LiVF4 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with six equivalent V(1)F6 octahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom.
LiVF4 is Hydrophilite-derived structured and crystallizes in the orthorhombic Pbcn space group. Li(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form LiF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with six equivalent V(1)F6 octahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. Both Li(1)-F(1) bond lengths are 2.12 Å. There are two shorter (2.12 Å) and two longer (2.16 Å) Li(1)-F(2) bond lengths. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with six equivalent Li(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. Both V(1)-F(2) bond lengths are 1.90 Å. There are two shorter (2.01 Å) and two longer (2.05 Å) V(1)-F(1) bond lengths. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom.