Crystal structure of (Na0.70)(Na0.70,Mn0.30)(Fe3+,Fe2+)2Fe2+(VO4)3, a sodium-, iron- and manganese-based vanadate with the alluaudite-type structure

The title compound, sodium (sodium,manganese) triiron(II,III) tris[vanadate(V)], (Na0.70)(Na0.70,Mn0.30)(Fe3+,Fe2+)2Fe2+(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 (Wyckoff position 4e) and one on an inversion centre (4b). Two sites on the twofold rotation axis are entirely filled by Fe2+ and V5+, whereas the third site has a partial occupancy of 70% by Na+. The site on the inversion centre is occupied by Na+ and Mn2+ cations in a 0.7:0.3 ratio. The remaining Fe2+ and Fe3+ atoms are statistically distributed on a general position. The three-dimensional framework of this structure is made up of kinked chains of edge-sharing [FeO6] octahedra stacked parallel to [10-1]. These chains are held together by VO4 tetrahedral groups, forming polyhedral sheets perpendicular to [010]. Within this framework, two types of channels extending along [001] are present. One is occupied by (Na+/Mn2+) while the second is partially occupied by Na+. The mixed site containing (Na+/Mn2+) has an octahedral coordination sphere, while the Na+ cations in the second channel are coordinated by eight O atoms.