New mixed-valence chromium structure type: NH4Cr(CrO4)2

Synthesis and crystal structure of a new structure type of mixed Cr(III)/Cr(VI) chromates is reported. NH4Cr(CrO4)2 was prepared from CrO3 in the presence of (NH4)2Ce(NO3)6. Since this is the first preparation of mixed valence ternary chromium oxides from aqueous solution, a reaction pathway for this synthesis is suggested. The crystal structure of NH4Cr(CrO4)2 has been determined from three-dimensional X-ray data collected at low temperature, 173 K. The structure belongs to the orthorhombic space group Pnma, with image, image, image and image. The title compound consists of corner-sharing chromium(III) octahedra and chromium(VI) tetrahedra forming a three-dimensional network with the composition [Cr(CrO4)2]nn–, containing channels in which zigzag rows of ammonium ions balance the net charge.