V3(OF3)2 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form a mixture of corner and edge-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 38-57°. In the second V site, V(2) is bonded to one O(1), one O(2), one F(1), one F(3), one F(5), and one F(6) atom to form VO2F4 octahedra that share corners with four equivalent V(3)O2F4 octahedra and corners with four equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-57°. In the third V site, V(3) is bonded to one O(1), one O(2), one F(2), one F(4), one F(5), and one F(6) atom to form VO2F4 octahedra that share corners with four equivalent V(2)O2F4 octahedra and edges with two equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-50°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a water-like geometry to one V(1) and one V(3) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(1) and one V(3) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(3) atom.
V3(OF3)2 crystallizes in the triclinic P-1 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form a mixture of corner and edge-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 38-57°. The V(1)-O(2) bond length is 1.96 Å. The V(1)-F(1) bond length is 1.98 Å. The V(1)-F(2) bond length is 1.99 Å. The V(1)-F(3) bond length is 1.96 Å. The V(1)-F(4) bond length is 1.99 Å. The V(1)-F(6) bond length is 2.18 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one F(1), one F(3), one F(5), and one F(6) atom to form VO2F4 octahedra that share corners with four equivalent V(3)O2F4 octahedra and corners with four equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-57°. The V(2)-O(1) bond length is 1.98 Å. The V(2)-O(2) bond length is 1.95 Å. The V(2)-F(1) bond length is 2.00 Å. The V(2)-F(3) bond length is 2.00 Å. The V(2)-F(5) bond length is 2.01 Å. The V(2)-F(6) bond length is 2.13 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one F(2), one F(4), one F(5), and one F(6) atom to form VO2F4 octahedra that share corners with four equivalent V(2)O2F4 octahedra and edges with two equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 32-50°. The V(3)-O(1) bond length is 1.71 Å. The V(3)-O(2) bond length is 2.03 Å. The V(3)-F(2) bond length is 1.97 Å. The V(3)-F(4) bond length is 1.97 Å. The V(3)-F(5) bond length is 1.97 Å. The V(3)-F(6) bond length is 2.08 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one V(1), one V(2), and one V(3) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the second F site, F(2) is bonded in a water-like geometry to one V(1) and one V(3) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(1) and one V(3) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(3) atom.