Li2V2O5F2 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one F(2), and two equivalent F(1) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one F(1), and one F(2) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), two equivalent O(3), and one F(2) atom to form distorted corner-sharing VO5F octahedra. The corner-sharing octahedral tilt angles are 43°. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one F(2) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Li(2) and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(2) and two equivalent Li(1) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(2) atom.
Li2V2O5F2 crystallizes in the monoclinic Cc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one F(2), and two equivalent F(1) atoms. The Li(1)-O(1) bond length is 2.20 Å. The Li(1)-F(2) bond length is 2.43 Å. Both Li(1)-F(1) bond lengths are 1.88 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one F(1), and one F(2) atom. The Li(2)-O(1) bond length is 2.30 Å. The Li(2)-O(3) bond length is 2.23 Å. The Li(2)-O(4) bond length is 2.02 Å. The Li(2)-F(1) bond length is 1.88 Å. The Li(2)-F(2) bond length is 2.11 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), two equivalent O(3), and one F(2) atom to form distorted corner-sharing VO5F octahedra. The corner-sharing octahedral tilt angles are 43°. The V(1)-O(1) bond length is 2.11 Å. The V(1)-O(2) bond length is 1.74 Å. The V(1)-O(5) bond length is 1.74 Å. There is one shorter (1.80 Å) and one longer (1.89 Å) V(1)-O(3) bond length. The V(1)-F(2) bond length is 2.33 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), one O(5), and one F(2) atom. The V(2)-O(1) bond length is 1.75 Å. The V(2)-O(2) bond length is 1.90 Å. The V(2)-O(4) bond length is 1.65 Å. The V(2)-O(5) bond length is 1.96 Å. The V(2)-F(2) bond length is 1.96 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one Li(2) and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Li(2) and two equivalent Li(1) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(2) atom.