V3(O2F)2 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), 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 44-52°. In the second V site, V(2) is bonded to one O(1), one O(4), two equivalent O(2), 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 44-56°. 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 44-54°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(3) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(3) 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(2) and two equivalent V(3) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(1) atoms.
V3(O2F)2 is Hydrophilite-derived structured and crystallizes in the monoclinic P2_1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), 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 44-52°. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(4) bond length is 1.94 Å. There is one shorter (1.85 Å) and one longer (1.89 Å) V(1)-O(3) bond length. There is one shorter (2.05 Å) and one longer (2.06 Å) V(1)-F(2) bond length. In the second V site, V(2) is bonded to one O(1), one O(4), two equivalent O(2), 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 44-56°. The V(2)-O(1) bond length is 1.90 Å. The V(2)-O(4) bond length is 1.93 Å. There is one shorter (1.90 Å) and one longer (1.95 Å) V(2)-O(2) bond length. The V(2)-F(1) bond length is 2.10 Å. The V(2)-F(2) bond length is 2.10 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 44-54°. The V(3)-O(1) bond length is 1.86 Å. The V(3)-O(2) bond length is 1.98 Å. The V(3)-O(3) bond length is 1.88 Å. The V(3)-O(4) bond length is 1.94 Å. There is one shorter (2.06 Å) and one longer (2.12 Å) V(3)-F(1) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(3) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(3) 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(2) and two equivalent V(3) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(1) atoms.