Li4Ti5V3O16 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-62°. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Ti(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-66°. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-66°. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Ti(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra, and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-64°. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-53°. In the second Ti site, Ti(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. In the third Ti site, Ti(3) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. In the fourth Ti site, Ti(4) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Ti(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-52°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(2), one Ti(3), and one V(2) atom. In the second O site, O(2) is bonded to one Li(4), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of distorted edge and corner-sharing OLiTi3 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one V(1) atom. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Ti(1), and one V(1) atom to form OLiTi2V tetrahedra that share corners with four equivalent O(6)LiTi2V tetrahedra and corners with two equivalent O(2)LiTi3 trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), one Ti(3), and two equivalent V(2) atoms to form corner-sharing OLiTiV2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one Ti(1), one Ti(2), and one V(1) atom to form distorted OLiTi2V tetrahedra that share  a cornercorner with one O(6)LiTi2V tetrahedra, corners with two equivalent O(4)LiTi2V tetrahedra,  a cornercorner with one O(2)LiTi3 trigonal pyramid,  an edgeedge with one O(6)LiTi2V tetrahedra, and  an edgeedge with one O(2)LiTi3 trigonal pyramid. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(4), and two equivalent Ti(1) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(2), and two equivalent V(2) atoms. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Ti(3), one Ti(4), and one V(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(3), and two equivalent V(2) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one Ti(4), and one V(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one Ti(4), and two equivalent V(2) atoms to form corner-sharing OLiTiV2 tetrahedra.
Li4Ti5V3O16 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-62°. The Li(1)-O(12) bond length is 2.00 Å. The Li(1)-O(3) bond length is 1.98 Å. Both Li(1)-O(9) bond lengths are 1.98 Å. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Ti(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Ti(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-66°. The Li(2)-O(5) bond length is 1.82 Å. The Li(2)-O(7) bond length is 2.02 Å. Both Li(2)-O(11) bond lengths are 1.99 Å. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra,  an edgeedge with one Ti(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-66°. The Li(3)-O(4) bond length is 1.82 Å. The Li(3)-O(8) bond length is 2.01 Å. Both Li(3)-O(1) bond lengths are 1.99 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Ti(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra, and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-64°. The Li(4)-O(10) bond length is 1.99 Å. The Li(4)-O(2) bond length is 2.01 Å. Both Li(4)-O(6) bond lengths are 1.99 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-53°. The Ti(1)-O(11) bond length is 2.18 Å. The Ti(1)-O(2) bond length is 1.98 Å. The Ti(1)-O(3) bond length is 1.96 Å. The Ti(1)-O(4) bond length is 1.96 Å. The Ti(1)-O(6) bond length is 1.89 Å. The Ti(1)-O(7) bond length is 2.07 Å. In the second Ti site, Ti(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted TiO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. The Ti(2)-O(2) bond length is 2.23 Å. The Ti(2)-O(8) bond length is 1.91 Å. Both Ti(2)-O(1) bond lengths are 1.92 Å. Both Ti(2)-O(6) bond lengths are 2.11 Å. In the third Ti site, Ti(3) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. The Ti(3)-O(10) bond length is 1.97 Å. The Ti(3)-O(5) bond length is 1.93 Å. Both Ti(3)-O(1) bond lengths are 2.19 Å. Both Ti(3)-O(9) bond lengths are 1.89 Å. In the fourth Ti site, Ti(4) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. The Ti(4)-O(12) bond length is 2.02 Å. The Ti(4)-O(7) bond length is 2.07 Å. Both Ti(4)-O(11) bond lengths are 1.88 Å. Both Ti(4)-O(9) bond lengths are 2.20 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Ti(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, edges with four equivalent Ti(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The V(1)-O(3) bond length is 2.06 Å. The V(1)-O(4) bond length is 2.05 Å. Both V(1)-O(11) bond lengths are 2.13 Å. Both V(1)-O(6) bond lengths are 2.11 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-52°. The V(2)-O(1) bond length is 2.10 Å. The V(2)-O(10) bond length is 2.00 Å. The V(2)-O(12) bond length is 2.03 Å. The V(2)-O(5) bond length is 2.00 Å. The V(2)-O(8) bond length is 2.09 Å. The V(2)-O(9) bond length is 2.08 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(2), one Ti(3), and one V(2) atom. In the second O site, O(2) is bonded to one Li(4), one Ti(2), and two equivalent Ti(1) atoms to form a mixture of distorted edge and corner-sharing OLiTi3 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one V(1) atom. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Ti(1), and one V(1) atom to form OLiTi2V tetrahedra that share corners with four equivalent O(6)LiTi2V tetrahedra and corners with two equivalent O(2)LiTi3 trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), one Ti(3), and two equivalent V(2) atoms to form corner-sharing OLiTiV2 tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one Ti(1), one Ti(2), and one V(1) atom to form distorted OLiTi2V tetrahedra that share  a cornercorner with one O(6)LiTi2V tetrahedra, corners with two equivalent O(4)LiTi2V tetrahedra,  a cornercorner with one O(2)LiTi3 trigonal pyramid,  an edgeedge with one O(6)LiTi2V tetrahedra, and  an edgeedge with one O(2)LiTi3 trigonal pyramid. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(4), and two equivalent Ti(1) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(2), and two equivalent V(2) atoms. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Ti(3), one Ti(4), and one V(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(3), and two equivalent V(2) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one Ti(4), and one V(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one Ti(4), and two equivalent V(2) atoms to form corner-sharing OLiTiV2 tetrahedra.