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 two equivalent O(1), two equivalent O(2), one F(1), and one F(2) atom to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(4), one F(1), and one F(2) atom to form a mixture of distorted edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the third V site, V(3) is bonded to one O(2), one O(4), two equivalent O(3), one F(1), and one F(2) atom to form a mixture of edge and corner-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 trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(3) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(2) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(3) atom. 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(3) atom.
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 two equivalent O(1), two equivalent O(2), one F(1), and one F(2) atom to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. There is one shorter (2.06 Å) and one longer (2.08 Å) V(1)-O(1) bond length. There is one shorter (2.00 Å) and one longer (2.02 Å) V(1)-O(2) bond length. The V(1)-F(1) bond length is 2.08 Å. The V(1)-F(2) bond length is 2.08 Å. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(4), one F(1), and one F(2) atom to form a mixture of distorted edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The V(2)-O(1) bond length is 1.89 Å. The V(2)-O(3) bond length is 1.88 Å. There is one shorter (1.77 Å) and one longer (2.08 Å) V(2)-O(4) bond length. The V(2)-F(1) bond length is 2.13 Å. The V(2)-F(2) bond length is 2.11 Å. In the third V site, V(3) is bonded to one O(2), one O(4), two equivalent O(3), one F(1), and one F(2) atom to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The V(3)-O(2) bond length is 1.95 Å. The V(3)-O(4) bond length is 2.06 Å. There is one shorter (1.94 Å) and one longer (2.03 Å) V(3)-O(3) bond length. The V(3)-F(1) bond length is 2.12 Å. The V(3)-F(2) bond length is 2.11 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(3) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(2) and two equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(2) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one V(1), one V(2), and one V(3) atom. 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(3) atom.