Li3Mn5O8 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Mn(3)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 range from 0-11°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(3)O6 octahedra. The corner-sharing octahedra are not tilted. In the second Mn site, Mn(2) is bonded to six equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(3)O6 octahedra. The corner-sharing octahedra are not tilted. In the third Mn site, Mn(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Li(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 range from 0-11°. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and three equivalent Mn(3) atoms to form OLi3Mn3 octahedra that share corners with six equivalent O(1)Li3Mn3 octahedra and edges with twelve equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) 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(2)Li2Mn4 octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with eight equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedra are not tilted.
Li3Mn5O8 is Caswellsilverite-like structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Mn(3)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 range from 0-11°. Both Li(1)-O(1) bond lengths are 2.30 Å. All Li(1)-O(2) bond lengths are 2.15 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(3)O6 octahedra. The corner-sharing octahedra are not tilted. All Mn(1)-O(2) bond lengths are 2.16 Å. In the second Mn site, Mn(2) is bonded to six equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(3)O6 octahedra. The corner-sharing octahedra are not tilted. All Mn(2)-O(2) bond lengths are 2.15 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Li(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 range from 0-11°. Both Mn(3)-O(1) bond lengths are 2.02 Å. All Mn(3)-O(2) bond lengths are 2.16 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(1) and three equivalent Mn(3) atoms to form OLi3Mn3 octahedra that share corners with six equivalent O(1)Li3Mn3 octahedra and edges with twelve equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) 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(2)Li2Mn4 octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with eight equivalent O(2)Li2Mn4 octahedra. The corner-sharing octahedra are not tilted.