Li2VF4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one F(1), one F(2), and one F(3) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(4), two equivalent F(2), and two equivalent F(3) atoms. V(1) is bonded to one F(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form edge-sharing VF6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted edge-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(2) and two equivalent V(1) atoms.
Li2VF4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one F(1), one F(2), and one F(3) atom. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(2) bond length is 1.93 Å. The Li(1)-F(3) bond length is 1.87 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(4), two equivalent F(2), and two equivalent F(3) atoms. The Li(2)-F(4) bond length is 1.93 Å. There is one shorter (1.96 Å) and one longer (2.33 Å) Li(2)-F(2) bond length. There is one shorter (1.90 Å) and one longer (2.31 Å) Li(2)-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 edge-sharing VF6 octahedra. The V(1)-F(2) bond length is 2.12 Å. The V(1)-F(3) bond length is 2.09 Å. There is one shorter (2.14 Å) and one longer (2.17 Å) V(1)-F(1) bond length. Both V(1)-F(4) bond lengths are 2.11 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the third F site, F(3) is bonded to one Li(1), two equivalent Li(2), and one V(1) atom to form distorted edge-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded in a trigonal non-coplanar geometry to one Li(2) and two equivalent V(1) atoms.