Ba3YRu0.73(2)Al1.27(2)O8 and Ba5Y2Ru1.52(2)Al1.47(2)O 13.5: New perovskite ruthenates with partial octahedra replacement

Abstract

Dark red single crystals of the new phases Ba3YRu0.73(2)Al1.27(2)O8 and Ba5Y2Ru1.52(2)Al1.47(2)O13.5 have been grown from powder mixtures of BaCO3, Y2O3, Al2O3, and RuO2 . The compositions given in the formulas result from the refinements of the crystal structures based on single crystal X-ray diffraction data (hexagonal P63/mmc (No. 194), Z = 2, Ba3 YRu0.73(2)Al1.27(2)O8: a = 5.871(1), c = 14.633(3) Å , R1 = 0.035, wR2 = 0.069 and Ba5Y2Ru1.52(2)Al1.47(2)O13.5: a = 5.907(1), c = 24.556(5) Å, R1 = 0.057, wR2 = 0.114). Ba3YRu0.73(2)Al1.27(2)O8 crystallizes in a 6H perovskite structure, Ba5Y2Ru1.52(2)Al1.47(2)O13.5 has been characterized as a 10H Perovskite. Due to similar spatial extensions of (Ru2O9) facesharing pairs of octahedra and (Al2O7) vertex-sharing pairs of tetrahedra, both structures show partial mutual substitution of these units. Consequently, the title compounds may be written as Ba3Y(Ru2O9)1−x(Al2O7)x, x = 0.64(1) and Ba5Y2RuO6(Ru2O9)1−x(Al2O7)x, x = 0.74(1). This interpretation is supported by the results of electron probe microanalysis using wavelength-dispersive X-ray spectroscopy. An oxidation state of Ru close to +5 for the (Ru2O9) units, as can be derived from the distances d(Ru-Ru), additionally leads to similar charges of both the (Ru2O9) and the (Al2O7) units.