,□)3(Ti,Fe)[Ti2(O,OH)4Si4O14](H2O,OH,O)2}, a member of the mero-plesiotype bafertisite series. The Canadian Mineralogist, 39, 13061316.
Gagné, O.C. and Hawthorne, F.C. (2015) Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen. Acta Crystallographica, B71, 562578.
Grice, J.D., Burns, P.C. and Hawthorne, F.C. (1999) Borate minerals. II. A hierarchy of structures based upon the borate fundamental building block. The Canadian Mineralogist, 37, 731762.
Jun, L., Shuping, X. and Shiyang, G. (1995) FT-IR and Raman spectroscopic study of hydrated borates. Spectrochimica Acta A, 51, 519532.
Kondrat'eva, V.V. (1964) New X-ray data regarding halurgite and inderborite. Soviet Physics – Crystallography, 9, 616617.
Kondrat'eva, V.V. (1969) Rentgenometricheskii Opredelitel' Boratov (= Reference Book for Identification of Borates from X-Ray Diffraction Data). Nedra Publishing, Leningrad, 248 pp. [in Russian].
Korotchenkova, O.V. and Chaikovskiy, I.I. (2016) Boron minerals of the Chelkar deposit. Problems of Mineralogy, Petrography and Metallogeny (P.N. Chirvinsky Scientific Conference, Perm University), 19, 5565 [in Russian].
Libowitzky, E. (1999) Correlation of O–H stretching frequencies and O–H···O hydrogen bond lengths in minerals. Monatshefte für Chemie, 130, 10471059.
Lobanova, V.V. (1962) Halurgite, a new borate. Doklady Akademii Nauk SSSR, 143, 693696 [in Russian].
Pakhomovsky, Y.A., Panikorovskii, T.L., Yakovenchuk, V.N., Ivanyuk, G.Y., Mikhailova, J.A., Krivovichev, S.V., Bocharov, V.N. and Kalashnikov, A.O. (2018) Selivanovaite, NaTi3(Ti,Na,Fe,Mn)4[(Si2O7)2O4(OH,H2O)4nH2O, a new rock-forming mineral from the eudialyte-rich malignite of the Lovozero alkaline massif (Kola Peninsula, Russia). European Journal of Mineralogy, 30, 525535.
Pekov, I.V. (1998) Minerals First Discovered on the Territory of the Former Soviet Union. OP, Moscow, 369 pp.
Pekov, I.V., Lykova, I.S. and Nikiforov, A.B. (2015) The collection of Victor I. Stepanov and its significance. Mineralogical Almanac, 20, 1245.
Petříček, V., Dušek, M. and Palatinus, L. (2006) Jana2006. Structure Determination Software Programs. Institute of Physics, Praha, Czech Republic.
Sheldrick, G.M. (2015) Crystal structure refinement with SHELXL. Acta Crystallographica, C71, 38.
Weir, C.E. (1966) Infrared spectra of the hydrated borates. Journal of Research of the National Bureau of Standards – A. Physics and Chemistry, 70, 153164.
Yamnova, N.A., Egorov-Tismenko, Yu.K. and Pekov, I.V. (1998) Crystal structure of perraultite from the coastal region of the sea of Azov. Crystallography Reports, 43, 401410.
Zhang, X., Li, D., Wu, H., Yang, Z. and Pan, S. (2016) M2Ca3B16O28 (M = Rb, Cs): structures analogous to SBBO with three-dimensional open-framework layers. RSC Advances, 6, 1420514210.

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