Dimorphism of MnHAsO₄(H₂O): natural monoclinic krautite and its synthetic triclinic modification

Abstract

The crystal structure of natural krautite, MnHAsO4(H2O), was re-evaluated from a cotype specimen, confirming the previously reported monoclinic symmetry for this mineral (space group P21, Z = 8, a = 8.0093(5), b = 15.9372(10), c = 6.8065(4) Å, β = 96.534(2)° at room temperature, 5662 structure factors, 302 parameters, R1 = 0.0295, wR2 = 0.0770). Although hydrogen atoms could not be located from the single crystal X-ray diffraction study, the higher accuracy and precision of the results allowed to derive the hydrogen-bonding scheme (O⋯O = 2.55–2.90 Å) in the crystal structure of krautite. Crystals of synthetic MnHAsO4(H2O) were grown by mixing aqueous solutions of NH4H2AsO4 and MnSO4 and keeping the formed gel at 105 °C for several days. The obtained triclinic crystals were systematically and polysynthetically twinned by contact on (010). Separation of reflections from two individual domains made it possible to determine and refine the crystal structure (space group P¯1 , Z = 8, a = 8.0105(16), b = 15.991(4), c = 6.8029(12) Å, α = 92.635(8), β = 96.534(2), γ = 90.151(8)° at room temperature, 7226 structure factors, 255 parameters, R1 = 0.0445, wR2 = 0.1381). The triclinic polymorph of MnHAsO4(H2O) does not show a direct group-subgroup relation with monoclinic krautite. Triclinic MnHAsO4(H2O) is closely related with other triclinic M IIHAsO4(H2O) (M = Co, Cu, Zn, Mg) mineral phases. Quantitative structural comparisons between the five M IIHAsO4(H2O) compounds revealed a high similarity between the Mn and Co members, and between the Zn and Mg members, respectively. Subtle distinctions between the two pairs are ascribed to a different hydrogen-bonding scheme. Although the Cu member has a similar hydrogen-bonding scheme as the Mn and Co pair, its structural similarity with triclinic MnHAsO4(H2O) is low due to the strain of the crystal structure caused by the Jahn-Teller distortions of the [CuO6] octahedra.