Li5V4O8 crystallizes in the trigonal R3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(4) atoms. In the third Li site, Li(3) is bonded to one O(3) and three equivalent O(4) atoms to form LiO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-59°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. There are four inequivalent O sites. In the first O site, O(4) is bonded in a 7-coordinate geometry to one Li(2), one Li(3), two equivalent Li(1), one V(2), and two equivalent V(1) atoms. In the second O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(2), and two equivalent V(1) atoms to form edge-sharing OLi3V3 octahedra. In the third O site, O(2) is bonded to three equivalent Li(1) and three equivalent V(1) atoms to form edge-sharing OLi3V3 octahedra. In the fourth O site, O(3) is bonded in a 7-coordinate geometry to one Li(3), three equivalent Li(1), and three equivalent V(1) atoms.
Li5V4O8 crystallizes in the trigonal R3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms. The Li(1)-O(2) bond length is 2.01 Å. The Li(1)-O(3) bond length is 2.34 Å. Both Li(1)-O(1) bond lengths are 2.05 Å. Both Li(1)-O(4) bond lengths are 2.43 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(4) atoms. All Li(2)-O(1) bond lengths are 2.02 Å. All Li(2)-O(4) bond lengths are 2.29 Å. In the third Li site, Li(3) is bonded to one O(3) and three equivalent O(4) atoms to form LiO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-59°. The Li(3)-O(3) bond length is 1.89 Å. All Li(3)-O(4) bond lengths are 1.94 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(1)-O(2) bond length is 2.12 Å. The V(1)-O(3) bond length is 2.13 Å. Both V(1)-O(1) bond lengths are 2.07 Å. Both V(1)-O(4) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to three equivalent O(1) and three equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. All V(2)-O(1) bond lengths are 2.15 Å. All V(2)-O(4) bond lengths are 2.15 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded in a 7-coordinate geometry to one Li(2), one Li(3), two equivalent Li(1), one V(2), and two equivalent V(1) atoms. In the second O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(2), and two equivalent V(1) atoms to form edge-sharing OLi3V3 octahedra. In the third O site, O(2) is bonded to three equivalent Li(1) and three equivalent V(1) atoms to form edge-sharing OLi3V3 octahedra. In the fourth O site, O(3) is bonded in a 7-coordinate geometry to one Li(3), three equivalent Li(1), and three equivalent V(1) atoms.