Cs2VCl6 crystallizes in the orthorhombic Immm space group. Cs(1) is bonded to four equivalent Cl(1) and eight equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with four equivalent V(1)Cl6 octahedra. V(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form VCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one V(1) atom. In the second Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one V(1) atom.
Cs2VCl6 crystallizes in the orthorhombic Immm space group. Cs(1) is bonded to four equivalent Cl(1) and eight equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with four equivalent V(1)Cl6 octahedra. There are two shorter (3.63 Å) and two longer (3.64 Å) Cs(1)-Cl(1) bond lengths. There are four shorter (3.65 Å) and four longer (3.66 Å) Cs(1)-Cl(2) bond lengths. V(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form VCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. Both V(1)-Cl(1) bond lengths are 2.34 Å. All V(1)-Cl(2) bond lengths are 2.32 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one V(1) atom. In the second Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one V(1) atom.