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(10), one F(2), one F(3), and one F(6) atom to form VOF5 octahedra that share corners with three equivalent V(3)F6 octahedra and corners with three equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 23-34°. In the second V site, V(2) is bonded to one O(1), one F(1), one F(11), one F(2), one F(7), and one F(9) 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 23-34°. In the third V site, V(3) is bonded to one F(10), one F(3), one F(6), one F(8), and two equivalent F(4) atoms to form VF6 octahedra that share corners with three equivalent V(3)F6 octahedra and corners with three equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-31°. In the fourth V site, V(4) is bonded to one F(11), one F(12), one F(7), one F(9), and two equivalent F(5) atoms to form VF6 octahedra that share corners with three equivalent V(4)F6 octahedra and corners with three equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 30-32°. O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) 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(1) and one V(3) atom. In the second F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the third F site, F(12) is bonded in a bent 150 degrees geometry to two equivalent V(4) atoms. In the fourth F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the seventh F site, F(4) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. In the eighth F site, F(5) is bonded in a bent 150 degrees geometry to two equivalent V(4) atoms. In the ninth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the tenth F site, F(7) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the eleventh F site, F(8) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. In the twelfth F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom.
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(10), one F(2), one F(3), and one F(6) atom to form VOF5 octahedra that share corners with three equivalent V(3)F6 octahedra and corners with three equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 23-34°. The V(1)-O(1) bond length is 1.71 Å. The V(1)-F(1) bond length is 1.96 Å. The V(1)-F(10) bond length is 2.00 Å. The V(1)-F(2) bond length is 1.97 Å. The V(1)-F(3) bond length is 1.97 Å. The V(1)-F(6) bond length is 1.97 Å. In the second V site, V(2) is bonded to one O(1), one F(1), one F(11), one F(2), one F(7), and one F(9) 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 23-34°. The V(2)-O(1) bond length is 1.95 Å. The V(2)-F(1) bond length is 2.00 Å. The V(2)-F(11) bond length is 1.98 Å. The V(2)-F(2) bond length is 1.97 Å. The V(2)-F(7) bond length is 1.97 Å. The V(2)-F(9) bond length is 1.98 Å. In the third V site, V(3) is bonded to one F(10), one F(3), one F(6), one F(8), and two equivalent F(4) atoms to form VF6 octahedra that share corners with three equivalent V(3)F6 octahedra and corners with three equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-31°. The V(3)-F(10) bond length is 2.01 Å. The V(3)-F(3) bond length is 1.98 Å. The V(3)-F(6) bond length is 1.98 Å. The V(3)-F(8) bond length is 1.98 Å. There is one shorter (1.95 Å) and one longer (1.98 Å) V(3)-F(4) bond length. In the fourth V site, V(4) is bonded to one F(11), one F(12), one F(7), one F(9), and two equivalent F(5) atoms to form VF6 octahedra that share corners with three equivalent V(4)F6 octahedra and corners with three equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 30-32°. The V(4)-F(11) bond length is 1.97 Å. The V(4)-F(12) bond length is 1.98 Å. The V(4)-F(7) bond length is 1.98 Å. The V(4)-F(9) bond length is 1.97 Å. There is one shorter (1.96 Å) and one longer (1.97 Å) V(4)-F(5) bond length. O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) 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(1) and one V(3) atom. In the second F site, F(11) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the third F site, F(12) is bonded in a bent 150 degrees geometry to two equivalent V(4) atoms. In the fourth F site, F(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the seventh F site, F(4) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. In the eighth F site, F(5) is bonded in a bent 150 degrees geometry to two equivalent V(4) atoms. In the ninth F site, F(6) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the tenth F site, F(7) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the eleventh F site, F(8) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. In the twelfth F site, F(9) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom.