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RhBi is alpha-derived structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Rh is bonded in a 12-coordinate geometry to six equivalent Bi atoms. All Rh–Bi bond lengths are 2.87 Å. Bi is bonded in a 12-coordinate geometry to six equivalent Rh atoms.
RhBi crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Rh is bonded to two equivalent Rh and six equivalent Bi atoms to form a mixture of distorted edge, face, and corner-sharing RhBi6Rh2 octahedra. The corner-sharing octahedra tilt angles range from 0–51°. Both Rh–Rh bond lengths are 2.88 Å. All Rh–Bi bond lengths are 2.81 Å. Bi is bonded in a 6-coordinate geometry to six equivalent Rh atoms.