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 Ag_0.99(Mn_0.92Pb _0.03Sb_0.02Bi_0.01)_Σ=0.98 _Pb3.00_Sb5. 00_S12.00 for R100213 and Ag _1.00(Mn_0.82Sb_0.11Ag_0.04Bi _0.02)_Σ=0.99Pb2.98vSb_5.00S _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⁺_2yAg_1/2-ySb_1/2-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.