LiVF4 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with six equivalent V(1)F7 pentagonal bipyramids, edges with two equivalent Li(1)F6 octahedra, and edges with two equivalent V(1)F7 pentagonal bipyramids. V(1) is bonded to one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF7 pentagonal bipyramids that share corners with six equivalent Li(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with three equivalent V(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-64°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. 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 to two equivalent Li(1) and two equivalent V(1) atoms to form edge-sharing FLi2V2 tetrahedra. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one V(1) atom.
LiVF4 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share corners with six equivalent V(1)F7 pentagonal bipyramids, edges with two equivalent Li(1)F6 octahedra, and edges with two equivalent V(1)F7 pentagonal bipyramids. The Li(1)-F(1) bond length is 2.06 Å. The Li(1)-F(2) bond length is 2.07 Å. There is one shorter (2.23 Å) and one longer (2.33 Å) Li(1)-F(3) bond length. There is one shorter (1.96 Å) and one longer (1.97 Å) Li(1)-F(4) bond length. V(1) is bonded to one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF7 pentagonal bipyramids that share corners with six equivalent Li(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and edges with three equivalent V(1)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-64°. The V(1)-F(4) bond length is 1.95 Å. There is one shorter (2.03 Å) and one longer (2.07 Å) V(1)-F(1) bond length. There is one shorter (2.03 Å) and one longer (2.07 Å) V(1)-F(2) bond length. There is one shorter (2.08 Å) and one longer (2.11 Å) V(1)-F(3) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent V(1) atoms. 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 to two equivalent Li(1) and two equivalent V(1) atoms to form edge-sharing FLi2V2 tetrahedra. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one V(1) atom.