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(2) atoms to form VO4F2 octahedra that share corners with four equivalent V(4)O3F3 octahedra, corners with four equivalent V(3)O4F2 octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), two equivalent O(2), and one F(1) atom to form distorted VO5F octahedra that share corners with two equivalent V(3)O4F2 octahedra, corners with six equivalent V(4)O3F3 octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 46-52°. 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 VO4F2 octahedra that share corners with four equivalent V(1)O4F2 octahedra, corners with four equivalent V(2)O5F octahedra, and edges with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(4), one F(2), and two equivalent F(1) atoms to form VO3F3 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with six equivalent V(2)O5F octahedra,  an edgeedge with one V(4)O3F3 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom. 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 3-coordinate geometry to one V(2) and two equivalent V(4) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(1), 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(2) atoms to form VO4F2 octahedra that share corners with four equivalent V(4)O3F3 octahedra, corners with four equivalent V(3)O4F2 octahedra, and edges with two equivalent V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 46-52°. Both V(1)-O(3) bond lengths are 2.00 Å. Both V(1)-O(4) bond lengths are 2.01 Å. Both V(1)-F(2) bond lengths are 2.11 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), two equivalent O(2), and one F(1) atom to form distorted VO5F octahedra that share corners with two equivalent V(3)O4F2 octahedra, corners with six equivalent V(4)O3F3 octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(2)O5F octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The V(2)-O(1) bond length is 1.79 Å. The V(2)-O(3) bond length is 1.97 Å. The V(2)-O(4) bond length is 1.97 Å. Both V(2)-O(2) bond lengths are 1.98 Å. The V(2)-F(1) bond length is 2.43 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 VO4F2 octahedra that share corners with four equivalent V(1)O4F2 octahedra, corners with four equivalent V(2)O5F octahedra, and edges with two equivalent V(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. Both V(3)-O(1) bond lengths are 2.05 Å. Both V(3)-O(3) bond lengths are 1.96 Å. Both V(3)-F(2) bond lengths are 2.06 Å. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(4), one F(2), and two equivalent F(1) atoms to form VO3F3 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with six equivalent V(2)O5F octahedra,  an edgeedge with one V(4)O3F3 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. The V(4)-O(1) bond length is 2.01 Å. The V(4)-O(2) bond length is 1.98 Å. The V(4)-O(4) bond length is 1.95 Å. The V(4)-F(2) bond length is 2.07 Å. There is one shorter (2.03 Å) and one longer (2.06 Å) V(4)-F(1) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom. 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 3-coordinate geometry to one V(2) and two equivalent V(4) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one V(4) atom.