V2OF5 crystallizes in the monoclinic C2 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(1), one F(2), one F(3), and two equivalent F(5) atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 24-30°. In the second V site, V(2) is bonded to one O(1), one F(4), one F(8), one F(9), and two equivalent F(6) atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 24-34°. In the third V site, V(3) is bonded to one O(2), one F(1), one F(10), one F(11), one F(2), and one F(7) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 24-34°. In the fourth V site, V(4) is bonded to one O(1), one F(10), one F(11), one F(4), one F(7), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 24-34°. There are two 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(1) and one V(3) atom. There are eleven inequivalent F sites. In the first F site, F(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the second F site, F(8) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the third F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the fourth F site, F(10) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the fifth F site, F(11) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the sixth F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the seventh F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the ninth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the tenth F site, F(5) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the eleventh F site, F(6) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.
V2OF5 crystallizes in the monoclinic C2 space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(1), one F(2), one F(3), and two equivalent F(5) atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 24-30°. The V(1)-O(2) bond length is 1.97 Å. The V(1)-F(1) bond length is 1.97 Å. The V(1)-F(2) bond length is 1.97 Å. The V(1)-F(3) bond length is 1.97 Å. There is one shorter (1.96 Å) and one longer (1.99 Å) V(1)-F(5) bond length. In the second V site, V(2) is bonded to one O(1), one F(4), one F(8), one F(9), and two equivalent F(6) atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 24-34°. The V(2)-O(1) bond length is 1.96 Å. The V(2)-F(4) bond length is 1.97 Å. The V(2)-F(8) bond length is 1.98 Å. The V(2)-F(9) bond length is 2.00 Å. There is one shorter (1.96 Å) and one longer (1.99 Å) V(2)-F(6) bond length. In the third V site, V(3) is bonded to one O(2), one F(1), one F(10), one F(11), one F(2), and one F(7) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 24-34°. The V(3)-O(2) bond length is 1.69 Å. The V(3)-F(1) bond length is 1.97 Å. The V(3)-F(10) bond length is 2.06 Å. The V(3)-F(11) bond length is 1.96 Å. The V(3)-F(2) bond length is 1.97 Å. The V(3)-F(7) bond length is 1.96 Å. In the fourth V site, V(4) is bonded to one O(1), one F(10), one F(11), one F(4), one F(7), and one F(9) atom to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 24-34°. The V(4)-O(1) bond length is 1.68 Å. The V(4)-F(10) bond length is 1.96 Å. The V(4)-F(11) bond length is 2.04 Å. The V(4)-F(4) bond length is 1.99 Å. The V(4)-F(7) bond length is 1.99 Å. The V(4)-F(9) bond length is 1.95 Å. There are two 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(1) and one V(3) atom. There are eleven inequivalent F sites. In the first F site, F(7) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the second F site, F(8) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the third F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the fourth F site, F(10) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the fifth F site, F(11) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the sixth F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the seventh F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the ninth F site, F(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the tenth F site, F(5) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the eleventh F site, F(6) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.