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 one O(2), one O(3), two equivalent O(4), 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 44-53°. In the second V site, V(2) 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 44-54°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one 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 45-54°. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(2), 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 44-53°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one V(2), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one V(4) atom. 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 distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), 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 one O(2), one O(3), two equivalent O(4), 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 44-53°. The V(1)-O(2) bond length is 1.89 Å. The V(1)-O(3) bond length is 1.99 Å. There is one shorter (1.92 Å) and one longer (1.99 Å) V(1)-O(4) bond length. The V(1)-F(1) bond length is 2.12 Å. The V(1)-F(2) bond length is 2.16 Å. In the second V site, V(2) 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 44-54°. Both V(2)-O(1) bond lengths are 1.90 Å. Both V(2)-O(3) bond lengths are 2.02 Å. Both V(2)-F(2) bond lengths are 2.01 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one 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 45-54°. The V(3)-O(1) bond length is 2.01 Å. The V(3)-O(2) bond length is 1.97 Å. The V(3)-O(3) bond length is 1.99 Å. The V(3)-O(4) bond length is 1.99 Å. Both V(3)-F(1) bond lengths are 2.10 Å. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(2), 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 44-53°. Both V(4)-O(1) bond lengths are 2.01 Å. Both V(4)-O(2) bond lengths are 1.96 Å. Both V(4)-F(2) bond lengths are 2.04 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(2), one V(3), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one V(4) atom. 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 distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom.