Ca10(CrVO4)6(CrVIO4), a disordered mixed-valence chromium compound exhibiting inversion twinning

Abstract

The structure analysis of so-called 9CaO·4CrO3·Cr2O3proved it to be the title compound, decacalcium hexakis[chromate(V)] chromate(VI), with the simultaneous presence of unusual chromium oxidation states. The structure determination was carried out on a crystal that had inversion twinning. The CrVIO4tetrahedron is situated on a threefold axis and is disordered over two possible orientations that share three O atoms, while the CrVO4tetrahedra are in general positions and are ordered. The charge is balanced by Ca2+cations, one of which is located on a threefold axis. The Ca2+ions are coordinated by six, seven or eight O atoms. The compound is a significant phase in the CaO–CrOxsystem and its formation reduces the refractoriness of calcium-rich compositions in an oxidizing atmosphere.