Cs4BiSbCl12 crystallizes in the tetragonal I4_1/amd space group. Cs(1) is bonded to two equivalent Cl(2), two equivalent Cl(3), four equivalent Cl(1), and four equivalent Cl(4) atoms to form distorted CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, faces with two equivalent Bi(1)Cl6 octahedra, and faces with two equivalent Sb(1)Cl6 octahedra. Bi(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form BiCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. Sb(1) is bonded to two equivalent Cl(3) and four equivalent Cl(4) atoms to form SbCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. There are four inequivalent Cl sites. In the first Cl site, Cl(4) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Sb(1) atom. In the second Cl site, Cl(1) is bonded to four equivalent Cs(1) and one Bi(1) atom to form a mixture of distorted face, corner, and edge-sharing ClCs4Bi square pyramids. In the third Cl site, Cl(2) is bonded to four equivalent Cs(1) and one Bi(1) atom to form a mixture of face, corner, and edge-sharing ClCs4Bi square pyramids. In the fourth Cl site, Cl(3) is bonded in a single-bond geometry to four equivalent Cs(1) and one Sb(1) atom.
Cs4BiSbCl12 crystallizes in the tetragonal I4_1/amd space group. Cs(1) is bonded to two equivalent Cl(2), two equivalent Cl(3), four equivalent Cl(1), and four equivalent Cl(4) atoms to form distorted CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, faces with two equivalent Bi(1)Cl6 octahedra, and faces with two equivalent Sb(1)Cl6 octahedra. Both Cs(1)-Cl(2) bond lengths are 3.61 Å. Both Cs(1)-Cl(3) bond lengths are 4.08 Å. There are two shorter (3.69 Å) and two longer (3.79 Å) Cs(1)-Cl(1) bond lengths. There are two shorter (3.90 Å) and two longer (4.08 Å) Cs(1)-Cl(4) bond lengths. Bi(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form BiCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. Both Bi(1)-Cl(2) bond lengths are 2.73 Å. All Bi(1)-Cl(1) bond lengths are 2.73 Å. Sb(1) is bonded to two equivalent Cl(3) and four equivalent Cl(4) atoms to form SbCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. Both Sb(1)-Cl(3) bond lengths are 2.42 Å. All Sb(1)-Cl(4) bond lengths are 2.42 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(4) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Sb(1) atom. In the second Cl site, Cl(1) is bonded to four equivalent Cs(1) and one Bi(1) atom to form a mixture of distorted face, corner, and edge-sharing ClCs4Bi square pyramids. In the third Cl site, Cl(2) is bonded to four equivalent Cs(1) and one Bi(1) atom to form a mixture of face, corner, and edge-sharing ClCs4Bi square pyramids. In the fourth Cl site, Cl(3) is bonded in a single-bond geometry to four equivalent Cs(1) and one Sb(1) atom.