V4(OF3)3 crystallizes in the triclinic P1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one F(2), one F(4), one F(5), one F(6), and one F(7) atom to form VOF5 octahedra that share corners with two equivalent V(2)O2F4 octahedra and corners with four equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 24-40°. In the second V site, V(2) is bonded to one O(1), one O(2), one F(3), one F(5), one F(6), and one F(8) atom to form distorted VO2F4 octahedra that share corners with two equivalent V(1)OF5 octahedra and corners with four equivalent V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 26-43°. In the third V site, V(3) is bonded to one O(3), one F(1), one F(2), one F(4), one F(7), and one F(9) atom to form VOF5 octahedra that share corners with two equivalent V(4)O2F4 octahedra and corners with four equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 24-38°. In the fourth V site, V(4) is bonded to one O(1), one O(2), one F(1), one F(3), one F(8), and one F(9) atom to form distorted VO2F4 octahedra that share corners with two equivalent V(3)OF5 octahedra and corners with four equivalent V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 26-43°. There are three 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(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees 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(2) and one V(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees 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(1) and one V(2) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom.
V4(OF3)3 crystallizes in the triclinic P1 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one F(2), one F(4), one F(5), one F(6), and one F(7) atom to form VOF5 octahedra that share corners with two equivalent V(2)O2F4 octahedra and corners with four equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 24-40°. The V(1)-O(3) bond length is 1.86 Å. The V(1)-F(2) bond length is 1.97 Å. The V(1)-F(4) bond length is 1.93 Å. The V(1)-F(5) bond length is 1.93 Å. The V(1)-F(6) bond length is 1.93 Å. The V(1)-F(7) bond length is 1.90 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one F(3), one F(5), one F(6), and one F(8) atom to form distorted VO2F4 octahedra that share corners with two equivalent V(1)OF5 octahedra and corners with four equivalent V(4)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 26-43°. The V(2)-O(1) bond length is 2.09 Å. The V(2)-O(2) bond length is 1.64 Å. The V(2)-F(3) bond length is 1.94 Å. The V(2)-F(5) bond length is 1.95 Å. The V(2)-F(6) bond length is 1.93 Å. The V(2)-F(8) bond length is 1.94 Å. In the third V site, V(3) is bonded to one O(3), one F(1), one F(2), one F(4), one F(7), and one F(9) atom to form VOF5 octahedra that share corners with two equivalent V(4)O2F4 octahedra and corners with four equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 24-38°. The V(3)-O(3) bond length is 1.68 Å. The V(3)-F(1) bond length is 1.94 Å. The V(3)-F(2) bond length is 1.98 Å. The V(3)-F(4) bond length is 1.94 Å. The V(3)-F(7) bond length is 1.96 Å. The V(3)-F(9) bond length is 1.96 Å. In the fourth V site, V(4) is bonded to one O(1), one O(2), one F(1), one F(3), one F(8), and one F(9) atom to form distorted VO2F4 octahedra that share corners with two equivalent V(3)OF5 octahedra and corners with four equivalent V(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 26-43°. The V(4)-O(1) bond length is 1.63 Å. The V(4)-O(2) bond length is 2.11 Å. The V(4)-F(1) bond length is 1.95 Å. The V(4)-F(3) bond length is 1.95 Å. The V(4)-F(8) bond length is 1.94 Å. The V(4)-F(9) bond length is 1.93 Å. There are three 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(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. There are nine inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees 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(2) and one V(4) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees 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(1) and one V(2) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom.