Li2V2O5F2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one F(1), and one F(2) atom to form distorted LiO2F2 tetrahedra that share  a cornercorner with one V(1)O4F trigonal bipyramid and corners with four equivalent V(2)O4F trigonal bipyramids. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(3), one O(5), two equivalent O(1), and one F(1) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), two equivalent O(1), and one F(1) atom to form distorted VO4F trigonal bipyramids that share  a cornercorner with one Li(1)O2F2 tetrahedra,  a cornercorner with one V(2)O4F trigonal bipyramid, and  an edgeedge with one V(1)O4F trigonal bipyramid. In the second V site, V(2) is bonded to one O(2), one O(3), two equivalent O(4), and one F(2) atom to form VO4F trigonal bipyramids that share corners with four equivalent Li(1)O2F2 tetrahedra,  a cornercorner with one V(1)O4F trigonal bipyramid, and  an edgeedge with one V(2)O4F trigonal bipyramid. There are five inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Li(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), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a linear geometry to one Li(2) and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(2) atom.
Li2V2O5F2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one F(1), and one F(2) atom to form distorted LiO2F2 tetrahedra that share  a cornercorner with one V(1)O4F trigonal bipyramid and corners with four equivalent V(2)O4F trigonal bipyramids. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(4) bond length is 2.08 Å. The Li(1)-F(1) bond length is 2.03 Å. The Li(1)-F(2) bond length is 1.89 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(3), one O(5), two equivalent O(1), and one F(1) atom. The Li(2)-O(3) bond length is 2.09 Å. The Li(2)-O(5) bond length is 2.03 Å. There is one shorter (2.07 Å) and one longer (2.35 Å) Li(2)-O(1) bond length. The Li(2)-F(1) bond length is 1.99 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(5), two equivalent O(1), and one F(1) atom to form distorted VO4F trigonal bipyramids that share  a cornercorner with one Li(1)O2F2 tetrahedra,  a cornercorner with one V(2)O4F trigonal bipyramid, and  an edgeedge with one V(1)O4F trigonal bipyramid. The V(1)-O(3) bond length is 1.82 Å. The V(1)-O(5) bond length is 1.64 Å. There is one shorter (1.83 Å) and one longer (1.94 Å) V(1)-O(1) bond length. The V(1)-F(1) bond length is 1.94 Å. In the second V site, V(2) is bonded to one O(2), one O(3), two equivalent O(4), and one F(2) atom to form VO4F trigonal bipyramids that share corners with four equivalent Li(1)O2F2 tetrahedra,  a cornercorner with one V(1)O4F trigonal bipyramid, and  an edgeedge with one V(2)O4F trigonal bipyramid. The V(2)-O(2) bond length is 1.65 Å. The V(2)-O(3) bond length is 1.87 Å. There is one shorter (1.78 Å) and one longer (1.98 Å) V(2)-O(4) bond length. The V(2)-F(2) bond length is 1.87 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Li(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), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a linear geometry to one Li(2) and one V(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Li(1) and one V(2) atom.