Rb2TlAlI6 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 Tl(1)I6 octahedra, and faces with four equivalent Al(1)I6 octahedra. Tl(1) is bonded to six equivalent I(1) atoms to form TlI6 octahedra that share corners with six equivalent Al(1)I6 octahedra and faces with eight equivalent Rb(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. Al(1) is bonded to six equivalent I(1) atoms to form AlI6 octahedra that share corners with six equivalent Tl(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 distorted linear geometry to four equivalent Rb(1), one Tl(1), and one Al(1) atom.
Rb2TlAlI6 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 Tl(1)I6 octahedra, and faces with four equivalent Al(1)I6 octahedra. All Rb(1)-I(1) bond lengths are 4.34 Å. Tl(1) is bonded to six equivalent I(1) atoms to form TlI6 octahedra that share corners with six equivalent Al(1)I6 octahedra and faces with eight equivalent Rb(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. All Tl(1)-I(1) bond lengths are 3.34 Å. Al(1) is bonded to six equivalent I(1) atoms to form AlI6 octahedra that share corners with six equivalent Tl(1)I6 octahedra and faces with eight equivalent Rb(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. All Al(1)-I(1) bond lengths are 2.78 Å. I(1) is bonded in a distorted linear geometry to four equivalent Rb(1), one Tl(1), and one Al(1) atom.