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The crystal structure of kutinaite was determined from powder data on a synthetic sample obtained from pure elements at 623 K. The data were collected on a Guinier diffractometer and reflection intensitites extracted by profile-fitting assuming a cubic P lattice. The structure was solved by direct methods and then refined by Rietveld method to Rp = 13.4% and RB = 1.8%. The cubic structure has a = 11.78079(2) Å and space group Pm3m, Z=4. Apart from partially ordered Cu vacancies, the atomic arrangement is practically consistent with Fm3m symmetry, and it is suggested that it is the true symmetry of the high-temperature modification which is supposed to host dynamically disordered vacancies. Cu atoms in partially occupied positions (24/32 per unit cell) are tetrahedrally coordinated by As, while the atoms in fully occupied positions have trigonal planar As coordinations. Ag forms octahedral Ag6 clusters (Ag-Ag bonds = 2.95-3.05 Å) in octahedral cavities of the Cu-As framework. In the latter, alternativelly, supertetrahedra and cuboctahedra of As-coordinated Cu clusters can be delineated. 1/7 of As atoms are hexahedrally coordinated by Cu atoms, while 6/7 are in somewhat distorted icosahedral coordinaitons by 8 Cu and 4 Ag atoms. A multitude of metal-metal (Cu-Cu, Ag-Ag, and Ag-Cu) and metal-semimetal contacts allows an alternative description of kutinaite as a complex alloy with predominantly icosahedral mutually interpenetrating coordinations.

Influence of fluorine content on the composition of Al-rich synthetic phlogopite investigated by solid state NMR