LiVF4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 6-coordinate geometry to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms. V(1) is bonded to one F(4), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing VF7 pentagonal bipyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar 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 in a 6-coordinate geometry to one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms. The Li(1)-F(1) bond length is 2.35 Å. The Li(1)-F(2) bond length is 2.06 Å. There is one shorter (2.29 Å) and one longer (2.30 Å) Li(1)-F(3) bond length. There is one shorter (1.93 Å) and one longer (1.98 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 edge-sharing VF7 pentagonal bipyramids. The V(1)-F(4) bond length is 1.96 Å. There is one shorter (2.03 Å) and one longer (2.04 Å) V(1)-F(1) bond length. There is one shorter (2.05 Å) and one longer (2.09 Å) V(1)-F(2) bond length. There is one shorter (2.08 Å) and one longer (2.09 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 non-coplanar 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.