Li4Ti5Nb3O16 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 Nb(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 Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-61°. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. 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 Nb(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 Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. 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 Nb(1)O6 octahedra, corners with two equivalent Nb(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 41-63°. 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, and edges with two equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. 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 Nb(2)O6 octahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. 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(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with four equivalent Nb(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 TiO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra, and edges with two equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form NbO6 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, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 52°. In the second Nb site, Nb(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 NbO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra,  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 Nb(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-54°. 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 Nb(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 corner and edge-sharing OLiTi3 tetrahedra. 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 Nb(1) atom. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Ti(1), and one Nb(1) atom to form distorted OLiTi2Nb tetrahedra that share corners with two equivalent O(2)LiTi3 tetrahedra and corners with four equivalent O(6)LiTi2Nb tetrahedra. In the fifth O site, O(5) is bonded in a distorted tetrahedral geometry to one Li(2), one Ti(3), and two equivalent Nb(2) atoms. In the sixth O site, O(6) is bonded to one Li(4), one Ti(1), one Ti(2), and one Nb(1) atom to form distorted OLiTi2Nb tetrahedra that share  a cornercorner with one O(6)LiTi2Nb tetrahedra,  a cornercorner with one O(2)LiTi3 tetrahedra, corners with two equivalent O(4)LiTi2Nb tetrahedra,  an edgeedge with one O(6)LiTi2Nb tetrahedra, and  an edgeedge with one O(2)LiTi3 tetrahedra. 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 distorted rectangular see-saw-like geometry to one Li(3), one Ti(2), and two equivalent Nb(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 Nb(2) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(4), one Ti(3), and two equivalent Nb(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 Nb(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Ti(4), and two equivalent Nb(2) atoms.
Li4Ti5Nb3O16 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 Nb(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 Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-61°. The Li(1)-O(12) bond length is 1.94 Å. The Li(1)-O(3) bond length is 1.99 Å. Both Li(1)-O(9) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. The Li(2)-O(5) bond length is 1.80 Å. The Li(2)-O(7) bond length is 1.99 Å. Both Li(2)-O(11) bond lengths are 2.05 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 Nb(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 Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. The Li(3)-O(4) bond length is 1.80 Å. The Li(3)-O(8) bond length is 2.04 Å. Both Li(3)-O(1) bond lengths are 1.98 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 Nb(1)O6 octahedra, corners with two equivalent Nb(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 41-63°. The Li(4)-O(10) bond length is 1.88 Å. The Li(4)-O(2) bond length is 2.02 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, and edges with two equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The Ti(1)-O(11) bond length is 2.12 Å. The Ti(1)-O(2) bond length is 1.99 Å. The Ti(1)-O(3) bond length is 2.00 Å. The Ti(1)-O(4) bond length is 1.99 Å. The Ti(1)-O(6) bond length is 2.01 Å. The Ti(1)-O(7) bond length is 2.09 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 Nb(2)O6 octahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. The Ti(2)-O(2) bond length is 2.20 Å. The Ti(2)-O(8) bond length is 1.92 Å. Both Ti(2)-O(1) bond lengths are 1.98 Å. Both Ti(2)-O(6) bond lengths are 2.12 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(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(4)O6 octahedra, edges with four equivalent Nb(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 2.01 Å. The Ti(3)-O(5) bond length is 1.99 Å. Both Ti(3)-O(1) bond lengths are 2.16 Å. Both Ti(3)-O(9) bond lengths are 2.01 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 TiO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra, and edges with two equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-52°. The Ti(4)-O(12) bond length is 2.06 Å. The Ti(4)-O(7) bond length is 2.02 Å. Both Ti(4)-O(11) bond lengths are 2.01 Å. Both Ti(4)-O(9) bond lengths are 2.11 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form NbO6 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, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 52°. The Nb(1)-O(3) bond length is 2.06 Å. The Nb(1)-O(4) bond length is 2.08 Å. Both Nb(1)-O(11) bond lengths are 2.09 Å. Both Nb(1)-O(6) bond lengths are 2.07 Å. In the second Nb site, Nb(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 NbO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra,  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 Nb(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-54°. The Nb(2)-O(1) bond length is 2.13 Å. The Nb(2)-O(10) bond length is 2.12 Å. The Nb(2)-O(12) bond length is 2.09 Å. The Nb(2)-O(5) bond length is 2.14 Å. The Nb(2)-O(8) bond length is 2.23 Å. The Nb(2)-O(9) bond length is 2.09 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 Nb(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 corner and edge-sharing OLiTi3 tetrahedra. 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 Nb(1) atom. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Ti(1), and one Nb(1) atom to form distorted OLiTi2Nb tetrahedra that share corners with two equivalent O(2)LiTi3 tetrahedra and corners with four equivalent O(6)LiTi2Nb tetrahedra. In the fifth O site, O(5) is bonded in a distorted tetrahedral geometry to one Li(2), one Ti(3), and two equivalent Nb(2) atoms. In the sixth O site, O(6) is bonded to one Li(4), one Ti(1), one Ti(2), and one Nb(1) atom to form distorted OLiTi2Nb tetrahedra that share  a cornercorner with one O(6)LiTi2Nb tetrahedra,  a cornercorner with one O(2)LiTi3 tetrahedra, corners with two equivalent O(4)LiTi2Nb tetrahedra,  an edgeedge with one O(6)LiTi2Nb tetrahedra, and  an edgeedge with one O(2)LiTi3 tetrahedra. 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 distorted rectangular see-saw-like geometry to one Li(3), one Ti(2), and two equivalent Nb(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 Nb(2) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(4), one Ti(3), and two equivalent Nb(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 Nb(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Ti(4), and two equivalent Nb(2) atoms.