CsSbCl6 crystallizes in the monoclinic Cc space group. Cs(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), two equivalent Cl(4), two equivalent Cl(5), and two equivalent Cl(6) atoms to form CsCl12 cuboctahedra that share corners with four equivalent Cs(1)Cl12 cuboctahedra, corners with two equivalent Sb(1)Cl6 octahedra, edges with four equivalent Cs(1)Cl12 cuboctahedra, edges with two equivalent Sb(1)Cl6 octahedra, and faces with two equivalent Sb(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 48°. Sb(1) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), and one Cl(6) atom to form SbCl6 octahedra that share corners with two equivalent Cs(1)Cl12 cuboctahedra, edges with two equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Cs(1)Cl12 cuboctahedra. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the fourth Cl site, Cl(4) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the fifth Cl site, Cl(5) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the sixth Cl site, Cl(6) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom.
CsSbCl6 crystallizes in the monoclinic Cc space group. Cs(1) is bonded to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), two equivalent Cl(4), two equivalent Cl(5), and two equivalent Cl(6) atoms to form CsCl12 cuboctahedra that share corners with four equivalent Cs(1)Cl12 cuboctahedra, corners with two equivalent Sb(1)Cl6 octahedra, edges with four equivalent Cs(1)Cl12 cuboctahedra, edges with two equivalent Sb(1)Cl6 octahedra, and faces with two equivalent Sb(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 48°. There is one shorter (3.73 Å) and one longer (3.78 Å) Cs(1)-Cl(1) bond length. There is one shorter (3.66 Å) and one longer (3.72 Å) Cs(1)-Cl(2) bond length. There is one shorter (3.73 Å) and one longer (3.77 Å) Cs(1)-Cl(3) bond length. There is one shorter (3.66 Å) and one longer (3.72 Å) Cs(1)-Cl(4) bond length. There is one shorter (3.73 Å) and one longer (3.77 Å) Cs(1)-Cl(5) bond length. There is one shorter (3.73 Å) and one longer (3.76 Å) Cs(1)-Cl(6) bond length. Sb(1) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), and one Cl(6) atom to form SbCl6 octahedra that share corners with two equivalent Cs(1)Cl12 cuboctahedra, edges with two equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Cs(1)Cl12 cuboctahedra. The Sb(1)-Cl(1) bond length is 2.40 Å. The Sb(1)-Cl(2) bond length is 2.40 Å. The Sb(1)-Cl(3) bond length is 2.40 Å. The Sb(1)-Cl(4) bond length is 2.39 Å. The Sb(1)-Cl(5) bond length is 2.39 Å. The Sb(1)-Cl(6) bond length is 2.39 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the fourth Cl site, Cl(4) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the fifth Cl site, Cl(5) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom. In the sixth Cl site, Cl(6) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one Sb(1) atom.