LiV3O8 crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form distorted corner-sharing LiO4 trigonal pyramids. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and two equivalent O(7) atoms. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(5), and two equivalent O(8) atoms. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(4), one O(6), one O(7), and two equivalent O(1) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one V(1), and two equivalent V(3) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(1) atoms. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.
LiV3O8 crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form distorted corner-sharing LiO4 trigonal pyramids. The Li(1)-O(1) bond length is 2.37 Å. The Li(1)-O(2) bond length is 1.96 Å. Both Li(1)-O(5) bond lengths are 1.93 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and two equivalent O(7) atoms. The V(1)-O(1) bond length is 2.38 Å. The V(1)-O(2) bond length is 1.68 Å. The V(1)-O(3) bond length is 2.15 Å. The V(1)-O(4) bond length is 1.73 Å. Both V(1)-O(7) bond lengths are 1.89 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(5), and two equivalent O(8) atoms. The V(2)-O(2) bond length is 2.32 Å. The V(2)-O(3) bond length is 1.67 Å. The V(2)-O(5) bond length is 1.71 Å. Both V(2)-O(8) bond lengths are 1.83 Å. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(4), one O(6), one O(7), and two equivalent O(1) atoms. The V(3)-O(4) bond length is 1.89 Å. The V(3)-O(6) bond length is 1.60 Å. The V(3)-O(7) bond length is 2.05 Å. Both V(3)-O(1) bond lengths are 1.86 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one V(1), and two equivalent V(3) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded in a linear geometry to one V(1) and one V(2) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(1) and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one V(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(1) atoms. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms.