An update on the mineral-like Sr-containing transition metal arsenates

Abstract

AbstractWe report on the crystal structures of three novel synthetic SrM-arsenates (M = Ni and Fe3+), isostructural or structurally related to the minerals from tsumcorite, carminite and brackebuschite groups. They were synthesised under mild hydrothermal conditions and further characterised using single-crystal X-ray diffraction (SXRD), scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and Raman spectroscopy. SXRD and SEM-EDS yielded formulae: (I) SrNi2(AsO4)2⋅2H2O, (II) Sr1.4Fe3+1.6(AsO4)2(OH)1.6 and (III) SrFe3+(AsO4)(AsO3OH). All three structures are built up of slightly distorted MO6 octahedra and AsO4 tetrahedra that are linked by Sr2+ with different coordination geometries and hydrogen bonds. I represent a basic structure type typical for tsumcorite-group minerals (space group C2/m) while II has a new intermediate structure between carminite, PbFe3+2(AsO4)2(OH)2 and arsenbrackebuschite, Pb2Fe3+(AsO4)2(OH) (s.g. Pm). III is triclinic and adopts a new structure-type (s.g. P$\bar{1}$). The structure of I is built up of infinite linear edge-sharing NiO4(OH2)2 octahedral chains, extending along [010] and linked by AsO4 tetrahedra, SrO8 polyhedra and hydrogen bonds. The structure of II is characterised by the carminite-like FeO4(OH)2 octahedral chains and Edshammar-polyhedral chains, which involves SrO11 coordination polyhedra similar to that of PbO11 in arsenbrackebuschite. Both chains in II are aligned parallel to the b axis of the monoclinic unit cell and connected together by the arsenate AsO4 tetrahedra, SrO8 polyhedra and the hydrogen-bonding network. The compound III has a new type of crystal structure based on the unusual corrugated octahedral–tetrahedral-quadruple chains. These are made up of a central double-sided chain linked to two single-sided chains into a quadruple chain extended along the a axis. The chains in III are built up of FeO6 octahedra and AsO4 tetrahedra further linked to each other by shared vertices. The quadruple chains are interconnected by additional AsO4 tetrahedra forming a heteropolyhedral 3D open framework. Strontium atoms are situated in the two channels. The structural connections to related minerals and inorganic compounds are discussed.