Dokuchaevite, Cu 8 O 2 (VO 4 ) 3 Cl 3 , a new mineral with remarkably diverse Cu 2+ mixed-ligand coordination environments

Oleg I. Siidra, Evgeny V. Nazarchuk, Anatoly N. Zaitsev, Yury S. Polekhovsky, Thomas J. Wenzel, John Spratt

Research output

Abstract

Dokuchaevite, ideally Cu 8 O 2 (VO 4) 3 Cl 3 , was found in a 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 sulphate exhalative minerals (kamchatkite, euchlorine) as individual prismatic crystals. Dokuchaevite is triclinic, P ̅ , 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)º, V = 801.9(7) Å 3 , R 1 = 0.057. The eight strongest lines of the X-ray powder diffraction pattern are (I-d-hkl): 18-15.4396-00 ̅ , 27-7.2762-0 ̅ 1, 43-5.5957-012, 33-4.8571-̅ ̅ 1, 29-3.1929-023, 30-2.7915-202, 21-2.5645-032, 100-2.5220-1 ̅ 0, 18-2.4906-130, 71-2.3267-2 ̅ 2. The chemical composition determined by electron-microprobe analysis is (wt. %): CuO 60.87, ZnO 0.50, FeO 0.36, V 2 O 5 19.85, As 2 O 5 6.96, SO 3 0.44, MoO 3 1.41, SiO 2 0.20, P 2 O 5 0.22, Cl 10.66,-O=Cl 2 2.41, total 99.06. The empirical formula calculated on the basis of 17 anions pfu is (Cu 7.72 Zn 0.06 Fe 0.05) 7.83 Crystal structure of dokuchaevite represents a new structure type with eight Cu sites, which demonstrate remarkable diversity of Cu 2+ mixed-ligand coordination environments. Crystal structure of dokuchaevite is based on OCu 4 tetrahedra that share common corners thus forming [O 2 Cu 6 ] 8+ single chains. Two of eight symmetrically independent copper atoms do not form Cu-O bonds with additional oxygen atoms, and thus are not part of the OCu 4 tetrahedra, but provide the three-dimensional integrity of the [O 2 Cu 6 ] 8+ chains into framework. TO 4 mixed tetrahedral groups are located within the cavities of the framework. The structural formula of dokuchaevite can be represented as Cu 2 [Cu 6 O 2 ](VO 4) 3 Cl 3 .
Original languageEnglish
Pages (from-to)749-755
JournalMineralogical Magazine
Volume83
Issue number5
Publication statusPublished - 10 Oct 2019

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@article{a887f4e0599541f6880ee0287fa999e7,
title = "Dokuchaevite, Cu 8 O 2 (VO 4 ) 3 Cl 3 , a new mineral with remarkably diverse Cu 2+ mixed-ligand coordination environments",
abstract = "Dokuchaevite, ideally Cu 8 O 2 (VO 4) 3 Cl 3 , was found in a 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 sulphate exhalative minerals (kamchatkite, euchlorine) as individual prismatic crystals. Dokuchaevite is triclinic, P ̅ , a = 6.332(3), b = 8.204(4), c = 15.562(8) {\AA}, α = 90.498(8), β = 97.173(7), γ = 90.896(13)º, V = 801.9(7) {\AA} 3 , R 1 = 0.057. The eight strongest lines of the X-ray powder diffraction pattern are (I-d-hkl): 18-15.4396-00 ̅ , 27-7.2762-0 ̅ 1, 43-5.5957-012, 33-4.8571-̅ ̅ 1, 29-3.1929-023, 30-2.7915-202, 21-2.5645-032, 100-2.5220-1 ̅ 0, 18-2.4906-130, 71-2.3267-2 ̅ 2. The chemical composition determined by electron-microprobe analysis is (wt. {\%}): CuO 60.87, ZnO 0.50, FeO 0.36, V 2 O 5 19.85, As 2 O 5 6.96, SO 3 0.44, MoO 3 1.41, SiO 2 0.20, P 2 O 5 0.22, Cl 10.66,-O=Cl 2 2.41, total 99.06. The empirical formula calculated on the basis of 17 anions pfu is (Cu 7.72 Zn 0.06 Fe 0.05) 7.83 Crystal structure of dokuchaevite represents a new structure type with eight Cu sites, which demonstrate remarkable diversity of Cu 2+ mixed-ligand coordination environments. Crystal structure of dokuchaevite is based on OCu 4 tetrahedra that share common corners thus forming [O 2 Cu 6 ] 8+ single chains. Two of eight symmetrically independent copper atoms do not form Cu-O bonds with additional oxygen atoms, and thus are not part of the OCu 4 tetrahedra, but provide the three-dimensional integrity of the [O 2 Cu 6 ] 8+ chains into framework. TO 4 mixed tetrahedral groups are located within the cavities of the framework. The structural formula of dokuchaevite can be represented as Cu 2 [Cu 6 O 2 ](VO 4) 3 Cl 3 .",
keywords = "dokuchaevite, new minerals, Copper, vanadates, Oxocentered tetrahedra, Tolbachik volcano",
author = "Siidra, {Oleg I.} and Nazarchuk, {Evgeny V.} and Zaitsev, {Anatoly N.} and Polekhovsky, {Yury S.} and Wenzel, {Thomas J.} and John Spratt",
year = "2019",
month = "10",
day = "10",
language = "English",
volume = "83",
pages = "749--755",
journal = "Mineralogical Magazine",
issn = "0026-461X",
publisher = "Mineralogical Society",
number = "5",

}

TY - JOUR

T1 - Dokuchaevite, Cu 8 O 2 (VO 4 ) 3 Cl 3 , a new mineral with remarkably diverse Cu 2+ mixed-ligand coordination environments

AU - Siidra, Oleg I.

AU - Nazarchuk, Evgeny V.

AU - Zaitsev, Anatoly N.

AU - Polekhovsky, Yury S.

AU - Wenzel, Thomas J.

AU - Spratt, John

PY - 2019/10/10

Y1 - 2019/10/10

N2 - Dokuchaevite, ideally Cu 8 O 2 (VO 4) 3 Cl 3 , was found in a 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 sulphate exhalative minerals (kamchatkite, euchlorine) as individual prismatic crystals. Dokuchaevite is triclinic, P ̅ , 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)º, V = 801.9(7) Å 3 , R 1 = 0.057. The eight strongest lines of the X-ray powder diffraction pattern are (I-d-hkl): 18-15.4396-00 ̅ , 27-7.2762-0 ̅ 1, 43-5.5957-012, 33-4.8571-̅ ̅ 1, 29-3.1929-023, 30-2.7915-202, 21-2.5645-032, 100-2.5220-1 ̅ 0, 18-2.4906-130, 71-2.3267-2 ̅ 2. The chemical composition determined by electron-microprobe analysis is (wt. %): CuO 60.87, ZnO 0.50, FeO 0.36, V 2 O 5 19.85, As 2 O 5 6.96, SO 3 0.44, MoO 3 1.41, SiO 2 0.20, P 2 O 5 0.22, Cl 10.66,-O=Cl 2 2.41, total 99.06. The empirical formula calculated on the basis of 17 anions pfu is (Cu 7.72 Zn 0.06 Fe 0.05) 7.83 Crystal structure of dokuchaevite represents a new structure type with eight Cu sites, which demonstrate remarkable diversity of Cu 2+ mixed-ligand coordination environments. Crystal structure of dokuchaevite is based on OCu 4 tetrahedra that share common corners thus forming [O 2 Cu 6 ] 8+ single chains. Two of eight symmetrically independent copper atoms do not form Cu-O bonds with additional oxygen atoms, and thus are not part of the OCu 4 tetrahedra, but provide the three-dimensional integrity of the [O 2 Cu 6 ] 8+ chains into framework. TO 4 mixed tetrahedral groups are located within the cavities of the framework. The structural formula of dokuchaevite can be represented as Cu 2 [Cu 6 O 2 ](VO 4) 3 Cl 3 .

AB - Dokuchaevite, ideally Cu 8 O 2 (VO 4) 3 Cl 3 , was found in a 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 sulphate exhalative minerals (kamchatkite, euchlorine) as individual prismatic crystals. Dokuchaevite is triclinic, P ̅ , 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)º, V = 801.9(7) Å 3 , R 1 = 0.057. The eight strongest lines of the X-ray powder diffraction pattern are (I-d-hkl): 18-15.4396-00 ̅ , 27-7.2762-0 ̅ 1, 43-5.5957-012, 33-4.8571-̅ ̅ 1, 29-3.1929-023, 30-2.7915-202, 21-2.5645-032, 100-2.5220-1 ̅ 0, 18-2.4906-130, 71-2.3267-2 ̅ 2. The chemical composition determined by electron-microprobe analysis is (wt. %): CuO 60.87, ZnO 0.50, FeO 0.36, V 2 O 5 19.85, As 2 O 5 6.96, SO 3 0.44, MoO 3 1.41, SiO 2 0.20, P 2 O 5 0.22, Cl 10.66,-O=Cl 2 2.41, total 99.06. The empirical formula calculated on the basis of 17 anions pfu is (Cu 7.72 Zn 0.06 Fe 0.05) 7.83 Crystal structure of dokuchaevite represents a new structure type with eight Cu sites, which demonstrate remarkable diversity of Cu 2+ mixed-ligand coordination environments. Crystal structure of dokuchaevite is based on OCu 4 tetrahedra that share common corners thus forming [O 2 Cu 6 ] 8+ single chains. Two of eight symmetrically independent copper atoms do not form Cu-O bonds with additional oxygen atoms, and thus are not part of the OCu 4 tetrahedra, but provide the three-dimensional integrity of the [O 2 Cu 6 ] 8+ chains into framework. TO 4 mixed tetrahedral groups are located within the cavities of the framework. The structural formula of dokuchaevite can be represented as Cu 2 [Cu 6 O 2 ](VO 4) 3 Cl 3 .

KW - dokuchaevite

KW - new minerals

KW - Copper

KW - vanadates

KW - Oxocentered tetrahedra

KW - Tolbachik volcano

UR - https://www.researchgate.net/publication/333981668_Dokuchaevite_Cu_8_O_2_VO_4_3_Cl_3_a_new_mineral_with_remarkably_diverse_Cu_2_mixed-ligand_coordination_environments

M3 - Article

VL - 83

SP - 749

EP - 755

JO - Mineralogical Magazine

JF - Mineralogical Magazine

SN - 0026-461X

IS - 5

ER -