Li4VF8 is beta indium sulfide-derived structured and crystallizes in the monoclinic P2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. In the second Li site, Li(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form LiF6 octahedra that share edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted LiF6 octahedra that share edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. In the fourth Li site, Li(4) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. V(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, and edges with two equivalent Li(4)F6 octahedra. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one V(1) atom. In the second F site, F(2) is bonded in a see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), and one V(1) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(1) atom.
Li4VF8 is beta indium sulfide-derived structured and crystallizes in the monoclinic P2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Li(1)-F(1) bond lengths are 2.42 Å. Both Li(1)-F(2) bond lengths are 1.89 Å. Both Li(1)-F(3) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form LiF6 octahedra that share edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. Both Li(2)-F(2) bond lengths are 1.91 Å. Both Li(2)-F(3) bond lengths are 2.20 Å. Both Li(2)-F(4) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted LiF6 octahedra that share edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(4)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. Both Li(3)-F(1) bond lengths are 2.09 Å. Both Li(3)-F(2) bond lengths are 1.91 Å. Both Li(3)-F(3) bond lengths are 2.28 Å. In the fourth Li site, Li(4) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(4) atoms to form distorted LiF6 octahedra that share edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, and edges with two equivalent V(1)F6 octahedra. Both Li(4)-F(1) bond lengths are 2.31 Å. Both Li(4)-F(2) bond lengths are 1.96 Å. Both Li(4)-F(4) bond lengths are 2.13 Å. V(1) is bonded to two equivalent F(1), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(3)F6 octahedra, and edges with two equivalent Li(4)F6 octahedra. Both V(1)-F(1) bond lengths are 1.90 Å. Both V(1)-F(3) bond lengths are 1.89 Å. Both V(1)-F(4) bond lengths are 1.86 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one V(1) atom. In the second F site, F(2) is bonded in a see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom. In the third F site, F(3) is bonded to one Li(1), one Li(2), one Li(3), and one V(1) atom to form a mixture of distorted edge and corner-sharing FLi3V trigonal pyramids. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Li(4), and one V(1) atom.