Elucidation of the Off-Center Displaced Mo in Octahedral Coordination in Ba₂MoO₅

The detailed crystal structure as well as the heat capacity at low temperature and standard entropy of Ba₂MoO₅ are reported for the first time. High-resolution X-ray and neutron diffraction were employed to reveal the structural features of this compound. Ba₂MoO₅ has a six-coordinated Mo and a strongly negative excess volume with respect to the binary oxides. X-ray absorption near edge structure (XANES) spectroscopy at the Mo K-edge shows Mo to be in the oxidation state 6+. The pre-edge peak in the XANES spectrum indicates a distorted octahedral environment, in line with the results from diffraction studies and FDMNES calculations. The standard entropy and heat capacity of Ba₂MoO₅ at 298.15 K, determined with a thermal-relaxation technique, are calculated to be respectively 223.2 ± 7 and 184.7 ± 5 J·K^-1·mol^-1. The obtained thermodynamic properties are discussed in the context of the literature reports on molybdate compounds.