Crystal structure of (Na(0.70))(Na(0.70),Mn(0.30))(Fe(3+),Fe(2+))(2)Fe(2+)(VO(4))(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)], (Na(0.70))(Na(0.70),Mn(0.30))(Fe(3+),Fe(2+))(2)Fe(2+)(VO(4))(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 Fe(2+) and V(5+), whereas the third site has a partial occupancy of 70% by Na(+). The site on the inversion centre is occupied by Na(+) and Mn(2+) cations in a 0.7:0.3 ratio. The remaining Fe(2+) and Fe(3+) atoms are statistically distributed on a general position. The three-dimensional framework of this structure is made up of kinked chains of edge-sharing [FeO(6)] octa­hedra stacked parallel to [10-1]. These chains are held together by VO(4) 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(+)/Mn(2+)) while the second is partially occupied by Na(+). The mixed site containing (Na(+)/Mn(2+)) has an octa­hedral coordination sphere, while the Na(+) cations in the second channel are coordinated by eight O atoms.