LiVF4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form LiF4 tetrahedra 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 12-28°. V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form VF6 octahedra that share corners with four equivalent Li(1)F4 tetrahedra, edges with two equivalent V(1)F6 octahedra, and  an edgeedge with one Li(1)F4 tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a T-shaped geometry to one Li(1) and two equivalent V(1) atoms.
LiVF4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form LiF4 tetrahedra 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 12-28°. Both Li(1)-F(1) bond lengths are 1.83 Å. Both Li(1)-F(2) bond lengths are 2.07 Å. V(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form VF6 octahedra that share corners with four equivalent Li(1)F4 tetrahedra, edges with two equivalent V(1)F6 octahedra, and  an edgeedge with one Li(1)F4 tetrahedra. Both V(1)-F(1) bond lengths are 1.90 Å. There are two shorter (2.04 Å) and two longer (2.05 Å) V(1)-F(2) bond lengths. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a T-shaped geometry to one Li(1) and two equivalent V(1) atoms.