Cs4TlSbCl12 crystallizes in the tetragonal P4/mmm space group. Cs(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), four equivalent Cl(3), 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 Tl(1)Cl6 octahedra, and faces with two equivalent Sb(1)Cl6 octahedra. Tl(1) is bonded to two equivalent Cl(1) and four equivalent Cl(4) atoms to form TlCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. Sb(1) is bonded to two equivalent Cl(2) and four equivalent Cl(3) 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(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Tl(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Sb(1) atom. In the third Cl site, Cl(3) is bonded in a single-bond geometry to four equivalent Cs(1) and one Sb(1) atom. In the fourth Cl site, Cl(4) is bonded to four equivalent Cs(1) and one Tl(1) atom to form a mixture of distorted edge, corner, and face-sharing ClCs4Tl square pyramids.
Cs4TlSbCl12 crystallizes in the tetragonal P4/mmm space group. Cs(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), four equivalent Cl(3), 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 Tl(1)Cl6 octahedra, and faces with two equivalent Sb(1)Cl6 octahedra. Both Cs(1)-Cl(1) bond lengths are 3.84 Å. Both Cs(1)-Cl(2) bond lengths are 3.87 Å. All Cs(1)-Cl(3) bond lengths are 4.01 Å. All Cs(1)-Cl(4) bond lengths are 3.60 Å. Tl(1) is bonded to two equivalent Cl(1) and four equivalent Cl(4) atoms to form TlCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. Both Tl(1)-Cl(1) bond lengths are 2.64 Å. All Tl(1)-Cl(4) bond lengths are 2.64 Å. Sb(1) is bonded to two equivalent Cl(2) and four equivalent Cl(3) atoms to form SbCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. Both Sb(1)-Cl(2) bond lengths are 2.42 Å. All Sb(1)-Cl(3) bond lengths are 2.42 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Tl(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Sb(1) atom. In the third Cl site, Cl(3) is bonded in a single-bond geometry to four equivalent Cs(1) and one Sb(1) atom. In the fourth Cl site, Cl(4) is bonded to four equivalent Cs(1) and one Tl(1) atom to form a mixture of distorted edge, corner, and face-sharing ClCs4Tl square pyramids.