Li2VO2F3 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 O(1) and two equivalent F(3) atoms. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to four equivalent O(1) and one F(2) atom. V(1) is bonded to two equivalent O(1), one F(2), one F(3), and two equivalent F(1) atoms to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedra are not tilted. O(1) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Li(2), and one V(1) atom. There are three 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 bent 150 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.
Li2VO2F3 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 O(1) and two equivalent F(3) atoms. Both Li(1)-O(1) bond lengths are 2.09 Å. There is one shorter (1.98 Å) and one longer (2.12 Å) Li(1)-F(3) bond length. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to four equivalent O(1) and one F(2) atom. There are two shorter (2.00 Å) and two longer (2.44 Å) Li(2)-O(1) bond lengths. The Li(2)-F(2) bond length is 1.88 Å. V(1) is bonded to two equivalent O(1), one F(2), one F(3), and two equivalent F(1) atoms to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedra are not tilted. Both V(1)-O(1) bond lengths are 1.68 Å. The V(1)-F(2) bond length is 1.87 Å. The V(1)-F(3) bond length is 1.97 Å. Both V(1)-F(1) bond lengths are 2.12 Å. O(1) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Li(2), and one V(1) atom. There are three 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 bent 150 degrees geometry to one Li(2) and one V(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.