LiV3O8 crystallizes in the monoclinic P2_1/m space group. Li(1) is bonded to one O(3), one O(7), two equivalent O(4), and two equivalent O(5) atoms to form edge-sharing LiO6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(3), one O(5), and three equivalent O(1) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(4), one O(6), one O(8), and three equivalent O(2) atoms. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(6), one O(7), and two equivalent O(8) atoms. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one V(3) and three equivalent V(2) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(2) and one V(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(3) atoms.
LiV3O8 crystallizes in the monoclinic P2_1/m space group. Li(1) is bonded to one O(3), one O(7), two equivalent O(4), and two equivalent O(5) atoms to form edge-sharing LiO6 octahedra. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-O(7) bond length is 2.04 Å. Both Li(1)-O(4) bond lengths are 2.29 Å. Both Li(1)-O(5) bond lengths are 2.26 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(3), one O(5), and three equivalent O(1) atoms. The V(1)-O(3) bond length is 1.73 Å. The V(1)-O(5) bond length is 1.63 Å. There are two shorter (1.88 Å) and one longer (2.01 Å) V(1)-O(1) bond length. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(4), one O(6), one O(8), and three equivalent O(2) atoms. The V(2)-O(4) bond length is 1.62 Å. The V(2)-O(6) bond length is 1.76 Å. The V(2)-O(8) bond length is 2.10 Å. There are two shorter (1.87 Å) and one longer (2.39 Å) V(2)-O(2) bond length. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(6), one O(7), and two equivalent O(8) atoms. The V(3)-O(2) bond length is 2.26 Å. The V(3)-O(3) bond length is 2.03 Å. The V(3)-O(6) bond length is 1.84 Å. The V(3)-O(7) bond length is 1.62 Å. Both V(3)-O(8) bond lengths are 1.87 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one V(3) and three equivalent V(2) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one V(1) atom. In the sixth O site, O(6) is bonded in a bent 120 degrees geometry to one V(2) and one V(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(3) atoms.