The crystal structure of vladimirite, with a revised chemical formula, Ca4(AsO4)2(AsO3OH)·4H 2O

Hexiong Yang, Stanley H. Evans, Robert T Downs, Robert A. Jenkins

Research output: Contribution to journalArticle

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Abstract

Two samples of vladimirite, one from Bou Azzer, Morocco, and the other from a new occurrence in Copiapó, Chile (designated as R100075 and R080001, respectively), were examined with an electron microprobe, single-crystal X-ray diffraction, and Raman spectroscopy. Our results show that vladimirite is monoclinic with space group P21/c and unit-cell parameters a 5.8279(2), b 10.1802(4), c 22.8944(10) Å, β 96.943(2)°, and V 1348.35(9) Å3 for R100075 and a 5.8220(1), b 10.1750(2), c 22.8816(6) Å, β 96.902(1)°, and V 1345.66(5) Å3 for R080001. The structure determinations, with R1, = 0.022 and 0.023 for R100075 and R080001, respectively, yielded an ideal chemical formula Ca4(AsO4)2(AsO3OH)·4H 2O (Z = 4) for this mineral, in contrast to Ca5(AsO 4)2(AsO3OH)2·5H2O (Z = 3) documented in the literature. The chemical compositions for R100075 and R080001 are Ca4.03(AsO4)2(As 0.99O3OH)·4H2O and Ca 3.97(AsO4)2(As1.01O 3OH)·4H2O, with trace Zn and Mn, respectively. The structure is characterized by undulating layers formed by the four nonequivalent, rather irregular Ca polyhedra [CalO6(H2O), Ca2O6(H2O), Ca3O4(H 2O)3, and Ca4O5(H2O)3] linked through the sharing of edges and vertices. These undulating layers are parallel to (010) and are interconnected by AsO4 and ASO 3OH tetrahedra, as well as hydrogen bonds, along the b axis. Vladimirite is remarkable inasmuch as one of the hydrogen-bonded O-H···O distances (012H-H···O3) is only 2.465(2) Å, which is the shortest donoracceptor distance of all known Ca-bearing arsenate minerals, similar to the short donor-acceptor distances observed in several synthetic compounds containing AsO3OH groups.

Original languageEnglish (US)
Pages (from-to)1055-1064
Number of pages10
JournalCanadian Mineralogist
Volume49
Issue number4
DOIs
StatePublished - Aug 2011

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crystal structure
Arsenate minerals
Bearings (structural)
Crystal structure
hydrogen
Raman spectroscopy
arsenate
mineral
electron probe analysis
Minerals
Hydrogen
Hydrogen bonds
chemical composition
X-ray diffraction
Single crystals
crystal
X ray diffraction
Electrons
Chemical analysis
chemical

Keywords

  • Arsenate
  • Crystal structure
  • Raman spectra
  • Vladimirite
  • X-ray diffraction

ASJC Scopus subject areas

  • Geochemistry and Petrology

Cite this

The crystal structure of vladimirite, with a revised chemical formula, Ca4(AsO4)2(AsO3OH)·4H 2O. / Yang, Hexiong; Evans, Stanley H.; Downs, Robert T; Jenkins, Robert A.

In: Canadian Mineralogist, Vol. 49, No. 4, 08.2011, p. 1055-1064.

Research output: Contribution to journalArticle

Yang, Hexiong ; Evans, Stanley H. ; Downs, Robert T ; Jenkins, Robert A. / The crystal structure of vladimirite, with a revised chemical formula, Ca4(AsO4)2(AsO3OH)·4H 2O. In: Canadian Mineralogist. 2011 ; Vol. 49, No. 4. pp. 1055-1064.
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title = "The crystal structure of vladimirite, with a revised chemical formula, Ca4(AsO4)2(AsO3OH)·4H 2O",
abstract = "Two samples of vladimirite, one from Bou Azzer, Morocco, and the other from a new occurrence in Copiap{\'o}, Chile (designated as R100075 and R080001, respectively), were examined with an electron microprobe, single-crystal X-ray diffraction, and Raman spectroscopy. Our results show that vladimirite is monoclinic with space group P21/c and unit-cell parameters a 5.8279(2), b 10.1802(4), c 22.8944(10) {\AA}, β 96.943(2)°, and V 1348.35(9) {\AA}3 for R100075 and a 5.8220(1), b 10.1750(2), c 22.8816(6) {\AA}, β 96.902(1)°, and V 1345.66(5) {\AA}3 for R080001. The structure determinations, with R1, = 0.022 and 0.023 for R100075 and R080001, respectively, yielded an ideal chemical formula Ca4(AsO4)2(AsO3OH)·4H 2O (Z = 4) for this mineral, in contrast to Ca5(AsO 4)2(AsO3OH)2·5H2O (Z = 3) documented in the literature. The chemical compositions for R100075 and R080001 are Ca4.03(AsO4)2(As 0.99O3OH)·4H2O and Ca 3.97(AsO4)2(As1.01O 3OH)·4H2O, with trace Zn and Mn, respectively. The structure is characterized by undulating layers formed by the four nonequivalent, rather irregular Ca polyhedra [CalO6(H2O), Ca2O6(H2O), Ca3O4(H 2O)3, and Ca4O5(H2O)3] linked through the sharing of edges and vertices. These undulating layers are parallel to (010) and are interconnected by AsO4 and ASO 3OH tetrahedra, as well as hydrogen bonds, along the b axis. Vladimirite is remarkable inasmuch as one of the hydrogen-bonded O-H···O distances (012H-H···O3) is only 2.465(2) {\AA}, which is the shortest donoracceptor distance of all known Ca-bearing arsenate minerals, similar to the short donor-acceptor distances observed in several synthetic compounds containing AsO3OH groups.",
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AU - Downs, Robert T

AU - Jenkins, Robert A.

PY - 2011/8

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N2 - Two samples of vladimirite, one from Bou Azzer, Morocco, and the other from a new occurrence in Copiapó, Chile (designated as R100075 and R080001, respectively), were examined with an electron microprobe, single-crystal X-ray diffraction, and Raman spectroscopy. Our results show that vladimirite is monoclinic with space group P21/c and unit-cell parameters a 5.8279(2), b 10.1802(4), c 22.8944(10) Å, β 96.943(2)°, and V 1348.35(9) Å3 for R100075 and a 5.8220(1), b 10.1750(2), c 22.8816(6) Å, β 96.902(1)°, and V 1345.66(5) Å3 for R080001. The structure determinations, with R1, = 0.022 and 0.023 for R100075 and R080001, respectively, yielded an ideal chemical formula Ca4(AsO4)2(AsO3OH)·4H 2O (Z = 4) for this mineral, in contrast to Ca5(AsO 4)2(AsO3OH)2·5H2O (Z = 3) documented in the literature. The chemical compositions for R100075 and R080001 are Ca4.03(AsO4)2(As 0.99O3OH)·4H2O and Ca 3.97(AsO4)2(As1.01O 3OH)·4H2O, with trace Zn and Mn, respectively. The structure is characterized by undulating layers formed by the four nonequivalent, rather irregular Ca polyhedra [CalO6(H2O), Ca2O6(H2O), Ca3O4(H 2O)3, and Ca4O5(H2O)3] linked through the sharing of edges and vertices. These undulating layers are parallel to (010) and are interconnected by AsO4 and ASO 3OH tetrahedra, as well as hydrogen bonds, along the b axis. Vladimirite is remarkable inasmuch as one of the hydrogen-bonded O-H···O distances (012H-H···O3) is only 2.465(2) Å, which is the shortest donoracceptor distance of all known Ca-bearing arsenate minerals, similar to the short donor-acceptor distances observed in several synthetic compounds containing AsO3OH groups.

AB - Two samples of vladimirite, one from Bou Azzer, Morocco, and the other from a new occurrence in Copiapó, Chile (designated as R100075 and R080001, respectively), were examined with an electron microprobe, single-crystal X-ray diffraction, and Raman spectroscopy. Our results show that vladimirite is monoclinic with space group P21/c and unit-cell parameters a 5.8279(2), b 10.1802(4), c 22.8944(10) Å, β 96.943(2)°, and V 1348.35(9) Å3 for R100075 and a 5.8220(1), b 10.1750(2), c 22.8816(6) Å, β 96.902(1)°, and V 1345.66(5) Å3 for R080001. The structure determinations, with R1, = 0.022 and 0.023 for R100075 and R080001, respectively, yielded an ideal chemical formula Ca4(AsO4)2(AsO3OH)·4H 2O (Z = 4) for this mineral, in contrast to Ca5(AsO 4)2(AsO3OH)2·5H2O (Z = 3) documented in the literature. The chemical compositions for R100075 and R080001 are Ca4.03(AsO4)2(As 0.99O3OH)·4H2O and Ca 3.97(AsO4)2(As1.01O 3OH)·4H2O, with trace Zn and Mn, respectively. The structure is characterized by undulating layers formed by the four nonequivalent, rather irregular Ca polyhedra [CalO6(H2O), Ca2O6(H2O), Ca3O4(H 2O)3, and Ca4O5(H2O)3] linked through the sharing of edges and vertices. These undulating layers are parallel to (010) and are interconnected by AsO4 and ASO 3OH tetrahedra, as well as hydrogen bonds, along the b axis. Vladimirite is remarkable inasmuch as one of the hydrogen-bonded O-H···O distances (012H-H···O3) is only 2.465(2) Å, which is the shortest donoracceptor distance of all known Ca-bearing arsenate minerals, similar to the short donor-acceptor distances observed in several synthetic compounds containing AsO3OH groups.

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KW - Crystal structure

KW - Raman spectra

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KW - X-ray diffraction

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