Cs2V(OF2)2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 11-coordinate geometry to one O(2), two equivalent O(1), and eight equivalent F(1) atoms. In the second Cs site, Cs(2) is bonded in a 11-coordinate geometry to one O(1), two equivalent O(2), and eight equivalent F(1) atoms. V(1) is bonded in an octahedral geometry to one O(1), one O(2), and four equivalent F(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Cs(2), two equivalent Cs(1), and one V(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Cs(1), two equivalent Cs(2), and one V(1) atom. F(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one V(1) atom.
Cs2V(OF2)2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 11-coordinate geometry to one O(2), two equivalent O(1), and eight equivalent F(1) atoms. The Cs(1)-O(2) bond length is 3.39 Å. Both Cs(1)-O(1) bond lengths are 3.19 Å. There are four shorter (3.22 Å) and four longer (3.30 Å) Cs(1)-F(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 11-coordinate geometry to one O(1), two equivalent O(2), and eight equivalent F(1) atoms. The Cs(2)-O(1) bond length is 3.25 Å. Both Cs(2)-O(2) bond lengths are 3.22 Å. There are four shorter (3.18 Å) and four longer (3.33 Å) Cs(2)-F(1) bond lengths. V(1) is bonded in an octahedral geometry to one O(1), one O(2), and four equivalent F(1) atoms. The V(1)-O(1) bond length is 1.68 Å. The V(1)-O(2) bond length is 1.98 Å. All V(1)-F(1) bond lengths are 1.90 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Cs(2), two equivalent Cs(1), and one V(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Cs(1), two equivalent Cs(2), and one V(1) atom. F(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one V(1) atom.