Li2VF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent F(3) and two equivalent F(4) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2) and four equivalent F(3) atoms. V(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedra are not tilted. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one 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 a mixture of distorted corner and edge-sharing FLi3V tetrahedra. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.
Li2VF5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent F(3) and two equivalent F(4) atoms. Both Li(1)-F(3) bond lengths are 1.94 Å. There is one shorter (1.94 Å) and one longer (2.40 Å) Li(1)-F(4) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one F(2) and four equivalent F(3) atoms. The Li(2)-F(2) bond length is 1.86 Å. There are two shorter (2.04 Å) and two longer (2.16 Å) Li(2)-F(3) bond lengths. V(1) is bonded to one F(2), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedra are not tilted. The V(1)-F(2) bond length is 1.91 Å. The V(1)-F(4) bond length is 1.97 Å. Both V(1)-F(1) bond lengths are 2.00 Å. Both V(1)-F(3) bond lengths are 1.99 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to one 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 a mixture of distorted corner and edge-sharing FLi3V tetrahedra. In the fourth F site, F(4) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.