Cs4Cu(SbCl6)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to one Cl(2), two equivalent Cl(1), three equivalent Cl(4), and six equivalent Cl(3) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, and faces with four equivalent Sb(1)Cl6 octahedra. In the second Cs site, Cs(2) is bonded to one Cl(4), two equivalent Cl(3), three equivalent Cl(2), and six equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, and faces with four equivalent Sb(1)Cl6 octahedra. Cu(1) is bonded in a square co-planar geometry to two equivalent Cl(2) and four equivalent Cl(1) atoms. Sb(1) is bonded to one Cl(2), one Cl(4), two equivalent Cl(1), and two equivalent Cl(3) atoms to form SbCl6 octahedra that share faces with four equivalent Cs(1)Cl12 cuboctahedra and faces with four equivalent Cs(2)Cl12 cuboctahedra. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to one Cs(1), three equivalent Cs(2), one Cu(1), and one Sb(1) atom. In the second Cl site, Cl(2) is bonded to one Cs(1), three equivalent Cs(2), one Cu(1), and one Sb(1) atom to form distorted ClCs4CuSb octahedra that share corners with three equivalent Cl(2)Cs4CuSb octahedra, corners with three equivalent Cl(4)Cs4Sb square pyramids, edges with two equivalent Cl(2)Cs4CuSb octahedra, and edges with two equivalent Cl(4)Cs4Sb square pyramids. The corner-sharing octahedral tilt angles range from 0-7°. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to one Cs(2), three equivalent Cs(1), and one Sb(1) atom. In the fourth Cl site, Cl(4) is bonded to one Cs(2), three equivalent Cs(1), and one Sb(1) atom to form distorted ClCs4Sb square pyramids that share corners with three equivalent Cl(2)Cs4CuSb octahedra, corners with two equivalent Cl(4)Cs4Sb square pyramids, edges with two equivalent Cl(2)Cs4CuSb octahedra, and edges with two equivalent Cl(4)Cs4Sb square pyramids. The corner-sharing octahedral tilt angles range from 2-7°.
Cs4Cu(SbCl6)2 crystallizes in the monoclinic C2/m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to one Cl(2), two equivalent Cl(1), three equivalent Cl(4), and six equivalent Cl(3) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, and faces with four equivalent Sb(1)Cl6 octahedra. The Cs(1)-Cl(2) bond length is 3.68 Å. Both Cs(1)-Cl(1) bond lengths are 3.85 Å. There are two shorter (3.72 Å) and one longer (3.74 Å) Cs(1)-Cl(4) bond length. There are a spread of Cs(1)-Cl(3) bond distances ranging from 3.83-3.92 Å. In the second Cs site, Cs(2) is bonded to one Cl(4), two equivalent Cl(3), three equivalent Cl(2), and six equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, and faces with four equivalent Sb(1)Cl6 octahedra. The Cs(2)-Cl(4) bond length is 3.74 Å. Both Cs(2)-Cl(3) bond lengths are 3.89 Å. There is one shorter (3.70 Å) and two longer (3.72 Å) Cs(2)-Cl(2) bond lengths. There are a spread of Cs(2)-Cl(1) bond distances ranging from 3.85-3.88 Å. Cu(1) is bonded in a square co-planar geometry to two equivalent Cl(2) and four equivalent Cl(1) atoms. Both Cu(1)-Cl(2) bond lengths are 3.06 Å. All Cu(1)-Cl(1) bond lengths are 2.33 Å. Sb(1) is bonded to one Cl(2), one Cl(4), two equivalent Cl(1), and two equivalent Cl(3) atoms to form SbCl6 octahedra that share faces with four equivalent Cs(1)Cl12 cuboctahedra and faces with four equivalent Cs(2)Cl12 cuboctahedra. The Sb(1)-Cl(2) bond length is 2.66 Å. The Sb(1)-Cl(4) bond length is 2.61 Å. Both Sb(1)-Cl(1) bond lengths are 2.89 Å. Both Sb(1)-Cl(3) bond lengths are 2.48 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to one Cs(1), three equivalent Cs(2), one Cu(1), and one Sb(1) atom. In the second Cl site, Cl(2) is bonded to one Cs(1), three equivalent Cs(2), one Cu(1), and one Sb(1) atom to form distorted ClCs4CuSb octahedra that share corners with three equivalent Cl(2)Cs4CuSb octahedra, corners with three equivalent Cl(4)Cs4Sb square pyramids, edges with two equivalent Cl(2)Cs4CuSb octahedra, and edges with two equivalent Cl(4)Cs4Sb square pyramids. The corner-sharing octahedral tilt angles range from 0-7°. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to one Cs(2), three equivalent Cs(1), and one Sb(1) atom. In the fourth Cl site, Cl(4) is bonded to one Cs(2), three equivalent Cs(1), and one Sb(1) atom to form distorted ClCs4Sb square pyramids that share corners with three equivalent Cl(2)Cs4CuSb octahedra, corners with two equivalent Cl(4)Cs4Sb square pyramids, edges with two equivalent Cl(2)Cs4CuSb octahedra, and edges with two equivalent Cl(4)Cs4Sb square pyramids. The corner-sharing octahedral tilt angles range from 2-7°.