Li5Mn3O8 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. There are five 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 Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)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 7-13°. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)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 7-11°. In the third Li site, Li(3) 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 Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)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 7-13°. In the fourth Li site, Li(4) 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 Li(3)O6 octahedra, edges with two equivalent Li(5)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 5-7°. In the fifth Li site, Li(5) 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(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 Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. There are three 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 Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)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 7-11°. In the second Mn site, Mn(2) 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(5)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 Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. 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(4)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 Li(5)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 5-7°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), one Mn(2), and one Mn(3) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(1)Li4Mn2 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), one Li(4), one Li(5), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi3Mn3 octahedra that share corners with six equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, edges with four equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(4)Li4Mn2 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 Li(3), one Li(4), one Mn(1), and one Mn(3) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(3)Li4Mn2 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(4)Li4Mn2 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedra are not tilted.
Li5Mn3O8 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. There are five 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 Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)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 7-13°. Both Li(1)-O(1) bond lengths are 2.13 Å. Both Li(1)-O(3) bond lengths are 2.07 Å. Both Li(1)-O(4) bond lengths are 2.06 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)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 7-11°. Both Li(2)-O(2) bond lengths are 2.05 Å. Both Li(2)-O(3) bond lengths are 2.15 Å. Both Li(2)-O(4) bond lengths are 2.15 Å. In the third Li site, Li(3) 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 Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)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 7-13°. Both Li(3)-O(1) bond lengths are 2.15 Å. Both Li(3)-O(3) bond lengths are 2.04 Å. Both Li(3)-O(4) bond lengths are 2.05 Å. In the fourth Li site, Li(4) 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 Li(3)O6 octahedra, edges with two equivalent Li(5)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 5-7°. Both Li(4)-O(1) bond lengths are 2.13 Å. Both Li(4)-O(2) bond lengths are 2.13 Å. Both Li(4)-O(3) bond lengths are 2.34 Å. In the fifth Li site, Li(5) 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(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 Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Li(5)-O(1) bond lengths are 2.13 Å. Both Li(5)-O(2) bond lengths are 2.13 Å. Both Li(5)-O(4) bond lengths are 2.34 Å. There are three 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 Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(5)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 7-11°. Both Mn(1)-O(2) bond lengths are 2.23 Å. Both Mn(1)-O(3) bond lengths are 1.96 Å. Both Mn(1)-O(4) bond lengths are 1.95 Å. In the second Mn site, Mn(2) 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(5)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 Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Mn(2)-O(1) bond lengths are 1.95 Å. Both Mn(2)-O(2) bond lengths are 1.96 Å. Both Mn(2)-O(4) bond lengths are 1.94 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(4)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 Li(5)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 5-7°. Both Mn(3)-O(1) bond lengths are 1.95 Å. Both Mn(3)-O(2) bond lengths are 1.96 Å. Both Mn(3)-O(3) bond lengths are 1.94 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), one Mn(2), and one Mn(3) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(1)Li4Mn2 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), one Li(4), one Li(5), one Mn(1), one Mn(2), and one Mn(3) atom to form OLi3Mn3 octahedra that share corners with six equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, edges with four equivalent O(3)Li4Mn2 octahedra, and edges with four equivalent O(4)Li4Mn2 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 Li(3), one Li(4), one Mn(1), and one Mn(3) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(3)Li4Mn2 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(4)Li4Mn2 octahedra. The corner-sharing octahedra are not tilted. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Mn(1), and one Mn(2) atom to form OLi4Mn2 octahedra that share corners with six equivalent O(4)Li4Mn2 octahedra, edges with four equivalent O(2)Li3Mn3 octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(3)Li4Mn2 octahedra. The corner-sharing octahedra are not tilted.