Abstract

The previously unknown crystal structure of mckinstryite, originally described as Ag1.18Cu0.82S or (Ag,Cu)2S, was solved and refined using single-crystal X-ray diffractometer data collected from a sample from the Clara mine, Black Forest (Mo-Kα radiation, CCD area detector, R1(F) = 3.85%). Mckinstryite has the refined formula Ag4.92Cu3.08S4 or Ag1.23Cu0.77S (idealized Ag5Cu3S4 or Ag1.25Cu0.75S) and crystallizes in space group Pnma (no. 62), with a = 14.047(3) Å, b = 7.805(2) Å, c = 15.691(3) Å, V = 1720.3(7) Å3, Z = 8. The structure contains five Ag, six Cu and eight S sites in the asymmetric unit. One of the Ag sites shows minor Cu-for-Ag substitution. The topology is based on flat, interrupted (010) layers of Cu and S atoms (all atoms on y = 0.25), in which the Cu atoms show triangular or two-coordination to S (interrupted {6,3} tiling). These layers alternate with uneven layers consisting of Ag atoms showing irregular three- to two-coordination to S. Some fairly short Ag-Cu contact distances (2.781-2.884 Å) strongly indicate that metal-metal interaction plays an important role in mckinstryite. The topology is related to that of stromeyerite (∼AgCuS) which contains complete flat layers of Cu atoms triangularly coordinated to S atoms, alternating with layers of loosely packed Ag atoms.

A critical evaluation of literature data on the chemical composition and unit-cell parameters of mckinstryite confirms the presence of a small compositional range of mckinstryite which extends approximately from Ag1.18Cu0.82StoAg1.25Cu0.75S, with the presently studied sample being fairly Ag-rich. The accurate limits of this range at ambient temperature are still to be determined.

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