LiV2O5 crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(4), two equivalent O(3), and two equivalent O(5) atoms. In the second V site, V(2) is bonded in a distorted trigonal bipyramidal geometry to one O(1), one O(2), one O(3), one O(4), and one O(5) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one O(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one O(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded to two equivalent Li(1), one V(2), and two equivalent V(1) atoms to form edge-sharing OLi2V3 square pyramids.
LiV2O5 crystallizes in the orthorhombic Cmc2_1 space group. Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), two equivalent O(4), and two equivalent O(5) atoms. The Li(1)-O(1) bond length is 1.95 Å. The Li(1)-O(2) bond length is 2.36 Å. Both Li(1)-O(4) bond lengths are 2.22 Å. Both Li(1)-O(5) bond lengths are 2.18 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(4), two equivalent O(3), and two equivalent O(5) atoms. The V(1)-O(4) bond length is 1.77 Å. Both V(1)-O(3) bond lengths are 1.96 Å. Both V(1)-O(5) bond lengths are 2.05 Å. In the second V site, V(2) is bonded in a distorted trigonal bipyramidal geometry to one O(1), one O(2), one O(3), one O(4), and one O(5) atom. The V(2)-O(1) bond length is 1.95 Å. The V(2)-O(2) bond length is 1.91 Å. The V(2)-O(3) bond length is 2.01 Å. The V(2)-O(4) bond length is 2.03 Å. The V(2)-O(5) bond length is 2.19 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one O(2) atom. The O(1)-O(2) bond length is 1.42 Å. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one O(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one V(2) atom. In the fifth O site, O(5) is bonded to two equivalent Li(1), one V(2), and two equivalent V(1) atoms to form edge-sharing OLi2V3 square pyramids.