V2O3F2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), one F(1), and one F(2) atom to form distorted VO3F2 trigonal bipyramids that share corners with five equivalent V(2)O4F2 octahedra and  an edgeedge with one V(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-59°. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with five equivalent V(1)O3F2 trigonal bipyramids and  an edgeedge with one V(2)O4F2 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in an L-shaped geometry to two equivalent V(2) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom.
V2O3F2 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), one F(1), and one F(2) atom to form distorted VO3F2 trigonal bipyramids that share corners with five equivalent V(2)O4F2 octahedra and  an edgeedge with one V(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-59°. The V(1)-O(3) bond length is 1.69 Å. There is one shorter (1.92 Å) and one longer (1.97 Å) V(1)-O(1) bond length. The V(1)-F(1) bond length is 2.00 Å. The V(1)-F(2) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), one F(1), and one F(2) atom to form VO4F2 octahedra that share corners with five equivalent V(1)O3F2 trigonal bipyramids and  an edgeedge with one V(2)O4F2 octahedra. The V(2)-O(1) bond length is 1.97 Å. The V(2)-O(3) bond length is 1.97 Å. There is one shorter (1.73 Å) and one longer (2.00 Å) V(2)-O(2) bond length. The V(2)-F(1) bond length is 2.01 Å. The V(2)-F(2) bond length is 2.07 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in an L-shaped geometry to two equivalent V(2) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one V(1) and one V(2) atom.