LiV2OF5 is Hydrophilite-derived structured and crystallizes in the trigonal P3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form LiF6 octahedra that share corners with six equivalent V(1)OF5 octahedra and edges with three equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the second Li site, Li(2) is bonded to three equivalent O(1) and three equivalent F(3) atoms to form LiO3F3 octahedra that share corners with six equivalent V(2)OF5 octahedra and edges with three equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. In the third Li site, Li(3) is bonded to three equivalent F(4) and three equivalent F(5) atoms to form LiF6 octahedra that share corners with six equivalent V(1)OF5 octahedra and edges with three equivalent 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 two equivalent Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with six equivalent V(2)OF5 octahedra, and  an edgeedge with one Li(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. 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 two equivalent Li(2)O3F3 octahedra, corners with six equivalent V(1)OF5 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-59°. O(1) is bonded in a distorted trigonal planar geometry to one Li(2), 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 distorted 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 trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2), 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(3), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom.
LiV2OF5 is Hydrophilite-derived structured and crystallizes in the trigonal P3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form LiF6 octahedra that share corners with six equivalent V(1)OF5 octahedra and edges with three equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 47-54°. All Li(1)-F(1) bond lengths are 1.99 Å. All Li(1)-F(2) bond lengths are 2.03 Å. In the second Li site, Li(2) is bonded to three equivalent O(1) and three equivalent F(3) atoms to form LiO3F3 octahedra that share corners with six equivalent V(2)OF5 octahedra and edges with three equivalent V(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. All Li(2)-O(1) bond lengths are 2.06 Å. All Li(2)-F(3) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded to three equivalent F(4) and three equivalent F(5) atoms to form LiF6 octahedra that share corners with six equivalent V(1)OF5 octahedra and edges with three equivalent V(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. All Li(3)-F(4) bond lengths are 2.07 Å. All Li(3)-F(5) bond lengths are 2.05 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 two equivalent Li(1)F6 octahedra, corners with two equivalent Li(3)F6 octahedra, corners with six equivalent V(2)OF5 octahedra, and  an edgeedge with one Li(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 41-54°. The V(1)-O(1) bond length is 1.87 Å. The V(1)-F(1) bond length is 2.02 Å. The V(1)-F(2) bond length is 2.04 Å. The V(1)-F(3) bond length is 2.07 Å. The V(1)-F(4) bond length is 2.03 Å. The V(1)-F(5) bond length is 2.10 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 two equivalent Li(2)O3F3 octahedra, corners with six equivalent V(1)OF5 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one Li(3)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-59°. The V(2)-O(1) bond length is 1.86 Å. The V(2)-F(1) bond length is 2.06 Å. The V(2)-F(2) bond length is 2.01 Å. The V(2)-F(3) bond length is 1.99 Å. The V(2)-F(4) bond length is 2.05 Å. The V(2)-F(5) bond length is 2.12 Å. O(1) is bonded in a distorted trigonal planar geometry to one Li(2), 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 distorted 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 trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted T-shaped geometry to one Li(2), 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(3), one V(1), and one V(2) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom.