LiVF4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one F(1), one F(2), one F(4), and three equivalent F(3) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent V(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with three equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 11-35°. V(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form VF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent V(1)F6 octahedra,  an edgeedge with one V(1)F6 octahedra, and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 11-28°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded to three equivalent Li(1) and one V(1) atom to form a mixture of edge and corner-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1) and two equivalent V(1) atoms.
LiVF4 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one F(1), one F(2), one F(4), and three equivalent F(3) atoms to form distorted LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent V(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with three equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 11-35°. The Li(1)-F(1) bond length is 2.02 Å. The Li(1)-F(2) bond length is 1.89 Å. The Li(1)-F(4) bond length is 2.29 Å. There are two shorter (2.09 Å) and one longer (2.23 Å) Li(1)-F(3) bond length. V(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form VF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent V(1)F6 octahedra,  an edgeedge with one V(1)F6 octahedra, and edges with three equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 11-28°. The V(1)-F(2) bond length is 1.87 Å. The V(1)-F(3) bond length is 1.93 Å. There is one shorter (2.03 Å) and one longer (2.08 Å) V(1)-F(1) bond length. Both V(1)-F(4) bond lengths are 2.01 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the third F site, F(3) is bonded to three equivalent Li(1) and one V(1) atom to form a mixture of edge and corner-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1) and two equivalent V(1) atoms.