The crystal structures of carlfrancisite, ideally Mn32+(Mn2+,Mg,Fe3+,Al)42(As3+O3)2(As5+O4)4[(Si,As5+)O4]8(OH)42, hexagonal (rhombohedral), Rm with Z = 6, and unit-cell parameters: a = 8.2238(2), c = 205.113(6) Å and V = 12013.5(4) Å3, from the Kombat mine, Otavi Valley, Namibia, and mcgovernite, ideally Zn3(Mn2+,Mg,Fe3+,Al)42(As3+O3)2(As5+O4)4[(Si,As5+)O4]8(OH)42, hexagonal (rhombohedral), Rm with Z = 6, and unit-cell parameters: a = 8.2061(3), c = 204.118(8) Å and V = 11903.8(6) Å3, from Sterling Hill, New Jersey, have been solved by direct methods and refined to R1 values of 3.37 and 5.02% for 3837 and 3772 unique observed reflections, respectively; they are isostructural. Chemical analysis by electron microprobe and crystal-structure refinement gave the following compositions: carlfrancisite: As2O5 12.89, As2O3 3.33, P2O5 0.50, V2O5 0.74, SiO2 8.96, Al2O3 0.78, FeO 0.22, MnO 53.25, MgO 9.37, H2O(calc) 8.42, sum 98.50 wt.%; mcgovernite: As2O5 13.06, As2O3 3.71, SiO2 9.34, Al2O3 0.20, FeO 1.38, MnO 44.58, ZnO 8.81, MgO 8.89, H2O(calc) 8.24, sum 98.21 wt.%. The H2O contents and the valence states of As were determined by crystal-structure analysis.

There are 18 crystallographically distinct cation sites in both carlfrancisite and mcgovernite. There are two [4]-coordinated As sites fully occupied by As5+, and four T sites occupied by Si and As5+ in solid solution. The As(3) site has triangular pyramidal coordination with <As(3)–O> distances of 1.808 and 1.817 Å, typical of As3+. The Z(1) site, occupied by Mn2+ in carlfrancisite and Zn in mcgovernite, has tetrahedral coordination, and the Z(2) site is only partly occupied by Mg and Mn2+ in both structures. There are nine M sites, all of which are octahedrally coordinated and contain dominantly Mn2+ and Mg, with minor Al and Fe. There are three cation sites with significant vacancies: As(3), Z(2), M(3), and there are complicated patterns of short-range order involving the cations and vacancies at these sites.

The carlfrancisite–mcgovernite structure contains 84 layers of approximately close-packed polyhedra along one translation on c. The anions in the structure are arranged in approximately close-packed layers orthogonal to the c axis. Fourteen layers stack along the c axis in the sequence |**hhchchhchchh| (* denotes a layer of anions displaced from close packed). There are eight distinct layers of cation-centred polyhedra that repeat via a centre of symmetry at the origin, and via the R-centering to give 84 layers per unit-cell.

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