Li3TiMn4O8 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second Li site, Li(2) 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(2)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, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Mn(4)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 9-12°. Ti(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six 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 Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 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 Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. In the second Mn site, Mn(2) 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(2)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, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third Mn site, Mn(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six 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(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. In the fourth Mn site, Mn(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six 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 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 9-12°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one Mn(2), and one Mn(4) atom to form OLi3TiMn2 octahedra that share corners with six equivalent O(1)Li3TiMn2 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(3)Li2TiMn3 octahedra, and edges with four equivalent O(4)Li2TiMn3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom to form OLi2Mn4 octahedra that share corners with six equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(3)Li2TiMn3 octahedra, edges with four equivalent O(4)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 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(3)Li2TiMn3 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(4)Li2TiMn3 octahedra, and edges with four equivalent O(1)Li3TiMn2 octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Ti(1), one Mn(1), one Mn(3), and one Mn(4) atom to form OLi2TiMn3 octahedra that share corners with six equivalent O(4)Li2TiMn3 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(3)Li2TiMn3 octahedra, and edges with four equivalent O(1)Li3TiMn2 octahedra. The corner-sharing octahedra are not tilted.
Li3TiMn4O8 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Both Li(1)-O(1) bond lengths are 2.35 Å. Both Li(1)-O(3) bond lengths are 2.31 Å. Both Li(1)-O(4) bond lengths are 2.36 Å. In the second Li site, Li(2) 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(2)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, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Both Li(2)-O(1) bond lengths are 2.32 Å. Both Li(2)-O(2) bond lengths are 2.39 Å. Both Li(2)-O(3) bond lengths are 2.07 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Mn(4)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 9-12°. Both Li(3)-O(1) bond lengths are 2.18 Å. Both Li(3)-O(2) bond lengths are 2.17 Å. Both Li(3)-O(4) bond lengths are 2.19 Å. Ti(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share corners with six 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 Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Both Ti(1)-O(1) bond lengths are 2.04 Å. Both Ti(1)-O(3) bond lengths are 2.01 Å. Both Ti(1)-O(4) bond lengths are 2.01 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 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 Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. Both Mn(1)-O(2) bond lengths are 2.20 Å. Both Mn(1)-O(3) bond lengths are 2.19 Å. Both Mn(1)-O(4) bond lengths are 2.17 Å. In the second Mn site, Mn(2) 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(2)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, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Both Mn(2)-O(1) bond lengths are 2.00 Å. Both Mn(2)-O(2) bond lengths are 1.97 Å. Both Mn(2)-O(3) bond lengths are 2.32 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six 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(2)O6 octahedra, and edges with two equivalent Mn(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. Both Mn(3)-O(2) bond lengths are 2.20 Å. Both Mn(3)-O(3) bond lengths are 2.20 Å. Both Mn(3)-O(4) bond lengths are 2.16 Å. In the fourth Mn site, Mn(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with six 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 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 9-12°. Both Mn(4)-O(1) bond lengths are 2.21 Å. Both Mn(4)-O(2) bond lengths are 2.17 Å. Both Mn(4)-O(4) bond lengths are 2.21 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Ti(1), one Mn(2), and one Mn(4) atom to form OLi3TiMn2 octahedra that share corners with six equivalent O(1)Li3TiMn2 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(3)Li2TiMn3 octahedra, and edges with four equivalent O(4)Li2TiMn3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Mn(1), one Mn(2), one Mn(3), and one Mn(4) atom to form OLi2Mn4 octahedra that share corners with six equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(3)Li2TiMn3 octahedra, edges with four equivalent O(4)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 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(3)Li2TiMn3 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(4)Li2TiMn3 octahedra, and edges with four equivalent O(1)Li3TiMn2 octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Ti(1), one Mn(1), one Mn(3), and one Mn(4) atom to form OLi2TiMn3 octahedra that share corners with six equivalent O(4)Li2TiMn3 octahedra, edges with four equivalent O(2)Li2Mn4 octahedra, edges with four equivalent O(3)Li2TiMn3 octahedra, and edges with four equivalent O(1)Li3TiMn2 octahedra. The corner-sharing octahedra are not tilted.