VOF2 crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one F(12), one F(3), one F(5), and one F(9) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 20-34°. In the second V site, V(2) is bonded to one O(1), one O(6), one F(10), one F(11), one F(4), and one F(7) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 22-42°. In the third V site, V(3) is bonded to one O(1), one O(4), one F(1), one F(11), one F(2), and one F(7) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 18-42°. In the fourth V site, V(4) is bonded to one O(3), one O(4), one F(1), one F(12), one F(2), and one F(5) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 18-38°. In the fifth V site, V(5) is bonded to one O(2), one O(5), one F(3), one F(6), one F(8), and one F(9) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-39°. In the sixth V site, V(6) is bonded to one O(2), one O(6), one F(10), one F(4), one F(6), and one F(8) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-39°. There are six 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 bent 150 degrees geometry to one V(5) and one V(6) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. There are twelve 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 linear geometry to one V(3) 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(5) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(5) and one V(6) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(5) and one V(6) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom.
VOF2 crystallizes in the triclinic P1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), one F(12), one F(3), one F(5), and one F(9) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 20-34°. The V(1)-O(3) bond length is 1.88 Å. The V(1)-O(5) bond length is 1.68 Å. The V(1)-F(12) bond length is 1.91 Å. The V(1)-F(3) bond length is 1.93 Å. The V(1)-F(5) bond length is 2.01 Å. The V(1)-F(9) bond length is 1.96 Å. In the second V site, V(2) is bonded to one O(1), one O(6), one F(10), one F(11), one F(4), and one F(7) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 22-42°. The V(2)-O(1) bond length is 2.03 Å. The V(2)-O(6) bond length is 1.67 Å. The V(2)-F(10) bond length is 1.97 Å. The V(2)-F(11) bond length is 1.96 Å. The V(2)-F(4) bond length is 1.95 Å. The V(2)-F(7) bond length is 1.89 Å. In the third V site, V(3) is bonded to one O(1), one O(4), one F(1), one F(11), one F(2), and one F(7) atom to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 18-42°. The V(3)-O(1) bond length is 1.66 Å. The V(3)-O(4) bond length is 1.65 Å. The V(3)-F(1) bond length is 2.04 Å. The V(3)-F(11) bond length is 1.91 Å. The V(3)-F(2) bond length is 1.90 Å. The V(3)-F(7) bond length is 2.08 Å. In the fourth V site, V(4) is bonded to one O(3), one O(4), one F(1), one F(12), one F(2), and one F(5) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 18-38°. The V(4)-O(3) bond length is 1.68 Å. The V(4)-O(4) bond length is 2.05 Å. The V(4)-F(1) bond length is 1.91 Å. The V(4)-F(12) bond length is 1.97 Å. The V(4)-F(2) bond length is 1.96 Å. The V(4)-F(5) bond length is 1.92 Å. In the fifth V site, V(5) is bonded to one O(2), one O(5), one F(3), one F(6), one F(8), and one F(9) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-39°. The V(5)-O(2) bond length is 1.67 Å. The V(5)-O(5) bond length is 1.86 Å. The V(5)-F(3) bond length is 2.00 Å. The V(5)-F(6) bond length is 1.99 Å. The V(5)-F(8) bond length is 1.95 Å. The V(5)-F(9) bond length is 1.93 Å. In the sixth V site, V(6) is bonded to one O(2), one O(6), one F(10), one F(4), one F(6), and one F(8) atom to form corner-sharing VO2F4 octahedra. The corner-sharing octahedral tilt angles range from 23-39°. The V(6)-O(2) bond length is 1.90 Å. The V(6)-O(6) bond length is 1.91 Å. The V(6)-F(10) bond length is 1.90 Å. The V(6)-F(4) bond length is 1.91 Å. The V(6)-F(6) bond length is 1.90 Å. The V(6)-F(8) bond length is 1.93 Å. There are six 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 bent 150 degrees geometry to one V(5) and one V(6) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. There are twelve 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 linear geometry to one V(3) 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(5) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the sixth F site, F(6) is bonded in a bent 150 degrees geometry to one V(5) and one V(6) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the eighth F site, F(8) is bonded in a bent 150 degrees geometry to one V(5) and one V(6) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(5) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(6) atom. In the eleventh F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the twelfth F site, F(12) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom.