LiVF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(2), one F(4), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with five equivalent V(1)F6 octahedra and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-58°. V(1) is bonded to one F(1), one F(4), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with five equivalent Li(1)F4 tetrahedra and edges with two equivalent V(1)F6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a water-like geometry to two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom.
LiVF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(2), one F(4), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with five equivalent V(1)F6 octahedra and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-58°. The Li(1)-F(2) bond length is 1.93 Å. The Li(1)-F(4) bond length is 1.85 Å. There is one shorter (1.95 Å) and one longer (1.96 Å) Li(1)-F(1) bond length. V(1) is bonded to one F(1), one F(4), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with five equivalent Li(1)F4 tetrahedra and edges with two equivalent V(1)F6 octahedra. The V(1)-F(1) bond length is 1.96 Å. The V(1)-F(4) bond length is 1.88 Å. There is one shorter (2.06 Å) and one longer (2.09 Å) V(1)-F(2) bond length. There is one shorter (1.96 Å) and one longer (2.03 Å) V(1)-F(3) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a water-like geometry to two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(1) atom.