We report the characterisation of two new tetrahedrite-group minerals, rozhdestvenskayaite, Ag10Zn2Sb4S13, and argentotetrahedrite, Ag6Cu4(Fe2+,Zn)2Sb4S13, and discuss the structural chemistry of the Ag-rich tetrahedrite group in order to identify correlations between structure and composition. Argentotetrahedrite is the Sb-analogue of argentotennantite. Rozhdestvenskayaite is named for Irina Rodzhdestvenskaya in recognition of her important contributions to mineralogy, and to the crystal chemistry of the tetrahedrite group in particular. Rozhdestvenskayaite is cubic I4¯3m with unit-cell parameter a = 10.9845(7) Å and V = 1325.37(15) Å3, and has a Mohs’ hardness of 3.0. Argentotetrahedrite is cubic I4¯3m with unit-cell parameter a = 10.6116(1) Å and V = 1194.92(2) Å3, and has a Mohs’ hardness of 3.9. The five strongest peaks in the X-ray powder diffraction patterns ([(hkl), dobs (Å), I/Imax (%)]) are: rozhdestvenskayaite [(222), 3.161, 100], [(004), 2.738, 35], [(044), 1.936, 24], [(226), 1.651, 19], [(134,015), 2.147, 18]; argentotetrahedrite [(222), 3.063, 100], [(044), 1.876, 35], [(004), 2.652, 28], [(226), 1.599, 25], [(134,015), 2.081, 19]. The large unit-cell volume of rozhdestvenskayaite is due to the high Ag content (70%) of the BS4 tetrahedron. A major issue for understanding the crystal chemistry of the tetrahedrite group relates to the occupancy of the Z site in which sulfur is coordinated octahedrally to monovalent metals (Cu or Ag). It is shown that this site can be completely empty, as in freibergite, and that this vacancy leads to a marked reduction in the volume of the Z(A6) octahedron from 16 Å3 in tetrahedrite with a fully occupied site to 11 Å3 in freibergite with a vacant Z site. In freibergite, the Ag–Ag distance of the Ag6 octahedron is 2.84 Å and is almost the same as that of silver metal (2.85 Å), strongly suggesting the presence of metallic bonding in this octahedral group. In contrast, the corresponding Ag–Ag distances of argentotetrahedrite and rozhdestvenskayaite are 3.23 Å and 3.24 Å, respectively, indicative of no metallic bonding. An important consequence of the metallically bonded Ag6 group of freibergite is that it has an aggregate formal charge of +4 (not +6), leading to a charge-balanced ideal formula (Ag6)4+(Cu+)4(Zn,Fe2+)2Sb4S12.

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