Preparation, thermal stability and crystal structure of a new ruthenium(V) oxide containing peroxide ions: Ba₅Ru₂O₉(O₂). Structural relationships to thehexagonal-type perovskite

Abstract

The compound Ba₅Ru₂O₁₁ has been synthesized by solid state reactions at 980 °C and 1 atm oxygen pressure. The crystal structure has been determined on a single crystal (R₁=0.027, wR₂=0.058). The symmetry is hexagonal (P6₃ /mmc) with the cell parameters a=5.9470(5) Å, c=18.0428(10) Å, Z=2. Perpendicular to the c-axis, the structure is built up by the periodic stacking of three hexagonal close packed [BaO₃ ] layers separated by a layer of composition [Ba₂O₂ ] containing (O₂)^2- peroxide ions. The detailed formula is then Ba₅Ru₂O₉(O₂) if we emphasize the formation of peroxide ions in the phase. The ruthenium(v) ions occupy the octahedral sites formed between the [BaO₃ ] layers (hexagonal perovskite slabs) and then constitute isolated [Ru₂O₉ ] pairs. Ba₅Ru₂O₉(O₂) belongs to a new family of compounds, generically formulated as [A₂(O₂)][A_nB_{n -1}O_3n] wheren represents the number of [AO₃ ] successive layers in the hexagonal perovskite slabs. Each member of the series is an intergrowth of [A₂(O₂)] and hexagonal perovskite layers; n=3 corresponds to Ba₅Ru₂O₉(O₂). The isostructural phase has been observed when ruthenium is replaced by niobium. The n=4 member and the intergrowth between the n=3 and n=4 members of this family has been observed in the Ba–Nb(Ta)–S ternary systems. The former proposed formula for the ternary barium sulfides is discussed in the light of the framework of this new family.

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