Rb3CrF6 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 Cr(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 Cr(1)F6 octahedra and faces with eight equivalent Rb(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Cr(1) is bonded to six equivalent F(1) atoms to form CrF6 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 2-coordinate geometry to one Rb(2), four equivalent Rb(1), and one Cr(1) atom.
Rb3CrF6 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 Cr(1)F6 octahedra. All Rb(1)-F(1) bond lengths are 3.21 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 Cr(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 2.60 Å. Cr(1) is bonded to six equivalent F(1) atoms to form CrF6 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 Cr(1)-F(1) bond lengths are 1.91 Å. F(1) is bonded in a 2-coordinate geometry to one Rb(2), four equivalent Rb(1), and one Cr(1) atom.