Li3TiMn3O8 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with five equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)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, and  a faceface with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-51°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with five equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and  a faceface with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-48°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and  a faceface with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-47°. Ti(1) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form distorted TiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-48°. In the second Mn site, Mn(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with five equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-60°. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  a faceface with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-54°. There are eight inequivalent O sites. In the first O site, O(4) is bonded to one Li(2), one Li(3), one Ti(1), one Mn(1), and one Mn(3) atom to form OLi2TiMn2 square pyramids that share  a cornercorner with one O(3)Li2TiMn2 square pyramid,  a cornercorner with one O(7)Li2TiMn2 square pyramid, corners with two equivalent O(2)Li2TiMn2 trigonal bipyramids, corners with four equivalent O(6)Li2TiMn2 trigonal bipyramids, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(3)Li2TiMn2 square pyramid,  an edgeedge with one O(7)Li2TiMn2 square pyramid, and  an edgeedge with one O(2)Li2TiMn2 trigonal bipyramid. In the second O site, O(5) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), and one Mn(3) atom. In the third O site, O(6) is bonded to one Li(2), one Li(3), one Ti(1), one Mn(2), and one Mn(3) atom to form distorted OLi2TiMn2 trigonal bipyramids that share  a cornercorner with one O(3)Li2TiMn2 square pyramid, corners with two equivalent O(7)Li2TiMn2 square pyramids, corners with four equivalent O(4)Li2TiMn2 square pyramids,  a cornercorner with one O(2)Li2TiMn2 trigonal bipyramid, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(3)Li2TiMn2 square pyramid,  an edgeedge with one O(7)Li2TiMn2 square pyramid, and  an edgeedge with one O(2)Li2TiMn2 trigonal bipyramid. In the fourth O site, O(7) is bonded to one Li(1), one Li(3), one Ti(1), one Mn(2), and one Mn(3) atom to form distorted OLi2TiMn2 square pyramids that share  a cornercorner with one O(3)Li2TiMn2 square pyramid,  a cornercorner with one O(4)Li2TiMn2 square pyramid, corners with two equivalent O(6)Li2TiMn2 trigonal bipyramids, corners with four equivalent O(2)Li2TiMn2 trigonal bipyramids, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(3)Li2TiMn2 square pyramid,  an edgeedge with one O(4)Li2TiMn2 square pyramid, and  an edgeedge with one O(6)Li2TiMn2 trigonal bipyramid. In the fifth O site, O(8) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Ti(1), one Mn(1), and one Mn(2) atom. In the sixth O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), and one Mn(3) atom to form edge-sharing OLi3Mn3 octahedra. In the seventh O site, O(2) is bonded to one Li(1), one Li(3), one Ti(1), one Mn(1), and one Mn(3) atom to form distorted OLi2TiMn2 trigonal bipyramids that share  a cornercorner with one O(3)Li2TiMn2 square pyramid, corners with two equivalent O(4)Li2TiMn2 square pyramids, corners with four equivalent O(7)Li2TiMn2 square pyramids,  a cornercorner with one O(6)Li2TiMn2 trigonal bipyramid, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(3)Li2TiMn2 square pyramid,  an edgeedge with one O(4)Li2TiMn2 square pyramid, and  an edgeedge with one O(6)Li2TiMn2 trigonal bipyramid. In the eighth O site, O(3) is bonded to one Li(1), one Li(2), one Ti(1), one Mn(1), and one Mn(2) atom to form OLi2TiMn2 square pyramids that share  a cornercorner with one O(4)Li2TiMn2 square pyramid,  a cornercorner with one O(7)Li2TiMn2 square pyramid,  a cornercorner with one O(2)Li2TiMn2 trigonal bipyramid,  a cornercorner with one O(6)Li2TiMn2 trigonal bipyramid, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(4)Li2TiMn2 square pyramid,  an edgeedge with one O(7)Li2TiMn2 square pyramid,  an edgeedge with one O(2)Li2TiMn2 trigonal bipyramid, and  an edgeedge with one O(6)Li2TiMn2 trigonal bipyramid.
Li3TiMn3O8 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with five equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)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, and  a faceface with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-51°. The Li(1)-O(1) bond length is 2.17 Å. The Li(1)-O(2) bond length is 2.16 Å. The Li(1)-O(3) bond length is 2.00 Å. The Li(1)-O(5) bond length is 2.20 Å. The Li(1)-O(7) bond length is 2.01 Å. The Li(1)-O(8) bond length is 2.20 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted LiO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra, corners with five equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and  a faceface with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-48°. The Li(2)-O(1) bond length is 2.07 Å. The Li(2)-O(3) bond length is 2.00 Å. The Li(2)-O(4) bond length is 2.00 Å. The Li(2)-O(5) bond length is 2.31 Å. The Li(2)-O(6) bond length is 2.21 Å. The Li(2)-O(8) bond length is 2.33 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and  a faceface with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-47°. The Li(3)-O(1) bond length is 2.13 Å. The Li(3)-O(2) bond length is 2.31 Å. The Li(3)-O(4) bond length is 1.98 Å. The Li(3)-O(5) bond length is 2.11 Å. The Li(3)-O(6) bond length is 2.36 Å. The Li(3)-O(7) bond length is 2.01 Å. Ti(1) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form distorted TiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. The Ti(1)-O(2) bond length is 1.88 Å. The Ti(1)-O(3) bond length is 2.06 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 2.27 Å. The Ti(1)-O(8) bond length is 1.90 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(8) atom to form MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with five equivalent Li(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-48°. The Mn(1)-O(1) bond length is 2.21 Å. The Mn(1)-O(2) bond length is 2.01 Å. The Mn(1)-O(3) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 1.96 Å. The Mn(1)-O(5) bond length is 2.25 Å. The Mn(1)-O(8) bond length is 2.01 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with five equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and  a faceface with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-60°. The Mn(2)-O(1) bond length is 1.96 Å. The Mn(2)-O(3) bond length is 2.28 Å. The Mn(2)-O(5) bond length is 1.95 Å. The Mn(2)-O(6) bond length is 2.02 Å. The Mn(2)-O(7) bond length is 1.98 Å. The Mn(2)-O(8) bond length is 2.32 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(7) atom to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  a faceface with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-54°. The Mn(3)-O(1) bond length is 1.95 Å. The Mn(3)-O(2) bond length is 2.28 Å. The Mn(3)-O(4) bond length is 2.25 Å. The Mn(3)-O(5) bond length is 1.94 Å. The Mn(3)-O(6) bond length is 2.02 Å. The Mn(3)-O(7) bond length is 2.00 Å. There are eight inequivalent O sites. In the first O site, O(4) is bonded to one Li(2), one Li(3), one Ti(1), one Mn(1), and one Mn(3) atom to form OLi2TiMn2 square pyramids that share  a cornercorner with one O(3)Li2TiMn2 square pyramid,  a cornercorner with one O(7)Li2TiMn2 square pyramid, corners with two equivalent O(2)Li2TiMn2 trigonal bipyramids, corners with four equivalent O(6)Li2TiMn2 trigonal bipyramids, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(3)Li2TiMn2 square pyramid,  an edgeedge with one O(7)Li2TiMn2 square pyramid, and  an edgeedge with one O(2)Li2TiMn2 trigonal bipyramid. In the second O site, O(5) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), and one Mn(3) atom. In the third O site, O(6) is bonded to one Li(2), one Li(3), one Ti(1), one Mn(2), and one Mn(3) atom to form distorted OLi2TiMn2 trigonal bipyramids that share  a cornercorner with one O(3)Li2TiMn2 square pyramid, corners with two equivalent O(7)Li2TiMn2 square pyramids, corners with four equivalent O(4)Li2TiMn2 square pyramids,  a cornercorner with one O(2)Li2TiMn2 trigonal bipyramid, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(3)Li2TiMn2 square pyramid,  an edgeedge with one O(7)Li2TiMn2 square pyramid, and  an edgeedge with one O(2)Li2TiMn2 trigonal bipyramid. In the fourth O site, O(7) is bonded to one Li(1), one Li(3), one Ti(1), one Mn(2), and one Mn(3) atom to form distorted OLi2TiMn2 square pyramids that share  a cornercorner with one O(3)Li2TiMn2 square pyramid,  a cornercorner with one O(4)Li2TiMn2 square pyramid, corners with two equivalent O(6)Li2TiMn2 trigonal bipyramids, corners with four equivalent O(2)Li2TiMn2 trigonal bipyramids, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(3)Li2TiMn2 square pyramid,  an edgeedge with one O(4)Li2TiMn2 square pyramid, and  an edgeedge with one O(6)Li2TiMn2 trigonal bipyramid. In the fifth O site, O(8) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Ti(1), one Mn(1), and one Mn(2) atom. In the sixth O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), one Mn(2), and one Mn(3) atom to form edge-sharing OLi3Mn3 octahedra. In the seventh O site, O(2) is bonded to one Li(1), one Li(3), one Ti(1), one Mn(1), and one Mn(3) atom to form distorted OLi2TiMn2 trigonal bipyramids that share  a cornercorner with one O(3)Li2TiMn2 square pyramid, corners with two equivalent O(4)Li2TiMn2 square pyramids, corners with four equivalent O(7)Li2TiMn2 square pyramids,  a cornercorner with one O(6)Li2TiMn2 trigonal bipyramid, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(3)Li2TiMn2 square pyramid,  an edgeedge with one O(4)Li2TiMn2 square pyramid, and  an edgeedge with one O(6)Li2TiMn2 trigonal bipyramid. In the eighth O site, O(3) is bonded to one Li(1), one Li(2), one Ti(1), one Mn(1), and one Mn(2) atom to form OLi2TiMn2 square pyramids that share  a cornercorner with one O(4)Li2TiMn2 square pyramid,  a cornercorner with one O(7)Li2TiMn2 square pyramid,  a cornercorner with one O(2)Li2TiMn2 trigonal bipyramid,  a cornercorner with one O(6)Li2TiMn2 trigonal bipyramid, edges with two equivalent O(1)Li3Mn3 octahedra,  an edgeedge with one O(4)Li2TiMn2 square pyramid,  an edgeedge with one O(7)Li2TiMn2 square pyramid,  an edgeedge with one O(2)Li2TiMn2 trigonal bipyramid, and  an edgeedge with one O(6)Li2TiMn2 trigonal bipyramid.