Crystal structure of uchucchacuaite, AgMnPb3Sb5S 12, and its relationship with ramdohrite and fzélyite
Uchucchacuaite, ideally AgMnPb3Sb5S12, was originally reported as orthorhombic, with possible space group Pmmm, P222, or Pmm2, and unit-cell parameters a = 12.67, b = 19.32, and c = 4.38 Å obtained from powder X-ray diffraction data (Moëlo et al. 1984a). Using single-crystal X-ray diffraction, we examined two uchucchacuaite samples, one from the type locality, Uchucchacua, Peru, and the other from Hokkaido, Japan (designated as R100213 and R070760, respectively). Our results show that uchucchacuaite is isostructural with ramdohrite and fizélyite, with monoclinic symmetry (P21/n) and the unit-cell parameters a = 19.3645(11), b = 12.7287(8), c = 8.7571(6) Å, β = 90.059(3)° for R100213 and a = 19.3462(7), b = 12.7251(5), c = 8.7472(3) Å, β = 90.017(2)° for R070760. Both samples are pervasively twinned and the twin refinements yielded the final R1 factors of 0.037 and 0.031 for R100213 and R070760, respectively. The chemical compositions determined from electron microprobe analysis are Ag0.99(Mn0.92Pb 0.03Sb0.02Bi0.01)Σ=0.98 Pb3.00Sb5. 00S12.00 for R100213 and Ag 1.00(Mn0.82Sb0.11Ag0.04Bi 0.02)Σ=0.99Pb2.98vSb5.00S 12.00 for R070760. The key structural difference among uchucchacuaite, ramdohrite, and fizélyite lies in the cations occupying the M2 site, which can be expressed with a general structural formula as Ag(M2+2yAg1/2-ySb1/2-y)Pb 3Sb5S12, where M2+ represents divalent cations with 0 ≤ y ≤ 1/2. From the current list of IMA-defined minerals, we consider M = Cd with y = 0.125 for ramdohrite, M = Pb with y = 0.25 for fizélyite, and M = Mn with y = 0.5 for uchucchacuaite. Associated with the variation in the average M2 cation size from fizélyite (1.078 Å) to ramdohrite (0.955 Å) and uchucchacuaite (0.83 Å) is the significant decrease in the average M2-S bond distance from 2.917 to 2.834, and 2.654 Å, respectively, as well as corresponding variations in the unit-cell b dimension from ∼13.23 to 13.06 and 12.73 Å.
Yang, H; Downs, RT; Evans, SH; Feinglos, MN; Tait, KT
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