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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: o.siidra@spbu.ru
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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

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