Ba19Cr12O45: A High Pressure Chromate with an Original Structure Solved by Electron Diffraction Tomography and Powder X-ray Diffraction

Abstract

We report on the discovery of a Ba-based chromate obtained by high pressure-high temperature treatment of the low pressure orthorhombic Ba2CrO4 phase. By combining transmission electron microscopy and powder X-ray diffraction measurements, we have determined its crystallographic structure. This new Cr-oxide has a cubic lattice with a = 13.3106(6) Å built from a three-dimensional network of two Cr sites, Cr1 and Cr2, both in octahedral environments, with face sharing between Cr1 and Cr2 octahedra and corner-sharing between two Cr1 octahedra. The resulting chemical composition Ba19Cr12O45 and bond valence sum analysis suggest a possible charge disproportion between Cr4+ in the Cr1 site and Cr5+ in the Cr2 site. Finally analysis of magnetization measurements indicates antiferromagnetic correlations between Cr cations and also points toward a probable charge disproportion between Cr sites.