Li4TiV3O8 is alpha Po-derived structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. In the second Li site, Li(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. In the second V site, V(2) 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 six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(2), one Ti(1), and two equivalent V(2) atoms to form OLi3TiV2 octahedra that share corners with six equivalent O(1)Li3TiV2 octahedra, edges with four equivalent O(2)Li3TiV2 octahedra, edges with four equivalent O(3)Li3TiV2 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one V(1), and one V(2) atom to form OLi3TiV2 octahedra that share corners with six equivalent O(3)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(3)Li3TiV2 octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one V(1), and one V(2) atom to form OLi3TiV2 octahedra that share corners with six equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(3)Li3TiV2 octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share corners with six equivalent O(4)Li3V3 octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, edges with four equivalent O(2)Li3TiV2 octahedra, and edges with four equivalent O(3)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li4TiV3O8 is alpha Po-derived structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. Both Li(1)-O(2) bond lengths are 2.13 Å. Both Li(1)-O(3) bond lengths are 2.14 Å. Both Li(1)-O(4) bond lengths are 2.15 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. The Li(2)-O(2) bond length is 2.14 Å. The Li(2)-O(3) bond length is 2.12 Å. There is one shorter (2.12 Å) and one longer (2.15 Å) Li(2)-O(1) bond length. There is one shorter (2.10 Å) and one longer (2.21 Å) Li(2)-O(4) bond length. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Both Li(3)-O(1) bond lengths are 2.16 Å. Both Li(3)-O(2) bond lengths are 2.14 Å. Both Li(3)-O(3) bond lengths are 2.17 Å. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Both Ti(1)-O(1) bond lengths are 2.03 Å. Both Ti(1)-O(2) bond lengths are 2.03 Å. Both Ti(1)-O(3) bond lengths are 2.04 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. Both V(1)-O(2) bond lengths are 2.06 Å. Both V(1)-O(3) bond lengths are 2.06 Å. Both V(1)-O(4) bond lengths are 2.04 Å. In the second V site, V(2) 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 six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. The V(2)-O(2) bond length is 2.06 Å. The V(2)-O(3) bond length is 2.06 Å. Both V(2)-O(1) bond lengths are 2.06 Å. There is one shorter (2.03 Å) and one longer (2.04 Å) V(2)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(2), one Ti(1), and two equivalent V(2) atoms to form OLi3TiV2 octahedra that share corners with six equivalent O(1)Li3TiV2 octahedra, edges with four equivalent O(2)Li3TiV2 octahedra, edges with four equivalent O(3)Li3TiV2 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one V(1), and one V(2) atom to form OLi3TiV2 octahedra that share corners with six equivalent O(3)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(3)Li3TiV2 octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one V(1), and one V(2) atom to form OLi3TiV2 octahedra that share corners with six equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(3)Li3TiV2 octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(4)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share corners with six equivalent O(4)Li3V3 octahedra, edges with four equivalent O(1)Li3TiV2 octahedra, edges with four equivalent O(2)Li3TiV2 octahedra, and edges with four equivalent O(3)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.