K2CuBiI6 crystallizes in the cubic Fm-3m space group. K(1) is bonded to twelve equivalent I(1) atoms to form distorted KI12 cuboctahedra that share corners with twelve equivalent K(1)I12 cuboctahedra, faces with six equivalent K(1)I12 cuboctahedra, faces with four equivalent Cu(1)I6 octahedra, and faces with four equivalent Bi(1)I6 octahedra. Cu(1) is bonded to six equivalent I(1) atoms to form CuI6 octahedra that share corners with six equivalent Bi(1)I6 octahedra and faces with eight equivalent K(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. Bi(1) is bonded to six equivalent I(1) atoms to form BiI6 octahedra that share corners with six equivalent Cu(1)I6 octahedra and faces with eight equivalent K(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. I(1) is bonded in a linear geometry to four equivalent K(1), one Cu(1), and one Bi(1) atom.
K2CuBiI6 crystallizes in the cubic Fm-3m space group. K(1) is bonded to twelve equivalent I(1) atoms to form distorted KI12 cuboctahedra that share corners with twelve equivalent K(1)I12 cuboctahedra, faces with six equivalent K(1)I12 cuboctahedra, faces with four equivalent Cu(1)I6 octahedra, and faces with four equivalent Bi(1)I6 octahedra. All K(1)-I(1) bond lengths are 4.20 Å. Cu(1) is bonded to six equivalent I(1) atoms to form CuI6 octahedra that share corners with six equivalent Bi(1)I6 octahedra and faces with eight equivalent K(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. All Cu(1)-I(1) bond lengths are 2.84 Å. Bi(1) is bonded to six equivalent I(1) atoms to form BiI6 octahedra that share corners with six equivalent Cu(1)I6 octahedra and faces with eight equivalent K(1)I12 cuboctahedra. The corner-sharing octahedra are not tilted. All Bi(1)-I(1) bond lengths are 3.09 Å. I(1) is bonded in a linear geometry to four equivalent K(1), one Cu(1), and one Bi(1) atom.