Crystal structure of glaucodot, (Co,Fe) AsS, and its relationship to marcasite and arsenopyrite

Hexiong Yang, Robert T Downs

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The crystal structure of glaucodot, (Co,Fe)AsS, an important member of the FcAsS-CoAsS-NiAsS system, was determined with single-crystal X-ray diffraction. It is orthorhombic with space group Pn21m and unit-cell parameters a = 14.158(1), b = 5.6462(4), c = 3.3196(2) Å, and V= 265.37(5) Å3. The structure is closely related to that of arsenopyrite or alloclasite, and represents a new derivative of the marcasite-type structure. The As and S atoms in glaucodot, which are ordered into six distinct sites (As1, As2, As3, S1, S2, and S3), form three types of layers [S, As, and mixed (S + As) layers] that are stacked along a in the sequence of (S + As)-(S + As)-S-(S + As)-(S + As)-As-(S + As)-(S + As)... In contrast, arsenopyrite contains the mixed (S + As) layers only and alloclasite consists of isolated S and As layers only. There are no As-As or S-S bonds in glaucodot; all dianion units are formed between S and As, like those in arsenopyrite and alloclasite. The (Co + Fe) cations in glaucodot occupy three nonequivalent octahedral sites (M1, M2, and M3), with M1(As5S), M2(As3S3), and M3(AsS5), which form three distinct edge-shared octahedral chains, A, B, and C, parallel to c, respectively. These chains are arranged along a in the sequence of A-A-B-C-C-B-A-A.... Whereas the configurations of the A and C chains are analogous to those in safflorite and marcasite, respectively, the configuration of the B chain matches that in alloclasite, leading us to propose that the M1, M2, and M3 sites are predominately occupied by Co, (Co + Fe), and Fe, respectively. Our study, together with previous observations, suggests that glaucodot is likely to have an ideal stoichiometry of (Co0.5 Fe0.5)AsS, with a limited tolerance for the variation of the Co/Fe ratio.

Original languageEnglish (US)
Pages (from-to)1183-1186
Number of pages4
JournalAmerican Mineralogist
Volume93
Issue number7
DOIs
StatePublished - Jul 2008

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marcasite
arsenopyrite
crystal structure
Crystal structure
Stoichiometry
Cations
stoichiometry
configurations
Single crystals
Derivatives
X ray diffraction
Atoms
tolerance
cation
X-ray diffraction
crystal
cations
single crystals
cells
diffraction

Keywords

  • Co-Fe sulfarsenide
  • Crystal structure
  • Glaucodot
  • Marcasite-type mineral
  • Single-crystal X-ray diffraction

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics

Cite this

Crystal structure of glaucodot, (Co,Fe) AsS, and its relationship to marcasite and arsenopyrite. / Yang, Hexiong; Downs, Robert T.

In: American Mineralogist, Vol. 93, No. 7, 07.2008, p. 1183-1186.

Research output: Contribution to journalArticle

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title = "Crystal structure of glaucodot, (Co,Fe) AsS, and its relationship to marcasite and arsenopyrite",
abstract = "The crystal structure of glaucodot, (Co,Fe)AsS, an important member of the FcAsS-CoAsS-NiAsS system, was determined with single-crystal X-ray diffraction. It is orthorhombic with space group Pn21m and unit-cell parameters a = 14.158(1), b = 5.6462(4), c = 3.3196(2) {\AA}, and V= 265.37(5) {\AA}3. The structure is closely related to that of arsenopyrite or alloclasite, and represents a new derivative of the marcasite-type structure. The As and S atoms in glaucodot, which are ordered into six distinct sites (As1, As2, As3, S1, S2, and S3), form three types of layers [S, As, and mixed (S + As) layers] that are stacked along a in the sequence of (S + As)-(S + As)-S-(S + As)-(S + As)-As-(S + As)-(S + As)... In contrast, arsenopyrite contains the mixed (S + As) layers only and alloclasite consists of isolated S and As layers only. There are no As-As or S-S bonds in glaucodot; all dianion units are formed between S and As, like those in arsenopyrite and alloclasite. The (Co + Fe) cations in glaucodot occupy three nonequivalent octahedral sites (M1, M2, and M3), with M1(As5S), M2(As3S3), and M3(AsS5), which form three distinct edge-shared octahedral chains, A, B, and C, parallel to c, respectively. These chains are arranged along a in the sequence of A-A-B-C-C-B-A-A.... Whereas the configurations of the A and C chains are analogous to those in safflorite and marcasite, respectively, the configuration of the B chain matches that in alloclasite, leading us to propose that the M1, M2, and M3 sites are predominately occupied by Co, (Co + Fe), and Fe, respectively. Our study, together with previous observations, suggests that glaucodot is likely to have an ideal stoichiometry of (Co0.5 Fe0.5)AsS, with a limited tolerance for the variation of the Co/Fe ratio.",
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N2 - The crystal structure of glaucodot, (Co,Fe)AsS, an important member of the FcAsS-CoAsS-NiAsS system, was determined with single-crystal X-ray diffraction. It is orthorhombic with space group Pn21m and unit-cell parameters a = 14.158(1), b = 5.6462(4), c = 3.3196(2) Å, and V= 265.37(5) Å3. The structure is closely related to that of arsenopyrite or alloclasite, and represents a new derivative of the marcasite-type structure. The As and S atoms in glaucodot, which are ordered into six distinct sites (As1, As2, As3, S1, S2, and S3), form three types of layers [S, As, and mixed (S + As) layers] that are stacked along a in the sequence of (S + As)-(S + As)-S-(S + As)-(S + As)-As-(S + As)-(S + As)... In contrast, arsenopyrite contains the mixed (S + As) layers only and alloclasite consists of isolated S and As layers only. There are no As-As or S-S bonds in glaucodot; all dianion units are formed between S and As, like those in arsenopyrite and alloclasite. The (Co + Fe) cations in glaucodot occupy three nonequivalent octahedral sites (M1, M2, and M3), with M1(As5S), M2(As3S3), and M3(AsS5), which form three distinct edge-shared octahedral chains, A, B, and C, parallel to c, respectively. These chains are arranged along a in the sequence of A-A-B-C-C-B-A-A.... Whereas the configurations of the A and C chains are analogous to those in safflorite and marcasite, respectively, the configuration of the B chain matches that in alloclasite, leading us to propose that the M1, M2, and M3 sites are predominately occupied by Co, (Co + Fe), and Fe, respectively. Our study, together with previous observations, suggests that glaucodot is likely to have an ideal stoichiometry of (Co0.5 Fe0.5)AsS, with a limited tolerance for the variation of the Co/Fe ratio.

AB - The crystal structure of glaucodot, (Co,Fe)AsS, an important member of the FcAsS-CoAsS-NiAsS system, was determined with single-crystal X-ray diffraction. It is orthorhombic with space group Pn21m and unit-cell parameters a = 14.158(1), b = 5.6462(4), c = 3.3196(2) Å, and V= 265.37(5) Å3. The structure is closely related to that of arsenopyrite or alloclasite, and represents a new derivative of the marcasite-type structure. The As and S atoms in glaucodot, which are ordered into six distinct sites (As1, As2, As3, S1, S2, and S3), form three types of layers [S, As, and mixed (S + As) layers] that are stacked along a in the sequence of (S + As)-(S + As)-S-(S + As)-(S + As)-As-(S + As)-(S + As)... In contrast, arsenopyrite contains the mixed (S + As) layers only and alloclasite consists of isolated S and As layers only. There are no As-As or S-S bonds in glaucodot; all dianion units are formed between S and As, like those in arsenopyrite and alloclasite. The (Co + Fe) cations in glaucodot occupy three nonequivalent octahedral sites (M1, M2, and M3), with M1(As5S), M2(As3S3), and M3(AsS5), which form three distinct edge-shared octahedral chains, A, B, and C, parallel to c, respectively. These chains are arranged along a in the sequence of A-A-B-C-C-B-A-A.... Whereas the configurations of the A and C chains are analogous to those in safflorite and marcasite, respectively, the configuration of the B chain matches that in alloclasite, leading us to propose that the M1, M2, and M3 sites are predominately occupied by Co, (Co + Fe), and Fe, respectively. Our study, together with previous observations, suggests that glaucodot is likely to have an ideal stoichiometry of (Co0.5 Fe0.5)AsS, with a limited tolerance for the variation of the Co/Fe ratio.

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KW - Crystal structure

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KW - Marcasite-type mineral

KW - Single-crystal X-ray diffraction

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