Single-crystal structure determination of two new ternary bismuthides: Rh₆Mn₅Bi₁₈ and RhMnBi₃

A study of the ternary Rh-Mn-Bi phase diagram revealed the existence of two new ternary bismuthides, viz. hexarhodium pentamanganese octadecabismuthide (Rh₆Mn₅Bi₁₈) and rhodium manganese tribismuthide (RhMnBi₃). Their crystal structures represent new structure types. Rh₆Mn₅Bi₁₈, with a Wyckoff sequence a f2 g2 i5, crystallizes in the tetragonal system (space group P4₂/mnm; Pearson symbol tP58), and RhMnBi₃, with a Wyckoff sequence a c g i q, crystallizes in the orthorhombic system (Cmmm; oS20). In the Rh₆Mn₅Bi₁₈ structure, the transition metal atoms are linked into ribbon-like structural units aligned along the [001] direction, whereas planar sheets are formed in RhMnBi₃. In both crystal structures, the units formed by the transition metal atoms are enveloped by Bi atoms, which themselves form a loosely bound network. The linkage results in a layer structure for RhMnBi₃, while in the case of Rh₆Mn₅Bi₁₈, a three-dimensional network is formed; the latter, however, contains several areas where Bi...Bi distances suggest van der Waals interactions. Both phases under discussion have analogous structural motifs.