LiV2O5 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with four equivalent V(2)O4 tetrahedra and edges with two equivalent Li(1)O6 octahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. In the second V site, V(2) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one V(2) atom.
LiV2O5 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with four equivalent V(2)O4 tetrahedra and edges with two equivalent Li(1)O6 octahedra. Both Li(1)-O(2) bond lengths are 2.25 Å. Both Li(1)-O(3) bond lengths are 2.00 Å. Both Li(1)-O(4) bond lengths are 2.18 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms. The V(1)-O(1) bond length is 1.90 Å. The V(1)-O(4) bond length is 2.01 Å. There is one shorter (1.65 Å) and one longer (2.37 Å) V(1)-O(2) bond length. Both V(1)-O(3) bond lengths are 1.94 Å. In the second V site, V(2) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-58°. The V(2)-O(1) bond length is 1.69 Å. The V(2)-O(4) bond length is 1.73 Å. Both V(2)-O(3) bond lengths are 1.73 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Li(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one V(2) atom.