Cs3V2O2F7 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to two equivalent O(1), two equivalent F(2), two equivalent F(3), two equivalent F(4), and four equivalent F(1) atoms to form distorted corner-sharing CsO2F10 cuboctahedra. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to three equivalent O(1), one F(2), two equivalent F(1), three equivalent F(3), and three equivalent F(4) atoms. V(1) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), and two equivalent F(1) atoms. O(1) is bonded in a single-bond geometry to one Cs(1), three equivalent Cs(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(3) is bonded in a distorted single-bond geometry to one Cs(1), three equivalent Cs(2), and one V(1) atom. In the second F site, F(4) is bonded in a distorted single-bond geometry to one Cs(1), three equivalent Cs(2), and one V(1) atom. In the third F site, F(1) is bonded in a distorted L-shaped geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent V(1) atoms. In the fourth F site, F(2) is bonded in a distorted L-shaped geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent V(1) atoms.
Cs3V2O2F7 crystallizes in the monoclinic C2/c space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to two equivalent O(1), two equivalent F(2), two equivalent F(3), two equivalent F(4), and four equivalent F(1) atoms to form distorted corner-sharing CsO2F10 cuboctahedra. Both Cs(1)-O(1) bond lengths are 3.12 Å. Both Cs(1)-F(2) bond lengths are 3.18 Å. Both Cs(1)-F(3) bond lengths are 3.06 Å. Both Cs(1)-F(4) bond lengths are 3.06 Å. There are two shorter (3.13 Å) and two longer (3.24 Å) Cs(1)-F(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to three equivalent O(1), one F(2), two equivalent F(1), three equivalent F(3), and three equivalent F(4) atoms. There are a spread of Cs(2)-O(1) bond distances ranging from 3.18-3.21 Å. The Cs(2)-F(2) bond length is 3.50 Å. There is one shorter (3.45 Å) and one longer (3.50 Å) Cs(2)-F(1) bond length. There are a spread of Cs(2)-F(3) bond distances ranging from 3.10-3.30 Å. There are a spread of Cs(2)-F(4) bond distances ranging from 3.12-3.25 Å. V(1) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(4), and two equivalent F(1) atoms. The V(1)-O(1) bond length is 1.63 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(3) bond length is 1.89 Å. The V(1)-F(4) bond length is 1.88 Å. There is one shorter (1.98 Å) and one longer (2.24 Å) V(1)-F(1) bond length. O(1) is bonded in a single-bond geometry to one Cs(1), three equivalent Cs(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(3) is bonded in a distorted single-bond geometry to one Cs(1), three equivalent Cs(2), and one V(1) atom. In the second F site, F(4) is bonded in a distorted single-bond geometry to one Cs(1), three equivalent Cs(2), and one V(1) atom. In the third F site, F(1) is bonded in a distorted L-shaped geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent V(1) atoms. In the fourth F site, F(2) is bonded in a distorted L-shaped geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent V(1) atoms.