V3(O2F)2 is Hydrophilite-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. In the second V site, V(2) is bonded to one O(3), one O(4), two equivalent O(2), one F(1), and one F(2) atom to form a mixture of distorted corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(2) atoms to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the fourth V site, V(4) is bonded to one O(2), one O(4), two equivalent O(1), one F(1), and one F(2) atom to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(4) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(4) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(4) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom.
V3(O2F)2 is Hydrophilite-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. Both V(1)-O(3) bond lengths are 2.00 Å. Both V(1)-O(4) bond lengths are 2.03 Å. Both V(1)-F(1) bond lengths are 2.08 Å. In the second V site, V(2) is bonded to one O(3), one O(4), two equivalent O(2), one F(1), and one F(2) atom to form a mixture of distorted corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(2)-O(3) bond length is 1.93 Å. The V(2)-O(4) bond length is 1.80 Å. There is one shorter (1.88 Å) and one longer (2.01 Å) V(2)-O(2) bond length. The V(2)-F(1) bond length is 2.18 Å. The V(2)-F(2) bond length is 2.10 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(2) atoms to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. Both V(3)-O(1) bond lengths are 1.97 Å. Both V(3)-O(3) bond lengths are 2.07 Å. Both V(3)-F(2) bond lengths are 2.07 Å. In the fourth V site, V(4) is bonded to one O(2), one O(4), two equivalent O(1), one F(1), and one F(2) atom to form a mixture of corner and edge-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 45-51°. The V(4)-O(2) bond length is 1.96 Å. The V(4)-O(4) bond length is 2.05 Å. There is one shorter (1.93 Å) and one longer (1.98 Å) V(4)-O(1) bond length. The V(4)-F(1) bond length is 2.14 Å. The V(4)-F(2) bond length is 2.12 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(4) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(4) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(4) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom.