Rb3BiF6 is (Cubic) Perovskite-like structured and crystallizes in the cubic Fm-3m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to twelve equivalent F(1) atoms to form RbF12 cuboctahedra that share corners with twelve equivalent Rb(1)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, faces with four equivalent Rb(2)F6 octahedra, and faces with four equivalent Bi(1)F6 octahedra. In the second Rb site, Rb(2) is bonded to six equivalent F(1) atoms to form RbF6 octahedra that share corners with six equivalent Bi(1)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Bi(1) is bonded to six equivalent F(1) atoms to form BiF6 octahedra that share corners with six equivalent Rb(2)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. F(1) is bonded in a linear geometry to one Rb(2), four equivalent Rb(1), and one Bi(1) atom.
Rb3BiF6 is (Cubic) Perovskite-like structured and crystallizes in the cubic Fm-3m space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded to twelve equivalent F(1) atoms to form RbF12 cuboctahedra that share corners with twelve equivalent Rb(1)F12 cuboctahedra, faces with six equivalent Rb(1)F12 cuboctahedra, faces with four equivalent Rb(2)F6 octahedra, and faces with four equivalent Bi(1)F6 octahedra. All Rb(1)-F(1) bond lengths are 3.44 Å. In the second Rb site, Rb(2) is bonded to six equivalent F(1) atoms to form RbF6 octahedra that share corners with six equivalent Bi(1)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Rb(2)-F(1) bond lengths are 2.61 Å. Bi(1) is bonded to six equivalent F(1) atoms to form BiF6 octahedra that share corners with six equivalent Rb(2)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Bi(1)-F(1) bond lengths are 2.24 Å. F(1) is bonded in a linear geometry to one Rb(2), four equivalent Rb(1), and one Bi(1) atom.