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 in a 6-coordinate geometry to one O(1), one O(2), one F(2), one F(3), one F(4), and one F(9) atom. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one F(1), one F(4), one F(6), and one F(9) atom. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(3), one F(1), one F(5), one F(6), one F(7), and one F(8) atom. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(2) 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(2) and one V(3) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) 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(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the sixth F site, F(6) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one V(3) and one V(4) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) 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 in a 6-coordinate geometry to one O(1), one O(2), one F(2), one F(3), one F(4), and one F(9) atom. The V(1)-O(1) bond length is 2.48 Å. The V(1)-O(2) bond length is 2.47 Å. The V(1)-F(2) bond length is 1.62 Å. The V(1)-F(3) bond length is 2.14 Å. The V(1)-F(4) bond length is 1.62 Å. The V(1)-F(9) bond length is 2.13 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), one F(1), one F(4), one F(6), and one F(9) atom. The V(2)-O(2) bond length is 2.20 Å. The V(2)-O(3) bond length is 1.65 Å. The V(2)-F(1) bond length is 2.05 Å. The V(2)-F(4) bond length is 1.57 Å. The V(2)-F(6) bond length is 2.63 Å. The V(2)-F(9) bond length is 1.97 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(3), one F(1), one F(5), one F(6), one F(7), and one F(8) atom. The V(3)-O(3) bond length is 1.38 Å. The V(3)-F(1) bond length is 2.17 Å. The V(3)-F(5) bond length is 2.06 Å. The V(3)-F(6) bond length is 2.45 Å. The V(3)-F(7) bond length is 2.42 Å. The V(3)-F(8) bond length is 1.71 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(1), one F(2), one F(3), one F(5), one F(7), and one F(8) atom. The V(4)-O(1) bond length is 2.18 Å. The V(4)-F(2) bond length is 1.56 Å. The V(4)-F(3) bond length is 1.97 Å. The V(4)-F(5) bond length is 2.06 Å. The V(4)-F(7) bond length is 2.64 Å. The V(4)-F(8) bond length is 1.68 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(1) and one V(4) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(2) 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(2) and one V(3) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) 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(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the sixth F site, F(6) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the eighth F site, F(8) is bonded in a bent 120 degrees geometry to one V(3) and one V(4) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom.