LiV3OF11 crystallizes in the triclinic P1 space group. Li(1) is bonded to one F(1), one F(11), one F(2), and one F(9) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(2)OF5 octahedra, and corners with two equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 25-61°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(10), one F(11), one F(3), and one F(8) atom to form VOF5 octahedra that share corners with two equivalent V(3)F6 octahedra, corners with two equivalent V(2)OF5 octahedra, and corners with two equivalent Li(1)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 27-39°. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), one F(4), one F(6), and one F(7) atom to form distorted VOF5 octahedra that share corners with two equivalent V(1)OF5 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-32°. In the third V site, V(3) is bonded to one F(10), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form VF6 octahedra that share corners with two equivalent V(1)OF5 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-39°. O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Li(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(2) and one V(3) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(3) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one V(2) atom. In the seventh F site, F(7) is bonded in a water-like 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(1) and one V(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the tenth F site, F(10) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the eleventh F site, F(11) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom.
LiV3OF11 crystallizes in the triclinic P1 space group. Li(1) is bonded to one F(1), one F(11), one F(2), and one F(9) atom to form distorted LiF4 trigonal pyramids that share  a cornercorner with one V(3)F6 octahedra,  a cornercorner with one V(2)OF5 octahedra, and corners with two equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 25-61°. The Li(1)-F(1) bond length is 1.94 Å. The Li(1)-F(11) bond length is 2.01 Å. The Li(1)-F(2) bond length is 1.97 Å. The Li(1)-F(9) bond length is 1.91 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(10), one F(11), one F(3), and one F(8) atom to form VOF5 octahedra that share corners with two equivalent V(3)F6 octahedra, corners with two equivalent V(2)OF5 octahedra, and corners with two equivalent Li(1)F4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 27-39°. The V(1)-O(1) bond length is 1.81 Å. The V(1)-F(1) bond length is 1.79 Å. The V(1)-F(10) bond length is 2.20 Å. The V(1)-F(11) bond length is 1.81 Å. The V(1)-F(3) bond length is 1.95 Å. The V(1)-F(8) bond length is 1.95 Å. In the second V site, V(2) is bonded to one O(1), one F(2), one F(3), one F(4), one F(6), and one F(7) atom to form distorted VOF5 octahedra that share corners with two equivalent V(1)OF5 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid, and  an edgeedge with one V(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 30-32°. The V(2)-O(1) bond length is 1.82 Å. The V(2)-F(2) bond length is 1.88 Å. The V(2)-F(3) bond length is 1.96 Å. The V(2)-F(4) bond length is 2.06 Å. The V(2)-F(6) bond length is 1.79 Å. The V(2)-F(7) bond length is 2.10 Å. In the third V site, V(3) is bonded to one F(10), one F(4), one F(5), one F(7), one F(8), and one F(9) atom to form VF6 octahedra that share corners with two equivalent V(1)OF5 octahedra,  a cornercorner with one Li(1)F4 trigonal pyramid, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 27-39°. The V(3)-F(10) bond length is 1.94 Å. The V(3)-F(4) bond length is 1.92 Å. The V(3)-F(5) bond length is 1.76 Å. The V(3)-F(7) bond length is 1.94 Å. The V(3)-F(8) bond length is 1.96 Å. The V(3)-F(9) bond length is 1.85 Å. O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are eleven inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 120 degrees geometry to one Li(1) and one V(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a water-like geometry to one V(2) and one V(3) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one V(3) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one V(2) atom. In the seventh F site, F(7) is bonded in a water-like 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(1) and one V(3) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the tenth F site, F(10) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(3) atom. In the eleventh F site, F(11) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom.