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Single crystals of Ti 2 Rh 6 B were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The new silver-like compound with metallic luster crystallizes in space group  Fm -3 m  (no. 225) with  a  = 7.8191(5) Å,  V  = 478.05(5) Å 3 , and  Z  = 4. The refinement converged to  R  1  = 0.0169 and  wR  2  = 0.0486 for all 96 unique reflections and 7 parameters. The structure can be described as a defect double perovskite, A 2 BB'O 6 , where the A site is occupied by titanium, the B site by boron, the O site by rhodium but the B' site is vacant leading to the formation of perfectly octahedral Rh 6  clusters and BRh 6  units. Rh—B, Rh—Ti, and Rh—Rh interactions are observed. According to density-functional (LMTO) electronic structure calculations, the strongest bonding occurs for the Rh—B contacts, and the Rh—Rh bonding within the clusters is more than two times stronger than in the BRh 6  units.

Ti 2 Rh 6 B – a new boride with a double perovskite-like structure containing octahedral Rh 6 clusters