LiV2F6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with eight equivalent V(1)F6 octahedra and edges with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles are 50°. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. There are two inequivalent F sites. In the first F site, F(2) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms.
LiV2F6 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Li(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with eight equivalent V(1)F6 octahedra and edges with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles are 50°. Both Li(1)-F(2) bond lengths are 2.00 Å. All Li(1)-F(1) bond lengths are 2.03 Å. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with four equivalent Li(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra,  an edgeedge with one Li(1)F6 octahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 49-50°. Both V(1)-F(2) bond lengths are 2.02 Å. There are two shorter (1.99 Å) and two longer (2.01 Å) V(1)-F(1) bond lengths. There are two inequivalent F sites. In the first F site, F(2) is bonded in a trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms.