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

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doi: 10.2138/am.2008.2966
Authors:Yang, Hexiong; Downs, Robert T.
Author Affiliations:Primary:
University of Arizona, Department of Geosciences, Tucson, AZ, United States
Volume Title:American Mineralogist
Source:American Mineralogist, 93(7), p.1183-1186. Publisher: Mineralogical Society of America, Washington, DC, United States. ISSN: 0003-004X
Publication Date:2008
Note:In English. 31 refs.; illus., incl. 3 tables
Summary:The crystal structure of glaucodot, (Co,Fe)AsS, an important member of the FeAsS-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)-(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 (Co0.5Fe0.5)AsS, with a limited tolerance for the variation of the Co/Fe ratio. [R.A.H.]
Sections:Crystal structure
Subjects:Arsenides; Arsenopyrite; Cell dimensions; Cobalt; Cobaltite; Crystal chemistry; Crystal structure; Formula; Gersdorffite; Iron; Lattice parameters; Marcasite; Metals; Single-crystal method; Space groups; Stoichiometry; Sulfides; Sulfosalts; X-ray diffraction data; Europe; Scandinavia; Sweden; Western Europe; Glaucodot; Hakansboda Sweden
Abstract Numbers:08M/2961
Record ID:2008104152
Copyright Information:GeoRef, Copyright 2019 American Geosciences Institute. Abstract, copyright, Mineralogical Society of America, Reference includes data from GeoScienceWorld, Alexandria, VA, United States
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