V4(OF3)3 crystallizes in the monoclinic P2 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one F(2), one F(3), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra and corners with four equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 24-33°. In the second V site, V(2) is bonded to one O(3), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with two equivalent V(2)OF5 octahedra and corners with four equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 28-33°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) 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 bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom.
V4(OF3)3 crystallizes in the monoclinic P2 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one F(2), one F(3), one F(4), and one F(5) atom to form VO2F4 octahedra that share corners with two equivalent V(1)O2F4 octahedra and corners with four equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 24-33°. The V(1)-O(1) bond length is 1.84 Å. The V(1)-O(2) bond length is 1.85 Å. The V(1)-F(2) bond length is 1.96 Å. The V(1)-F(3) bond length is 1.98 Å. The V(1)-F(4) bond length is 1.99 Å. The V(1)-F(5) bond length is 1.97 Å. In the second V site, V(2) is bonded to one O(3), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with two equivalent V(2)OF5 octahedra and corners with four equivalent V(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 28-33°. The V(2)-O(3) bond length is 1.78 Å. The V(2)-F(1) bond length is 1.95 Å. The V(2)-F(2) bond length is 1.99 Å. The V(2)-F(3) bond length is 1.97 Å. The V(2)-F(4) bond length is 1.97 Å. The V(2)-F(5) bond length is 1.99 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the second O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. There are five inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) 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 bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom.