LiVF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 5-coordinate geometry to one F(3), two equivalent F(1), and two equivalent F(2) atoms. V(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form distorted edge-sharing VF6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing FLi2V2 trigonal pyramids. In the second F site, F(2) is bonded in a trigonal non-coplanar geometry to two equivalent Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a water-like geometry to two equivalent V(1) atoms.
LiVF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a 5-coordinate geometry to one F(3), two equivalent F(1), and two equivalent F(2) atoms. The Li(1)-F(3) bond length is 1.88 Å. There is one shorter (2.11 Å) and one longer (2.43 Å) Li(1)-F(1) bond length. There is one shorter (1.95 Å) and one longer (2.09 Å) Li(1)-F(2) 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 distorted edge-sharing VF6 octahedra. The V(1)-F(2) bond length is 1.95 Å. The V(1)-F(3) bond length is 1.86 Å. There is one shorter (2.02 Å) and one longer (2.14 Å) V(1)-F(1) bond length. There is one shorter (1.95 Å) and one longer (2.06 Å) V(1)-F(4) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing FLi2V2 trigonal pyramids. In the second F site, F(2) is bonded in a trigonal non-coplanar geometry to two equivalent Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the fourth F site, F(4) is bonded in a water-like geometry to two equivalent V(1) atoms.