LiVF3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with two equivalent V(2)F6 octahedra, corners with three equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 21-62°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, edges with two equivalent V(1)F6 octahedra, and edges with three equivalent V(2)F6 octahedra. In the second V site, V(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted VF6 octahedra that share corners with four equivalent Li(1)F4 tetrahedra, edges with three equivalent V(1)F6 octahedra, and edges with two equivalent Li(1)F4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FLiV3 tetrahedra. In the second F site, F(2) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom.
LiVF3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to one F(1), one F(2), and two equivalent F(3) atoms to form LiF4 tetrahedra that share corners with two equivalent V(2)F6 octahedra, corners with three equivalent V(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, and  an edgeedge with one V(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 21-62°. The Li(1)-F(1) bond length is 1.99 Å. The Li(1)-F(2) bond length is 1.92 Å. There is one shorter (1.84 Å) and one longer (1.91 Å) Li(1)-F(3) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, edges with two equivalent V(1)F6 octahedra, and edges with three equivalent V(2)F6 octahedra. Both V(1)-F(2) bond lengths are 2.07 Å. All V(1)-F(1) bond lengths are 2.19 Å. In the second V site, V(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted VF6 octahedra that share corners with four equivalent Li(1)F4 tetrahedra, edges with three equivalent V(1)F6 octahedra, and edges with two equivalent Li(1)F4 tetrahedra. Both V(2)-F(1) bond lengths are 2.26 Å. Both V(2)-F(2) bond lengths are 2.13 Å. Both V(2)-F(3) bond lengths are 2.07 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one V(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FLiV3 tetrahedra. In the second F site, F(2) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom.