The alluaudite-type crystal structures of Na2(Fe/Co)2Co(VO4)3 and Ag2(Fe/Co)2Co(VO4)3
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چکیده
Single crystals of the title compounds, disodium di(cobalt/iron) cobalt tris-(orthovanadate), Na2(Fe/Co)2Co(VO4)3, and disilver di(cobalt/iron) cobalt tris-(orthovanadate), Ag2(Fe/Co)2Co(VO4)3, were grown from a melt consisting of stoichiometric mixtures of three metallic cation precursors and vanadium pentoxide. The difficulty to distinguish between cobalt and iron by using X-ray diffraction alone forced us to explore several models, assuming an oxidation state of +II for Co and +III for Fe and a partial cationic disorder in the Wyckoff site 8f containing a mixture of Co and Fe with a statistical distribution for the Na compound and an occupancy ratio of 0.4875:0.5125 (Co:Fe) for the Ag compound. The alluaudite-type structure is made up from [10-1] chains of [(Co,Fe)2O10] double octa-hedra linked by highly distorted [CoO6] octa-hedra via a common edge. The chains are linked through VO4 tetra-hedra, forming polyhedral sheets perpendicular to [010]. The stacking of the sheets defines two types of channels parallel to [001] where the Na(+) cations (both with full occupancy) or Ag(+) cations (one with occupancy 0.97) are located.
منابع مشابه
Crystal structure of (Na0.70)(Na0.70,Mn0.30)(Fe(3+),Fe(2+))2Fe(2+)(VO4)3, a sodium-, iron- and manganese-based vanadate with the alluaudite-type structure.
The title compound, sodium (sodium,manganese) triiron(II,III) tris[vana-date(V)], (Na0.70)(Na0.70,Mn0.30)(Fe(3+),Fe(2+))2Fe(2+)(VO4)3, was prepared by solid-state reactions. It crystallizes in an alluaudite-like structure, characterized by a partial cationic disorder. In the structure, four of the 12 sites in the asymmetric unit are located on special positions, three on a twofold rotation axis...
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