Li3TiMn4O8 is alpha Po-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Mn(3)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, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. Ti(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the second Mn site, Mn(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with six 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 Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent Mn(3) atoms to form OLi3TiMn2 octahedra that share corners with six equivalent O(1)Li3TiMn2 octahedra, edges with four equivalent O(3)Li2Mn4 octahedra, and edges with eight equivalent O(2)Li2TiMn3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Ti(1), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi2TiMn3 octahedra that share corners with six equivalent O(2)Li2TiMn3 octahedra, edges with four equivalent O(3)Li2Mn4 octahedra, edges with four equivalent O(2)Li2TiMn3 octahedra, and edges with four equivalent O(1)Li3TiMn2 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to two equivalent Li(1), one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi2Mn4 octahedra that share corners with six equivalent O(3)Li2Mn4 octahedra, edges with four equivalent O(1)Li3TiMn2 octahedra, and edges with eight equivalent O(2)Li2TiMn3 octahedra. The corner-sharing octahedra are not tilted.
Li3TiMn4O8 is alpha Po-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Mn(3)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, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. Both Li(1)-O(1) bond lengths are 2.20 Å. Both Li(1)-O(2) bond lengths are 2.13 Å. Both Li(1)-O(3) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. Both Li(2)-O(1) bond lengths are 2.36 Å. All Li(2)-O(2) bond lengths are 2.31 Å. Ti(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. Both Ti(1)-O(1) bond lengths are 1.98 Å. All Ti(1)-O(2) bond lengths are 2.04 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. Both Mn(1)-O(3) bond lengths are 2.18 Å. All Mn(1)-O(2) bond lengths are 2.17 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. Both Mn(2)-O(3) bond lengths are 2.16 Å. All Mn(2)-O(2) bond lengths are 2.18 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with six 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 Ti(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. Both Mn(3)-O(1) bond lengths are 2.16 Å. Both Mn(3)-O(2) bond lengths are 2.22 Å. Both Mn(3)-O(3) bond lengths are 2.11 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent Mn(3) atoms to form OLi3TiMn2 octahedra that share corners with six equivalent O(1)Li3TiMn2 octahedra, edges with four equivalent O(3)Li2Mn4 octahedra, and edges with eight equivalent O(2)Li2TiMn3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Ti(1), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi2TiMn3 octahedra that share corners with six equivalent O(2)Li2TiMn3 octahedra, edges with four equivalent O(3)Li2Mn4 octahedra, edges with four equivalent O(2)Li2TiMn3 octahedra, and edges with four equivalent O(1)Li3TiMn2 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to two equivalent Li(1), one Mn(1), one Mn(2), and two equivalent Mn(3) atoms to form OLi2Mn4 octahedra that share corners with six equivalent O(3)Li2Mn4 octahedra, edges with four equivalent O(1)Li3TiMn2 octahedra, and edges with eight equivalent O(2)Li2TiMn3 octahedra. The corner-sharing octahedra are not tilted.