Cs3VH8(O2Cl3)2 crystallizes in the orthorhombic Immm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a body-centered cubic geometry to four equivalent Cl(1) and four equivalent Cl(2) atoms. In the second Cs site, Cs(2) is bonded in a body-centered cubic geometry to two equivalent Cl(2) and six equivalent Cl(1) atoms. V(1) is bonded in an octahedral geometry to four equivalent O(1) and two equivalent Cl(2) atoms. H(1) is bonded in a single-bond geometry to one O(1) and one Cl(1) atom. O(1) is bonded in a trigonal planar geometry to one V(1) and two equivalent H(1) atoms. There are two 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), and two equivalent H(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one V(1) atom.
Cs3VH8(O2Cl3)2 crystallizes in the orthorhombic Immm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a body-centered cubic geometry to four equivalent Cl(1) and four equivalent Cl(2) atoms. All Cs(1)-Cl(1) bond lengths are 3.48 Å. All Cs(1)-Cl(2) bond lengths are 3.56 Å. In the second Cs site, Cs(2) is bonded in a body-centered cubic geometry to two equivalent Cl(2) and six equivalent Cl(1) atoms. Both Cs(2)-Cl(2) bond lengths are 3.81 Å. There are two shorter (3.53 Å) and four longer (3.72 Å) Cs(2)-Cl(1) bond lengths. V(1) is bonded in an octahedral geometry to four equivalent O(1) and two equivalent Cl(2) atoms. All V(1)-O(1) bond lengths are 2.03 Å. Both V(1)-Cl(2) bond lengths are 2.41 Å. H(1) is bonded in a single-bond geometry to one O(1) and one Cl(1) atom. The H(1)-O(1) bond length is 1.00 Å. The H(1)-Cl(1) bond length is 2.06 Å. O(1) is bonded in a trigonal planar geometry to one V(1) and two equivalent H(1) atoms. There are two 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), and two equivalent H(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one V(1) atom.