LiV4OF11 crystallizes in the monoclinic C2 space group. Li(1) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(2), one F(4), one F(7), and one F(8) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(11), one F(2), one F(4), one F(5), 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(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. In the second V site, V(2) is bonded to one O(1), one F(1), one F(10), one F(2), one F(3), and one F(5) atom to form VOF5 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 31-42°. In the third V site, V(3) is bonded to one F(1), one F(10), one F(3), one F(9), and two equivalent F(6) atoms to form VF6 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 31-34°. In the fourth V site, V(4) is bonded to one F(11), one F(12), one F(4), one F(8), and two equivalent F(7) atoms to form VF6 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 29-43°. O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. There are twelve inequivalent F sites. In the first F site, F(6) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. In the second F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(4) atoms. In the third F site, F(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one V(4) atom. In the fourth F site, F(9) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. In the fifth F site, F(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth F site, F(11) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the seventh F site, F(12) is bonded in a bent 150 degrees geometry to two equivalent V(4) atoms. In the eighth F site, F(1) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the ninth F site, F(2) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the tenth F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the eleventh F site, F(4) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the twelfth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom.
LiV4OF11 crystallizes in the monoclinic C2 space group. Li(1) is bonded in a 6-coordinate geometry to one O(1), one F(11), one F(2), one F(4), one F(7), and one F(8) atom. The Li(1)-O(1) bond length is 1.93 Å. The Li(1)-F(11) bond length is 2.32 Å. The Li(1)-F(2) bond length is 2.01 Å. The Li(1)-F(4) bond length is 2.43 Å. The Li(1)-F(7) bond length is 2.11 Å. The Li(1)-F(8) bond length is 1.98 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(11), one F(2), one F(4), one F(5), 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(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. The V(1)-O(1) bond length is 1.83 Å. The V(1)-F(11) bond length is 2.15 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(4) bond length is 2.10 Å. The V(1)-F(5) bond length is 1.92 Å. The V(1)-F(8) bond length is 2.16 Å. In the second V site, V(2) is bonded to one O(1), one F(1), one F(10), one F(2), one F(3), and one F(5) atom to form VOF5 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 31-42°. The V(2)-O(1) bond length is 1.92 Å. The V(2)-F(1) bond length is 1.98 Å. The V(2)-F(10) bond length is 2.00 Å. The V(2)-F(2) bond length is 2.08 Å. The V(2)-F(3) bond length is 1.98 Å. The V(2)-F(5) bond length is 2.04 Å. In the third V site, V(3) is bonded to one F(1), one F(10), one F(3), one F(9), and two equivalent F(6) atoms to form VF6 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 31-34°. The V(3)-F(1) bond length is 2.00 Å. The V(3)-F(10) bond length is 1.98 Å. The V(3)-F(3) bond length is 2.00 Å. The V(3)-F(9) bond length is 1.99 Å. There is one shorter (1.97 Å) and one longer (1.98 Å) V(3)-F(6) bond length. In the fourth V site, V(4) is bonded to one F(11), one F(12), one F(4), one F(8), and two equivalent F(7) atoms to form VF6 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 29-43°. The V(4)-F(11) bond length is 1.94 Å. The V(4)-F(12) bond length is 1.98 Å. The V(4)-F(4) bond length is 1.96 Å. The V(4)-F(8) bond length is 1.99 Å. There is one shorter (2.02 Å) and one longer (2.05 Å) V(4)-F(7) bond length. O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. There are twelve inequivalent F sites. In the first F site, F(6) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. In the second F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(4) atoms. In the third F site, F(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one V(4) atom. In the fourth F site, F(9) is bonded in a bent 150 degrees geometry to two equivalent V(3) atoms. In the fifth F site, F(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth F site, F(11) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the seventh F site, F(12) is bonded in a bent 150 degrees geometry to two equivalent V(4) atoms. In the eighth F site, F(1) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the ninth F site, F(2) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the tenth F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the eleventh F site, F(4) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(4) atom. In the twelfth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom.