V3(O2F)2 is Hydrophilite-derived structured and crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), one O(6), one O(7), one F(1), and one F(4) atom to form VO4F2 octahedra that share corners with two equivalent V(3)O4F2 octahedra, corners with three equivalent V(6)O3F3 octahedra, corners with three equivalent V(2)O4F2 octahedra,  an edgeedge with one V(5)O4F2 octahedra, and  an edgeedge with one V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 44-56°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), one O(7), one F(1), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent V(4)O5F octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(5)O4F2 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the third V site, V(3) is bonded to one O(2), one O(4), one O(5), one O(8), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with three equivalent V(5)O4F2 octahedra, corners with three equivalent V(4)O5F octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the fourth V site, V(4) is bonded to one O(2), one O(3), one O(5), one O(6), one O(8), and one F(4) atom to form VO5F octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with three equivalent V(6)O3F3 octahedra, corners with three equivalent V(3)O4F2 octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(7), one O(8), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent V(6)O3F3 octahedra, corners with three equivalent V(2)O4F2 octahedra, corners with three equivalent V(3)O4F2 octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 45-55°. In the sixth V site, V(6) is bonded to one O(3), one O(4), one O(6), one F(2), one F(3), and one F(4) atom to form VO3F3 octahedra that share corners with two equivalent V(5)O4F2 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(4)O5F octahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. There are eight 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(5) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one V(5) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(2), one V(4), and one V(6) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(6) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one V(5) atom. There are four 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(3), one V(5), and one V(6) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(6) atom.
V3(O2F)2 is Hydrophilite-derived structured and crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), one O(6), one O(7), one F(1), and one F(4) atom to form VO4F2 octahedra that share corners with two equivalent V(3)O4F2 octahedra, corners with three equivalent V(6)O3F3 octahedra, corners with three equivalent V(2)O4F2 octahedra,  an edgeedge with one V(5)O4F2 octahedra, and  an edgeedge with one V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 44-56°. The V(1)-O(1) bond length is 1.93 Å. The V(1)-O(4) bond length is 1.84 Å. The V(1)-O(6) bond length is 1.97 Å. The V(1)-O(7) bond length is 1.87 Å. The V(1)-F(1) bond length is 2.18 Å. The V(1)-F(4) bond length is 2.15 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), one O(7), one F(1), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent V(4)O5F octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(5)O4F2 octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The V(2)-O(1) bond length is 1.98 Å. The V(2)-O(3) bond length is 2.00 Å. The V(2)-O(5) bond length is 2.04 Å. The V(2)-O(7) bond length is 2.01 Å. The V(2)-F(1) bond length is 2.07 Å. The V(2)-F(3) bond length is 2.05 Å. In the third V site, V(3) is bonded to one O(2), one O(4), one O(5), one O(8), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with three equivalent V(5)O4F2 octahedra, corners with three equivalent V(4)O5F octahedra,  an edgeedge with one V(6)O3F3 octahedra, and  an edgeedge with one V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The V(3)-O(2) bond length is 1.90 Å. The V(3)-O(4) bond length is 1.96 Å. The V(3)-O(5) bond length is 1.88 Å. The V(3)-O(8) bond length is 1.87 Å. The V(3)-F(1) bond length is 2.13 Å. The V(3)-F(2) bond length is 2.17 Å. In the fourth V site, V(4) is bonded to one O(2), one O(3), one O(5), one O(6), one O(8), and one F(4) atom to form VO5F octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with three equivalent V(6)O3F3 octahedra, corners with three equivalent V(3)O4F2 octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(5)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. The V(4)-O(2) bond length is 2.05 Å. The V(4)-O(3) bond length is 2.01 Å. The V(4)-O(5) bond length is 2.07 Å. The V(4)-O(6) bond length is 2.01 Å. The V(4)-O(8) bond length is 2.05 Å. The V(4)-F(4) bond length is 2.13 Å. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(7), one O(8), one F(2), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent V(6)O3F3 octahedra, corners with three equivalent V(2)O4F2 octahedra, corners with three equivalent V(3)O4F2 octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The V(5)-O(1) bond length is 1.98 Å. The V(5)-O(2) bond length is 2.01 Å. The V(5)-O(7) bond length is 2.01 Å. The V(5)-O(8) bond length is 2.01 Å. The V(5)-F(2) bond length is 2.05 Å. The V(5)-F(3) bond length is 2.05 Å. In the sixth V site, V(6) is bonded to one O(3), one O(4), one O(6), one F(2), one F(3), and one F(4) atom to form VO3F3 octahedra that share corners with two equivalent V(5)O4F2 octahedra, corners with three equivalent V(1)O4F2 octahedra, corners with three equivalent V(4)O5F octahedra,  an edgeedge with one V(2)O4F2 octahedra, and  an edgeedge with one V(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The V(6)-O(3) bond length is 1.95 Å. The V(6)-O(4) bond length is 2.09 Å. The V(6)-O(6) bond length is 1.91 Å. The V(6)-F(2) bond length is 2.05 Å. The V(6)-F(3) bond length is 2.05 Å. The V(6)-F(4) bond length is 2.08 Å. There are eight 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(5) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one V(5) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(2), one V(4), and one V(6) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(6) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one V(1), one V(4), and one V(6) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one V(4), and one V(5) atom. There are four 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(3), one V(5), and one V(6) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(5), and one V(6) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(6) atom.