Li3TiMn2O6 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with four equivalent Ti(1)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. In the second Li site, Li(2) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with four equivalent Mn(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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the third Li site, Li(3) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with four equivalent Mn(1)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. Ti(1) is bonded to one O(1), one O(2), two equivalent O(5), and two equivalent O(6) atoms to form TiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four equivalent Li(1)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(4), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Li(3)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the second Mn site, Mn(2) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four 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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. There are six 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 Mn(2) atoms to form distorted OLi3TiMn2 octahedra that share  a cornercorner with one O(6)Li3Ti2Mn octahedra,  a cornercorner with one O(2)Li3TiMn2 octahedra, corners with four equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), one Ti(1), and two equivalent Mn(1) atoms to form distorted OLi3TiMn2 octahedra that share  a cornercorner with one O(5)Li3Ti2Mn octahedra,  a cornercorner with one O(1)Li3TiMn2 octahedra, corners with four equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(3), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(4)Li3Mn3 octahedra,  a cornercorner with one O(6)Li3Ti2Mn octahedra, corners with four equivalent O(2)Li3TiMn2 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(5)Li3Ti2Mn octahedra, corners with four equivalent O(1)Li3TiMn2 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(1), two equivalent Ti(1), and one Mn(1) atom to form OLi3Ti2Mn octahedra that share  a cornercorner with one O(4)Li3Mn3 octahedra,  a cornercorner with one O(2)Li3TiMn2 octahedra, corners with four equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the sixth O site, O(6) is bonded to one Li(3), two equivalent Li(1), two equivalent Ti(1), and one Mn(2) atom to form OLi3Ti2Mn octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(1)Li3TiMn2 octahedra, corners with four equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°.
Li3TiMn2O6 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with four equivalent Ti(1)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. The Li(1)-O(3) bond length is 2.21 Å. The Li(1)-O(4) bond length is 2.21 Å. Both Li(1)-O(5) bond lengths are 2.21 Å. Both Li(1)-O(6) bond lengths are 2.21 Å. In the second Li site, Li(2) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with four equivalent Mn(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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Li(2)-O(2) bond length is 2.56 Å. The Li(2)-O(5) bond length is 2.10 Å. Both Li(2)-O(1) bond lengths are 2.18 Å. Both Li(2)-O(4) bond lengths are 2.12 Å. In the third Li site, Li(3) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, corners with four equivalent Mn(1)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Li(3)-O(1) bond length is 2.56 Å. The Li(3)-O(6) bond length is 2.10 Å. Both Li(3)-O(2) bond lengths are 2.18 Å. Both Li(3)-O(3) bond lengths are 2.12 Å. Ti(1) is bonded to one O(1), one O(2), two equivalent O(5), and two equivalent O(6) atoms to form TiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four equivalent Li(1)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. The Ti(1)-O(1) bond length is 2.01 Å. The Ti(1)-O(2) bond length is 2.00 Å. Both Ti(1)-O(5) bond lengths are 2.00 Å. Both Ti(1)-O(6) bond lengths are 2.00 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(4), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Li(3)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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Mn(1)-O(4) bond length is 2.23 Å. The Mn(1)-O(5) bond length is 2.33 Å. Both Mn(1)-O(2) bond lengths are 2.09 Å. Both Mn(1)-O(3) bond lengths are 2.04 Å. In the second Mn site, Mn(2) is bonded to one O(3), one O(6), two equivalent O(1), and two equivalent O(4) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra, corners with four 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 Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Mn(2)-O(3) bond length is 2.23 Å. The Mn(2)-O(6) bond length is 2.33 Å. Both Mn(2)-O(1) bond lengths are 2.09 Å. Both Mn(2)-O(4) bond lengths are 2.03 Å. There are six 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 Mn(2) atoms to form distorted OLi3TiMn2 octahedra that share  a cornercorner with one O(6)Li3Ti2Mn octahedra,  a cornercorner with one O(2)Li3TiMn2 octahedra, corners with four equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), one Ti(1), and two equivalent Mn(1) atoms to form distorted OLi3TiMn2 octahedra that share  a cornercorner with one O(5)Li3Ti2Mn octahedra,  a cornercorner with one O(1)Li3TiMn2 octahedra, corners with four equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(3), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(4)Li3Mn3 octahedra,  a cornercorner with one O(6)Li3Ti2Mn octahedra, corners with four equivalent O(2)Li3TiMn2 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Li(2), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(5)Li3Ti2Mn octahedra, corners with four equivalent O(1)Li3TiMn2 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(1), two equivalent Ti(1), and one Mn(1) atom to form OLi3Ti2Mn octahedra that share  a cornercorner with one O(4)Li3Mn3 octahedra,  a cornercorner with one O(2)Li3TiMn2 octahedra, corners with four equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the sixth O site, O(6) is bonded to one Li(3), two equivalent Li(1), two equivalent Ti(1), and one Mn(2) atom to form OLi3Ti2Mn octahedra that share  a cornercorner with one O(3)Li3Mn3 octahedra,  a cornercorner with one O(1)Li3TiMn2 octahedra, corners with four equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(4)Li3Mn3 octahedra, edges with two equivalent O(5)Li3Ti2Mn octahedra, edges with two equivalent O(6)Li3Ti2Mn octahedra, edges with two equivalent O(1)Li3TiMn2 octahedra, and edges with two equivalent O(2)Li3TiMn2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°.