The actual structure of K6(VO)2(V2O3)2(PO4)4(P2O7): Ordered distribution of P2O7 groups and charge ordering of vanadium

The actual structure of the vanadium phosphate K6(VO)2(V2O3)2(PO4)4(P2O7) has been determined, using a much larger single crystal than previously used for the isostructural Rb-phase. The actual supercell is four times larger than the corresponding orthorhombic subcell with a=26.777Å, b=28.480Å, c=6.972Å, α=β=γ=90°α=β=γ=90°. The structure resolution, performed in the triclinic space group C-1, shows that the P2O7 groups alone are responsible for the superstructure, all the other atoms keeping the atomic positions of the orthorhombic subcell. This structural study shows a perfect ordering of the P2O7 groups in the actual structure, in contrast to the results obtained from the subcell. Concomitantly, the V4+ and V5+ are found to be ordered in the form of [110] stripes.

Partial projection showing the ordering of the P2O7 units (in dark gray) and the ordering of the V5+ (light gray) and of the V4+ (medium gray) species.Figure optionsDownload as PowerPoint slide