V2(OF)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(1), one O(3), one O(5), one F(3), one F(4), and one F(5) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 8-34°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one F(2), one F(4), and one F(6) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 8-31°. In the third V site, V(3) is bonded to one O(1), one O(5), one O(6), one F(1), one F(3), and one F(5) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 8-34°. In the fourth V site, V(4) is bonded to one O(2), one O(4), one O(6), one F(1), one F(2), and one F(6) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 11-31°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a distorted 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(2) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one V(2) and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a linear 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(2) and one V(4) atom. In the third F site, F(3) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fourth F site, F(4) is bonded in a linear 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(3) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom.
V2(OF)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(1), one O(3), one O(5), one F(3), one F(4), and one F(5) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 8-34°. The V(1)-O(1) bond length is 2.18 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(5) bond length is 1.66 Å. The V(1)-F(3) bond length is 1.98 Å. The V(1)-F(4) bond length is 1.96 Å. The V(1)-F(5) bond length is 1.99 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one F(2), one F(4), and one F(6) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 8-31°. The V(2)-O(2) bond length is 2.22 Å. The V(2)-O(3) bond length is 1.69 Å. The V(2)-O(4) bond length is 1.66 Å. The V(2)-F(2) bond length is 1.91 Å. The V(2)-F(4) bond length is 2.05 Å. The V(2)-F(6) bond length is 1.93 Å. In the third V site, V(3) is bonded to one O(1), one O(5), one O(6), one F(1), one F(3), and one F(5) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 8-34°. The V(3)-O(1) bond length is 1.66 Å. The V(3)-O(5) bond length is 2.20 Å. The V(3)-O(6) bond length is 1.69 Å. The V(3)-F(1) bond length is 2.05 Å. The V(3)-F(3) bond length is 1.92 Å. The V(3)-F(5) bond length is 1.92 Å. In the fourth V site, V(4) is bonded to one O(2), one O(4), one O(6), one F(1), one F(2), and one F(6) atom to form distorted corner-sharing VO3F3 octahedra. The corner-sharing octahedral tilt angles range from 11-31°. The V(4)-O(2) bond length is 1.65 Å. The V(4)-O(4) bond length is 2.20 Å. The V(4)-O(6) bond length is 1.98 Å. The V(4)-F(1) bond length is 1.96 Å. The V(4)-F(2) bond length is 1.99 Å. The V(4)-F(6) bond length is 1.98 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a distorted 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(2) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one V(2) and one V(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a linear 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(2) and one V(4) atom. In the third F site, F(3) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fourth F site, F(4) is bonded in a linear 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(3) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom.