LiVF6 crystallizes in the tetragonal P4_2nm space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-40°. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with four equivalent Li(1)F6 octahedra and  an edgeedge with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-40°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.
LiVF6 crystallizes in the tetragonal P4_2nm space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with four equivalent V(1)F6 octahedra and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-40°. Both Li(1)-F(1) bond lengths are 2.14 Å. Both Li(1)-F(2) bond lengths are 2.08 Å. Both Li(1)-F(3) bond lengths are 2.03 Å. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with four equivalent Li(1)F6 octahedra and  an edgeedge with one Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 35-40°. Both V(1)-F(1) bond lengths are 1.82 Å. Both V(1)-F(2) bond lengths are 1.82 Å. Both V(1)-F(3) bond lengths are 1.82 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom.