Li4Ti3V3Mn2O16 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(2)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. In the second Li site, Li(2) is bonded in a distorted 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 in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. 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(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-65°. There are two 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 Mn(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the second Ti site, Ti(2) 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 Mn(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 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 Mn(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. 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 Mn(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent V(2)O6 octahedra, 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 53-54°. In the second Mn site, Mn(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form MnO6 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,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. 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 V(2), and one Mn(1) atom. In the second O site, O(2) is bonded to one Li(4), two equivalent Ti(1), and one Mn(1) atom to form distorted OLiTi2Mn tetrahedra that share corners with two equivalent O(4)LiTi2V tetrahedra, corners with two equivalent O(6)LiTiMnV tetrahedra,  a cornercorner with one O(8)LiMnV2 trigonal pyramid, and edges with two equivalent O(6)LiTiMnV 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 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 distorted OLiTi2V tetrahedra that share corners with two equivalent O(2)LiTi2Mn tetrahedra, corners with four equivalent O(6)LiTiMnV tetrahedra, and  a cornercorner with one O(8)LiMnV2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(2), one Ti(2), and two equivalent V(2) atoms to form distorted OLiTiV2 tetrahedra that share corners with two equivalent O(12)LiMnV2 tetrahedra, corners with four equivalent O(9)LiTiMnV tetrahedra, and  an edgeedge with one O(8)LiMnV2 trigonal pyramid. In the sixth O site, O(6) is bonded to one Li(4), one Ti(1), one V(1), and one Mn(1) atom to form distorted OLiTiMnV tetrahedra that share  a cornercorner with one O(2)LiTi2Mn tetrahedra,  a cornercorner with one O(6)LiTiMnV tetrahedra, corners with two equivalent O(4)LiTi2V tetrahedra,  a cornercorner with one O(8)LiMnV2 trigonal pyramid,  an edgeedge with one O(2)LiTi2Mn tetrahedra, and  an edgeedge with one O(6)LiTiMnV tetrahedra. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Ti(1), and one Mn(2) atom. In the eighth O site, O(8) is bonded to one Li(3), two equivalent V(2), and one Mn(1) atom to form OLiMnV2 trigonal pyramids that share  a cornercorner with one O(2)LiTi2Mn tetrahedra,  a cornercorner with one O(4)LiTi2V tetrahedra, corners with two equivalent O(12)LiMnV2 tetrahedra, corners with two equivalent O(6)LiTiMnV tetrahedra, corners with two equivalent O(9)LiTiMnV tetrahedra, and  an edgeedge with one O(5)LiTiV2 tetrahedra. In the ninth O site, O(9) is bonded to one Li(1), one Ti(2), one V(2), and one Mn(2) atom to form distorted OLiTiMnV tetrahedra that share  a cornercorner with one O(12)LiMnV2 tetrahedra,  a cornercorner with one O(9)LiTiMnV tetrahedra, corners with two equivalent O(5)LiTiV2 tetrahedra,  a cornercorner with one O(8)LiMnV2 trigonal pyramid,  an edgeedge with one O(12)LiMnV2 tetrahedra, and  an edgeedge with one O(9)LiTiMnV tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(2), 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 V(1), and one Mn(2) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Mn(2) atom to form distorted OLiMnV2 tetrahedra that share corners with two equivalent O(9)LiTiMnV tetrahedra, corners with two equivalent O(5)LiTiV2 tetrahedra, corners with two equivalent O(8)LiMnV2 trigonal pyramids, and edges with two equivalent O(9)LiTiMnV tetrahedra.
Li4Ti3V3Mn2O16 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(2)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. The Li(1)-O(12) bond length is 1.97 Å. The Li(1)-O(3) bond length is 2.05 Å. Both Li(1)-O(9) bond lengths are 1.98 Å. In the second Li site, Li(2) is bonded in a distorted 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 1.94 Å. Both Li(2)-O(11) bond lengths are 1.94 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. The Li(3)-O(4) bond length is 1.80 Å. The Li(3)-O(8) bond length is 1.92 Å. Both Li(3)-O(1) bond lengths are 1.94 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(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-65°. The Li(4)-O(10) bond length is 2.04 Å. The Li(4)-O(2) bond length is 1.97 Å. Both Li(4)-O(6) bond lengths are 1.97 Å. There are two 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 Mn(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Ti(1)-O(11) bond length is 2.07 Å. The Ti(1)-O(2) bond length is 1.96 Å. The Ti(1)-O(3) bond length is 1.99 Å. The Ti(1)-O(4) bond length is 1.96 Å. The Ti(1)-O(6) bond length is 1.93 Å. The Ti(1)-O(7) bond length is 1.99 Å. In the second Ti site, Ti(2) 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 Mn(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Ti(2)-O(10) bond length is 2.04 Å. The Ti(2)-O(5) bond length is 1.94 Å. Both Ti(2)-O(1) bond lengths are 2.03 Å. Both Ti(2)-O(9) bond lengths are 1.95 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 Mn(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(4) bond length is 2.00 Å. Both V(1)-O(11) bond lengths are 1.92 Å. Both V(1)-O(6) bond lengths are 1.99 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 Mn(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. The V(2)-O(1) bond length is 1.95 Å. The V(2)-O(10) bond length is 1.96 Å. The V(2)-O(12) bond length is 1.92 Å. The V(2)-O(5) bond length is 2.01 Å. The V(2)-O(8) bond length is 2.00 Å. The V(2)-O(9) bond length is 1.98 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent V(2)O6 octahedra, 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 53-54°. The Mn(1)-O(2) bond length is 2.24 Å. The Mn(1)-O(8) bond length is 2.09 Å. Both Mn(1)-O(1) bond lengths are 2.06 Å. Both Mn(1)-O(6) bond lengths are 2.20 Å. In the second Mn site, Mn(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form MnO6 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,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-53°. The Mn(2)-O(12) bond length is 2.24 Å. The Mn(2)-O(7) bond length is 2.11 Å. Both Mn(2)-O(11) bond lengths are 2.07 Å. Both Mn(2)-O(9) bond lengths are 2.15 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 V(2), and one Mn(1) atom. In the second O site, O(2) is bonded to one Li(4), two equivalent Ti(1), and one Mn(1) atom to form distorted OLiTi2Mn tetrahedra that share corners with two equivalent O(4)LiTi2V tetrahedra, corners with two equivalent O(6)LiTiMnV tetrahedra,  a cornercorner with one O(8)LiMnV2 trigonal pyramid, and edges with two equivalent O(6)LiTiMnV 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 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 distorted OLiTi2V tetrahedra that share corners with two equivalent O(2)LiTi2Mn tetrahedra, corners with four equivalent O(6)LiTiMnV tetrahedra, and  a cornercorner with one O(8)LiMnV2 trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(2), one Ti(2), and two equivalent V(2) atoms to form distorted OLiTiV2 tetrahedra that share corners with two equivalent O(12)LiMnV2 tetrahedra, corners with four equivalent O(9)LiTiMnV tetrahedra, and  an edgeedge with one O(8)LiMnV2 trigonal pyramid. In the sixth O site, O(6) is bonded to one Li(4), one Ti(1), one V(1), and one Mn(1) atom to form distorted OLiTiMnV tetrahedra that share  a cornercorner with one O(2)LiTi2Mn tetrahedra,  a cornercorner with one O(6)LiTiMnV tetrahedra, corners with two equivalent O(4)LiTi2V tetrahedra,  a cornercorner with one O(8)LiMnV2 trigonal pyramid,  an edgeedge with one O(2)LiTi2Mn tetrahedra, and  an edgeedge with one O(6)LiTiMnV tetrahedra. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Ti(1), and one Mn(2) atom. In the eighth O site, O(8) is bonded to one Li(3), two equivalent V(2), and one Mn(1) atom to form OLiMnV2 trigonal pyramids that share  a cornercorner with one O(2)LiTi2Mn tetrahedra,  a cornercorner with one O(4)LiTi2V tetrahedra, corners with two equivalent O(12)LiMnV2 tetrahedra, corners with two equivalent O(6)LiTiMnV tetrahedra, corners with two equivalent O(9)LiTiMnV tetrahedra, and  an edgeedge with one O(5)LiTiV2 tetrahedra. In the ninth O site, O(9) is bonded to one Li(1), one Ti(2), one V(2), and one Mn(2) atom to form distorted OLiTiMnV tetrahedra that share  a cornercorner with one O(12)LiMnV2 tetrahedra,  a cornercorner with one O(9)LiTiMnV tetrahedra, corners with two equivalent O(5)LiTiV2 tetrahedra,  a cornercorner with one O(8)LiMnV2 trigonal pyramid,  an edgeedge with one O(12)LiMnV2 tetrahedra, and  an edgeedge with one O(9)LiTiMnV tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(2), 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 V(1), and one Mn(2) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Mn(2) atom to form distorted OLiMnV2 tetrahedra that share corners with two equivalent O(9)LiTiMnV tetrahedra, corners with two equivalent O(5)LiTiV2 tetrahedra, corners with two equivalent O(8)LiMnV2 trigonal pyramids, and edges with two equivalent O(9)LiTiMnV tetrahedra.