New Ba5M5-xPtxClO13 (M=Fe, Co) oxychlorides with layered perovskite-related structure

Crystals of Ba5Fe5-xPtxClO13 and Ba5Co5-yPtyClO13 were prepared for x=1.31, 1.51, 1.57, 1.59 and y=0, 0.97 and 1.08 in a BaCl2 flux and investigated by X-ray diffraction methods. These compounds adopt a 10H perovskite structure built from the stacking of BaO3 and BaOCl layers in the sequence (BaO3)4(BaOCl) with space group P63/mmc. The cation sites within the trimeric unit of face-sharing octahedra are occupied by Co or Fe and Pt ions, while the tetrahedral sites formed between BaO3 and BaOCl layers are only occupied by Fe or Co. Moreover, oxygen stoichiometry indicates an average oxidation state for Co and Fe higher than +III, indicating the stabilization of Co4+ and Fe4+