LiV2OF5 is Hydrophilite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(10), one F(3), one F(4), and one F(9) atom to form LiOF5 octahedra that share corners with four equivalent V(3)OF5 octahedra, corners with four equivalent V(4)OF5 octahedra,  an edgeedge with one V(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. In the second Li site, Li(2) is bonded to one O(2), one F(2), one F(5), one F(6), one F(7), and one F(8) atom to form LiOF5 octahedra that share corners with four equivalent V(1)OF5 octahedra, corners with four equivalent V(2)OF5 octahedra,  an edgeedge with one V(3)OF5 octahedra, and  an edgeedge with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(1), one F(10), one F(2), one F(5), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent Li(2)OF5 octahedra, corners with four equivalent V(3)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-58°. In the second V site, V(2) is bonded to one O(1), one F(2), one F(6), one F(7), one F(8), and one F(9) atom to form VOF5 octahedra that share corners with four equivalent Li(2)OF5 octahedra, corners with four equivalent V(4)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-52°. In the third V site, V(3) is bonded to one O(2), one F(1), one F(10), one F(3), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with four equivalent Li(1)OF5 octahedra, corners with four equivalent V(1)OF5 octahedra,  an edgeedge with one Li(2)OF5 octahedra, and  an edgeedge with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-52°. In the fourth V site, V(4) is bonded to one O(1), one F(3), one F(4), one F(6), one F(7), and one F(9) atom to form VOF5 octahedra that share corners with four equivalent Li(1)OF5 octahedra, corners with four equivalent V(2)OF5 octahedra,  an edgeedge with one Li(2)OF5 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-58°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(3) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one V(4) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom.
LiV2OF5 is Hydrophilite-derived structured and crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(10), one F(3), one F(4), and one F(9) atom to form LiOF5 octahedra that share corners with four equivalent V(3)OF5 octahedra, corners with four equivalent V(4)OF5 octahedra,  an edgeedge with one V(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. The Li(1)-O(1) bond length is 2.25 Å. The Li(1)-F(1) bond length is 2.05 Å. The Li(1)-F(10) bond length is 2.07 Å. The Li(1)-F(3) bond length is 2.08 Å. The Li(1)-F(4) bond length is 2.08 Å. The Li(1)-F(9) bond length is 2.12 Å. In the second Li site, Li(2) is bonded to one O(2), one F(2), one F(5), one F(6), one F(7), and one F(8) atom to form LiOF5 octahedra that share corners with four equivalent V(1)OF5 octahedra, corners with four equivalent V(2)OF5 octahedra,  an edgeedge with one V(3)OF5 octahedra, and  an edgeedge with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-58°. The Li(2)-O(2) bond length is 2.24 Å. The Li(2)-F(2) bond length is 2.08 Å. The Li(2)-F(5) bond length is 2.13 Å. The Li(2)-F(6) bond length is 2.06 Å. The Li(2)-F(7) bond length is 2.06 Å. The Li(2)-F(8) bond length is 2.08 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one F(1), one F(10), one F(2), one F(5), and one F(8) atom to form VOF5 octahedra that share corners with four equivalent Li(2)OF5 octahedra, corners with four equivalent V(3)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-58°. The V(1)-O(2) bond length is 1.82 Å. The V(1)-F(1) bond length is 2.04 Å. The V(1)-F(10) bond length is 2.04 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(5) bond length is 2.10 Å. The V(1)-F(8) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(1), one F(2), one F(6), one F(7), one F(8), and one F(9) atom to form VOF5 octahedra that share corners with four equivalent Li(2)OF5 octahedra, corners with four equivalent V(4)OF5 octahedra,  an edgeedge with one Li(1)OF5 octahedra, and  an edgeedge with one V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-52°. The V(2)-O(1) bond length is 1.82 Å. The V(2)-F(2) bond length is 2.08 Å. The V(2)-F(6) bond length is 2.03 Å. The V(2)-F(7) bond length is 2.03 Å. The V(2)-F(8) bond length is 2.09 Å. The V(2)-F(9) bond length is 2.04 Å. In the third V site, V(3) is bonded to one O(2), one F(1), one F(10), one F(3), one F(4), and one F(5) atom to form VOF5 octahedra that share corners with four equivalent Li(1)OF5 octahedra, corners with four equivalent V(1)OF5 octahedra,  an edgeedge with one Li(2)OF5 octahedra, and  an edgeedge with one V(4)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-52°. The V(3)-O(2) bond length is 1.83 Å. The V(3)-F(1) bond length is 2.04 Å. The V(3)-F(10) bond length is 2.03 Å. The V(3)-F(3) bond length is 2.09 Å. The V(3)-F(4) bond length is 2.08 Å. The V(3)-F(5) bond length is 2.03 Å. In the fourth V site, V(4) is bonded to one O(1), one F(3), one F(4), one F(6), one F(7), and one F(9) atom to form VOF5 octahedra that share corners with four equivalent Li(1)OF5 octahedra, corners with four equivalent V(2)OF5 octahedra,  an edgeedge with one Li(2)OF5 octahedra, and  an edgeedge with one V(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 36-58°. The V(4)-O(1) bond length is 1.82 Å. The V(4)-F(3) bond length is 2.04 Å. The V(4)-F(4) bond length is 2.03 Å. The V(4)-F(6) bond length is 2.04 Å. The V(4)-F(7) bond length is 2.04 Å. The V(4)-F(9) bond length is 2.10 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one V(3) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one V(4) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one V(4) atom. In the fifth F site, F(5) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one V(3) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(2), and one V(4) atom. In the eighth F site, F(8) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(2) atom. In the ninth F site, F(9) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one V(4) atom. In the tenth F site, F(10) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(3) atom.