Li3VF8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted linear geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share edges with two equivalent V(1)F6 octahedra. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share edges with two equivalent Li(2)F6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(1), and one V(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a distorted L-shaped geometry to one Li(2) and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2) and two equivalent Li(1) atoms.
Li3VF8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted linear geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms. Both Li(1)-F(1) bond lengths are 2.42 Å. Both Li(1)-F(2) bond lengths are 2.48 Å. Both Li(1)-F(4) bond lengths are 1.83 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share edges with two equivalent V(1)F6 octahedra. Both Li(2)-F(1) bond lengths are 2.11 Å. Both Li(2)-F(3) bond lengths are 2.43 Å. Both Li(2)-F(4) bond lengths are 1.85 Å. V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share edges with two equivalent Li(2)F6 octahedra. Both V(1)-F(1) bond lengths are 1.85 Å. Both V(1)-F(2) bond lengths are 1.81 Å. Both V(1)-F(3) bond lengths are 1.79 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Li(1), and one V(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Li(1) and one V(1) atom. In the third F site, F(3) is bonded in a distorted L-shaped geometry to one Li(2) and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2) and two equivalent Li(1) atoms.