V2O3F is Hydrophilite-derived structured and crystallizes in the orthorhombic Amm2 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), two equivalent O(2), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with four equivalent V(3)O5F octahedra, corners with four equivalent V(4)O5F octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. 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 VO4F2 octahedra that share corners with eight equivalent V(4)O5F octahedra and edges with two equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. In the third V site, V(3) is bonded to one O(4), four equivalent O(2), and one F(1) atom to form distorted VO5F octahedra that share corners with eight equivalent V(1)O4F2 octahedra and edges with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 48-50°. In the fourth V site, V(4) is bonded to one O(1), two equivalent O(2), two equivalent O(3), and one F(2) atom to form distorted VO5F octahedra that share corners with four equivalent V(1)O4F2 octahedra, corners with four equivalent V(2)O4F2 octahedra,  an edgeedge with one V(3)O5F octahedra, and  an edgeedge with one V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-52°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a 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(2) and two equivalent V(4) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar 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 3-coordinate geometry to one V(3) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(4) atom.
V2O3F is Hydrophilite-derived structured and crystallizes in the orthorhombic Amm2 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), two equivalent O(2), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with four equivalent V(3)O5F octahedra, corners with four equivalent V(4)O5F octahedra,  an edgeedge with one V(1)O4F2 octahedra, and  an edgeedge with one V(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The V(1)-O(1) bond length is 1.99 Å. The V(1)-O(4) bond length is 1.98 Å. Both V(1)-O(2) bond lengths are 1.91 Å. The V(1)-F(1) bond length is 2.01 Å. The V(1)-F(2) bond length is 1.99 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 VO4F2 octahedra that share corners with eight equivalent V(4)O5F octahedra and edges with two equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 47-50°. Both V(2)-O(1) bond lengths are 1.93 Å. Both V(2)-O(3) bond lengths are 1.90 Å. Both V(2)-F(2) bond lengths are 2.07 Å. In the third V site, V(3) is bonded to one O(4), four equivalent O(2), and one F(1) atom to form distorted VO5F octahedra that share corners with eight equivalent V(1)O4F2 octahedra and edges with two equivalent V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 48-50°. The V(3)-O(4) bond length is 1.76 Å. All V(3)-O(2) bond lengths are 1.95 Å. The V(3)-F(1) bond length is 2.34 Å. In the fourth V site, V(4) is bonded to one O(1), two equivalent O(2), two equivalent O(3), and one F(2) atom to form distorted VO5F octahedra that share corners with four equivalent V(1)O4F2 octahedra, corners with four equivalent V(2)O4F2 octahedra,  an edgeedge with one V(3)O5F octahedra, and  an edgeedge with one V(4)O5F octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The V(4)-O(1) bond length is 1.78 Å. Both V(4)-O(2) bond lengths are 1.96 Å. Both V(4)-O(3) bond lengths are 1.95 Å. The V(4)-F(2) bond length is 2.29 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a 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(2) and two equivalent V(4) atoms. In the fourth O site, O(4) is bonded in a distorted trigonal planar 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 3-coordinate geometry to one V(3) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one V(4) atom.