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Dokuchaevite, Cu8O2(VO4)3Cl3, a new mineral with remarkably diverse Cu2+ mixed-ligand coordination environments

Published online by Cambridge University Press:  24 June 2019

Oleg I. Siidra Open the ORCID record for Oleg I. Siidra [Opens in a new window] ,
Evgeny V. Nazarchuk ,
Anatoly N. Zaitsev ,
Yury S. Polekhovsky ,
Thomas Wenzel  and
John Spratt
Oleg I. Siidra*
Affiliation:
Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034 St. Petersburg, Russia Nanomaterials Research Center, Kola Science Center, Russian Academy of Sciences, Apatity, Murmansk Region, 184200Russia
Evgeny V. Nazarchuk
Affiliation:
Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034 St. Petersburg, Russia
Anatoly N. Zaitsev
Affiliation:
Core Research Laboratories, Imaging and Analysis Centre, Natural History Museum, Cromwell Road, London SW7 5BD, UK Department of Mineralogy, St. Petersburg State University, University Embankment 7/9, 199034 St. Petersburg, Russia
Yury S. Polekhovsky
Affiliation:
Department of Mineral Deposits, St. Petersburg State University, University Embankment 7/9, 199034 St. Petersburg, Russia
Thomas Wenzel
Affiliation:
Mathematisch-Naturwissenschaftliche Fakultät, FB Geowissenschaften, Universität Tübingen, Wilhelmstr. 56, Tübingen, 72074, Germany
John Spratt
Affiliation:
Core Research Laboratories, Imaging and Analysis Centre, Natural History Museum, Cromwell Road, London SW7 5BD, UK
*
*Author for correspondence: Oleg I. Siidra, Email: [email protected]
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Abstract

Dokuchaevite, ideally Cu8O2(VO4)3Cl3, was found in the Yadovitaya fumarole of the Second scoria cone of the North Breach of the Great Tolbachik Fissure Eruption (1975–1976), Tolbachik volcano, Kamchatka Peninsula, Russia. Dokuchaevite occurs on the crusts of various copper sulfate exhalative minerals (such as kamchatkite and euchlorine) as individual prismatic crystals. Dokuchaevite is triclinic, P$\bar{1}$, a = 6.332(3), b = 8.204(4), c = 15.562(8) Å, α = 90.498(8), β = 97.173(7), γ = 90.896(13)°, V = 801.9(7) Å3 and R1 = 0.057. The eight strongest lines of the X-ray powder diffraction pattern are (d, Å (I)(hkl): (15.4396)(18)(00$\bar{1}$), (7.2762)(27)(0$\bar{1}$1), (5.5957)(43)(012), (4.8571)(33)($\bar{1}\bar{1}$1), (3.1929) (29)(023), (2.7915)(30)(202), (2.5645)(21)(032), (2.5220)(100)(1$\bar{3}$0), (2.4906)(18)(130) and (2.3267)(71)(2$\bar{2}$2). The chemical composition determined by electron-microprobe analysis is (wt.%): CuO 60.87, ZnO 0.50, FeO 0.36, V2O5 19.85, As2O5 6.96, SO3 0.44, MoO3 1.41, SiO2 0.20, P2O5 0.22, Cl 10.66, –O = Cl2 2.41, total 99.06. The empirical formula calculated on the basis of 17 anions per formula unit is (Cu7.72Zn0.06Fe0.05)Σ7.83(V2.20As0.61Mo0.10S0.06P0.03Si0.03)Σ3.03O13.96Cl3.04.

The crystal structure of dokuchaevite represents a new structure type with eight Cu sites, which demonstrate the remarkable diversity of Cu2+ mixed-ligand coordination environments. The crystal structure of dokuchaevite is based on OCu4 tetrahedra that share common corners thus forming [O2Cu6]8+ single chains. Two of the eight symmetrically independent copper atoms do not form Cu–O bonds with additional oxygen atoms, and thus are not part of the OCu4 tetrahedra, but provide the three-dimensional integrity of the [O2Cu6]8+ chains into a framework. TO4 mixed tetrahedral groups are located within the cavities of the framework. The structural formula of dokuchaevite can be represented as Cu2[Cu6O2](VO4)3Cl3.

Keywords

dokuchaevitenew mineralscoppervanadatesoxocentred tetrahedraTolbachik volcano
Type
Article
Information
Mineralogical Magazine , Volume 83 , Issue 5 , October 2019 , pp. 749 - 755
Copyright
Copyright © Mineralogical Society of Great Britain and Ireland 2019 

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Footnotes

†

Deceased

Associate Editor: Daniel Atencio

References

Birnie, R.W. and Hughes, J.M. (1979) Stoiberite, Cu5V2O10, a new copper vanadate from Izalco volcano, El Salvador, Central America. American Mineralogist, 64, 941–944.Google Scholar
Brese, N.E. and O'Keeffe, M. (1991) Bond-valence parameters for solids. Acta Crystallographica, B47, 192–197.Google Scholar
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. Proceedings of the Russian Mineralogical Society, 146, 104–107.Google Scholar
Bruker-AXS (2014) APEX2. Version 2014.11-0. Madison, Wisconsin, USA.Google Scholar
Fedotov, S.A. and Markhinin, Y.K. (editors) (1983) The Great Tolbachik Fissure Eruption. Cambridge University Press, New York,Google Scholar
Filatov, S.K., Semenova, T.F. and Vergasova, L.P. (1992) Types of polymerization of [OCu4]6+ tetrahedra in inorganic compounds with additional oxygen atoms. Doklady Akademii Nauk SSSR, 322, 536–539 [in Russian].Google Scholar
Finger, L.W. (1985) Fingerite, Cu11O2(VO4)6, a new vanadium sublimate from Izalco volcano, El Salvador: crystal structure. American Mineralogist, 70, 197–199.Google Scholar
Hughes, J.M. and Birnie, R.W. (1980) Ziesite, β-Cu2V2O7, a new copper vanadate and fumarole temperature indicator. American Mineralogist, 65, 1146–1149.Google Scholar
Hughes, J.M. and Stoiber, R.E. (1985) Vanadium sublimates from the fumaroles of Izalco volcano, El Salvador. Journal of Volcanology and Geothermal Research, 24, 283–291.Google Scholar
Kovrugin, V.M., Colmont, M., Siidra, O.I., Mentré, O., Al-Shuray, A., Gurzhiy, V.V. and Krivovichev, S.V. (2015) Oxocentered Cu(II) lead selenite honeycomb lattices hosting Cu(I)Cl2 groups obtained by chemical vapor transport reactions. Chemical Communications, 51, 9563–9566.Google Scholar
Krivovichev, S.V., Filatov, S.K. and Vergasova, L.P. (2013 a) The crystal structure of ilinskite, NaCu5O2(SeO3)2Cl3, and review of mixed-ligand CuOmCln coordination geometries in minerals and inorganic compounds. Mineralogy and Petrology, 107, 235–242.Google Scholar
Krivovichev, S.V., Mentré, O., Siidra, O.I., Colmont, M. and Filatov, S.K. (2013 b) Anion-centered tetrahedra in inorganic compounds. Chemical Reviews, 113, 6459–6535.Google Scholar
Krivovichev, S.V., Filatov, S.K. and Vergasova, L.P. (2015) Refinement of the crystal structure of averievite Cu5O2(VO4)·nMClx (M = Cu, Cs, Rb, K). Proceedings of the Russian Mineralogical Society, 144, 101–109.Google Scholar
Liebau, F. (1985) Structural Chemistry of Silicates. Structure, Bonding and Classification. Springer Verlag, Berlin.Google Scholar
Pekov, I.V., Zubkova, N.V., Zelenski, M.E., Yapaskurt, V.O., Polekhovsky, Yu.S., Fadeeva, O.A. and Pushcharovsky, D.Yu. (2013) Yaroshevskite, Cu9O2(VO4)4Cl2, a new mineral from the Tolbachik volcano, Kamchatka, Russia. Mineralogical Magazine, 77, 107–116.Google Scholar
Pekov, I.V., Koshlyakova, N.N., Zubkova, N.V., Lykova, I.S., Britvin, S.N., Yapaskurt, V.O., Agakhanov, A.A., Shchipalkina, N.V., Turchkova, A.G. and Sidorov, E.G. (2018) Fumarolic arsenates – a special type of arsenic mineralization. European Journal of Mineralogy, 30, 305–322.Google Scholar
Siidra, O.I., Krivovichev, S.V., Armbruster, T., Filatov, S.K. and Pekov, I.V. (2007) The crystal structure of leningradite, PbCu3(VO4)2Cl2. The Canadian Mineralogist, 45, 445–449.Google Scholar
Siidra, O.I., Kozin, M.S., Depmeier, W., Kayukov, R.A. and Kovrugin, V.M. (2018 a) Copper-lead selenite bromides: A new large family of compounds partly having Cu2+ substructures derivable from Kagome–nets. Acta Crystallographica, B74, 712–724.Google Scholar
Siidra, O.I., Nazarchuk, E.V., Zaitsev, A.N., Polekhovsky, Y.S., Wenzel, T. and Spratt, J. (2018 b) Dokuchaevite, IMA 2018-012. CNMNC Newsletter No 43, June 2018, page 783; Mineralogical Magazine, 82, 779–785.Google Scholar
Siidra, O.I., Nazarchuk, E.V., Agakhanov, A.A. and Polekhovsky, Yu.S. (2019) Aleutite [Cu5O2](AsO4)(VO4)·(Cu0.5□0.5)Cl, a new complex salt-inclusion mineral with Cu2+ substructure derived from Kagome-net. Mineralogical Magazine, DOI: https://doi.org/10.1180/mgm.2019.42Google Scholar
Starova, G.L., Krivovichev, S.V. and Filatov, S.K. (1998) Crystal chemistry of inorganic compounds based on chains of oxocentered tetrahedra. II. Crystal structure of Cu4O2((As,V)O4)Cl. Zeitschrift für Kristallographie – Crystalline materials, 213, 650–653.Google Scholar
Vergasova, L.P. and Filatov, S.K. (2016) A study of volcanogenic exhalation mineralization. Journal of Volcanology and Seismology, 10, 71–85.Google Scholar
Witzke, T. and Ruger, F. (1998) Die Minerale der Ronneburger und Culmitzscher Lagerstatten in Thuringen. Lapis, 23, 26– 64.Google Scholar
Zelenski, M.E., Zubkova, N.V., Pekov, I.V., Boldyreva, M.M., Pushcharovsky, D.Yu. and Nekrasov, A.N. (2011) Pseudolyonsite, Cu3(VO4)2, a new mineral species from the Tolbachik volcano, Kamchatka Peninsula, Russia. European Journal of Mineralogy, 23, 475–481.Google Scholar
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