LiVF4 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(4) atoms to form distorted LiF4 tetrahedra that share corners with three equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-68°. 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 four equivalent V(1)F6 octahedra, corners with three equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-35°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom.
LiVF4 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(4) atoms to form distorted LiF4 tetrahedra that share corners with three equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 52-68°. The Li(1)-F(1) bond length is 1.91 Å. The Li(1)-F(2) bond length is 2.05 Å. There is one shorter (1.95 Å) and one longer (2.04 Å) Li(1)-F(4) 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 four equivalent V(1)F6 octahedra, corners with three equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 32-35°. The V(1)-F(1) bond length is 1.90 Å. The V(1)-F(4) bond length is 1.95 Å. There is one shorter (1.99 Å) and one longer (2.06 Å) V(1)-F(2) bond length. There is one shorter (1.95 Å) and one longer (2.01 Å) V(1)-F(3) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to two equivalent V(1) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom.