Rb2NaSbI6 crystallizes in the cubic Fm-3m space group. Rb(1) is bonded to twelve equivalent I(1) atoms to form distorted RbI12 cuboctahedra that share corners with twelve equivalent Rb(1)I12 cuboctahedra, faces with six equivalent Rb(1)I12 cuboctahedra, faces with four equivalent Na(1)I6 octahedra, and faces with four equivalent Sb(1)I6 octahedra. Na(1) is bonded to six equivalent I(1) atoms to form NaI6 octahedra that share corners with six equivalent Sb(1)I6 octahedra and faces with eight equivalent Rb(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. Sb(1) is bonded to six equivalent I(1) atoms to form SbI6 octahedra that share corners with six equivalent Na(1)I6 octahedra and faces with eight equivalent Rb(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. I(1) is bonded in a linear geometry to four equivalent Rb(1), one Na(1), and one Sb(1) atom.
Rb2NaSbI6 crystallizes in the cubic Fm-3m space group. Rb(1) is bonded to twelve equivalent I(1) atoms to form distorted RbI12 cuboctahedra that share corners with twelve equivalent Rb(1)I12 cuboctahedra, faces with six equivalent Rb(1)I12 cuboctahedra, faces with four equivalent Na(1)I6 octahedra, and faces with four equivalent Sb(1)I6 octahedra. All Rb(1)-I(1) bond lengths are 4.36 Å. Na(1) is bonded to six equivalent I(1) atoms to form NaI6 octahedra that share corners with six equivalent Sb(1)I6 octahedra and faces with eight equivalent Rb(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. All Na(1)-I(1) bond lengths are 3.15 Å. Sb(1) is bonded to six equivalent I(1) atoms to form SbI6 octahedra that share corners with six equivalent Na(1)I6 octahedra and faces with eight equivalent Rb(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. All Sb(1)-I(1) bond lengths are 3.02 Å. I(1) is bonded in a linear geometry to four equivalent Rb(1), one Na(1), and one Sb(1) atom.