LiV2OF5 is Hydrophilite-derived structured and crystallizes in the monoclinic Pc space group. Li(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) 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(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(2), 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(2)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 42-54°. In the second V site, V(2) is bonded to one O(1), one F(1), one F(2), 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(1)OF5 octahedra, and  an edgeedge with one V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-52°. O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1), 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(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom.
LiV2OF5 is Hydrophilite-derived structured and crystallizes in the monoclinic Pc space group. Li(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) 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(1)OF5 octahedra, and  an edgeedge with one V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Li(1)-O(1) bond length is 2.10 Å. The Li(1)-F(1) bond length is 2.05 Å. The Li(1)-F(2) bond length is 2.09 Å. The Li(1)-F(3) bond length is 2.07 Å. The Li(1)-F(4) bond length is 2.14 Å. The Li(1)-F(5) bond length is 2.07 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one F(1), one F(2), 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(2)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 42-54°. The V(1)-O(1) bond length is 1.86 Å. The V(1)-F(1) bond length is 2.01 Å. The V(1)-F(2) bond length is 2.07 Å. The V(1)-F(3) bond length is 2.06 Å. The V(1)-F(4) bond length is 2.04 Å. The V(1)-F(5) bond length is 2.04 Å. In the second V site, V(2) is bonded to one O(1), one F(1), one F(2), 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(1)OF5 octahedra, and  an edgeedge with one V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 42-52°. The V(2)-O(1) bond length is 1.85 Å. The V(2)-F(1) bond length is 2.08 Å. The V(2)-F(2) bond length is 2.06 Å. The V(2)-F(3) bond length is 2.01 Å. The V(2)-F(4) bond length is 2.01 Å. The V(2)-F(5) bond length is 2.07 Å. O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1), 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(1), and one V(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(2) atom.