Li2V4O5F8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a 6-coordinate geometry to one O(1), one F(1), two equivalent F(2), and two equivalent F(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), three equivalent O(2), one F(1), and one F(4) atom to form VO4F2 octahedra that share  a cornercorner with one V(2)O3F3 octahedra, corners with three equivalent V(1)O4F2 octahedra, and edges with two equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-28°. In the second V site, V(2) is bonded to three equivalent O(1), one F(2), one F(3), and one F(4) atom to form VO3F3 octahedra that share  a cornercorner with one V(1)O4F2 octahedra, corners with two equivalent V(2)O3F3 octahedra, and edges with two equivalent V(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 3-22°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent V(1) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent V(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to one V(1) and one V(2) atom.
Li2V4O5F8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a 6-coordinate geometry to one O(1), one F(1), two equivalent F(2), and two equivalent F(3) atoms. The Li(1)-O(1) bond length is 2.43 Å. The Li(1)-F(1) bond length is 1.89 Å. There is one shorter (1.86 Å) and one longer (2.45 Å) Li(1)-F(2) bond length. Both Li(1)-F(3) bond lengths are 1.94 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), three equivalent O(2), one F(1), and one F(4) atom to form VO4F2 octahedra that share  a cornercorner with one V(2)O3F3 octahedra, corners with three equivalent V(1)O4F2 octahedra, and edges with two equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 0-28°. The V(1)-O(3) bond length is 1.81 Å. There are two shorter (1.90 Å) and one longer (2.15 Å) V(1)-O(2) bond length. The V(1)-F(1) bond length is 1.86 Å. The V(1)-F(4) bond length is 2.13 Å. In the second V site, V(2) is bonded to three equivalent O(1), one F(2), one F(3), and one F(4) atom to form VO3F3 octahedra that share  a cornercorner with one V(1)O4F2 octahedra, corners with two equivalent V(2)O3F3 octahedra, and edges with two equivalent V(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 3-22°. There are two shorter (1.88 Å) and one longer (2.12 Å) V(2)-O(1) bond length. The V(2)-F(2) bond length is 1.88 Å. The V(2)-F(3) bond length is 1.93 Å. The V(2)-F(4) bond length is 1.89 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing OLiV3 trigonal pyramids. In the second O site, O(2) is bonded in a distorted T-shaped geometry to three equivalent V(1) atoms. In the third O site, O(3) is bonded in a linear geometry to two equivalent V(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to one Li(1) and one V(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(2) atom. In the third F site, F(3) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a linear geometry to one V(1) and one V(2) atom.