V4OF11 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(1), one F(1), one F(2), one F(4), and two equivalent F(6) atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 25-34°. In the second V site, V(2) is bonded to one F(10), one F(3), one F(5), one F(9), and two equivalent F(7) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 35-38°. In the third V site, V(3) is bonded to one O(1), one F(1), one F(11), one F(12), one F(2), and one F(8) atom to form VOF5 octahedra that share corners with three equivalent V(4)F6 octahedra and corners with three equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 25-41°. In the fourth V site, V(4) is bonded to one F(10), one F(11), one F(12), one F(3), one F(5), and one F(8) atom to form VF6 octahedra that share corners with three equivalent V(2)F6 octahedra and corners with three equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-41°. O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. There are twelve inequivalent F sites. In the first F site, F(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the second F site, F(11) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the third F site, F(12) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the fourth F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fifth F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the sixth F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the seventh F site, F(4) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the eighth F site, F(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the ninth F site, F(6) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the tenth F site, F(7) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the eleventh F site, F(8) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the twelfth F site, F(9) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.
V4OF11 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(1), one F(1), one F(2), one F(4), and two equivalent F(6) atoms to form corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 25-34°. The V(1)-O(1) bond length is 1.85 Å. The V(1)-F(1) bond length is 1.90 Å. The V(1)-F(2) bond length is 1.90 Å. The V(1)-F(4) bond length is 1.93 Å. There is one shorter (1.90 Å) and one longer (2.01 Å) V(1)-F(6) bond length. In the second V site, V(2) is bonded to one F(10), one F(3), one F(5), one F(9), and two equivalent F(7) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 35-38°. The V(2)-F(10) bond length is 1.97 Å. The V(2)-F(3) bond length is 1.92 Å. The V(2)-F(5) bond length is 1.92 Å. The V(2)-F(9) bond length is 1.93 Å. There is one shorter (1.91 Å) and one longer (1.97 Å) V(2)-F(7) bond length. In the third V site, V(3) is bonded to one O(1), one F(1), one F(11), one F(12), one F(2), and one F(8) atom to form VOF5 octahedra that share corners with three equivalent V(4)F6 octahedra and corners with three equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 25-41°. The V(3)-O(1) bond length is 1.68 Å. The V(3)-F(1) bond length is 1.97 Å. The V(3)-F(11) bond length is 1.99 Å. The V(3)-F(12) bond length is 1.94 Å. The V(3)-F(2) bond length is 1.97 Å. The V(3)-F(8) bond length is 1.94 Å. In the fourth V site, V(4) is bonded to one F(10), one F(11), one F(12), one F(3), one F(5), and one F(8) atom to form VF6 octahedra that share corners with three equivalent V(2)F6 octahedra and corners with three equivalent V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-41°. The V(4)-F(10) bond length is 1.92 Å. The V(4)-F(11) bond length is 1.95 Å. The V(4)-F(12) bond length is 1.94 Å. The V(4)-F(3) bond length is 1.94 Å. The V(4)-F(5) bond length is 1.97 Å. The V(4)-F(8) bond length is 1.94 Å. O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. There are twelve inequivalent F sites. In the first F site, F(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the second F site, F(11) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the third F site, F(12) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the fourth F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the fifth F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the sixth F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the seventh F site, F(4) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the eighth F site, F(5) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the ninth F site, F(6) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the tenth F site, F(7) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the eleventh F site, F(8) is bonded in a bent 150 degrees geometry to one V(3) and one V(4) atom. In the twelfth F site, F(9) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.