Li4Mn3CoO8 is Caswellsilverite-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(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the second Li site, Li(2) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form LiO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Co(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. 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(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Co(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Mn(1), one Mn(2), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with six equivalent O(1)Li3Mn2Co octahedra, edges with four equivalent O(1)Li3Mn2Co octahedra, edges with four equivalent O(3)Li3Mn2Co octahedra, and edges with four equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share corners with three equivalent O(3)Li3Mn2Co octahedra, corners with three equivalent O(2)Li3Mn3 octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with three equivalent O(3)Li3Mn2Co octahedra, and edges with eight equivalent O(1)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(2), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with three equivalent O(3)Li3Mn2Co octahedra, corners with three equivalent O(2)Li3Mn3 octahedra,  an edgeedge with one O(3)Li3Mn2Co octahedra, edges with three equivalent O(2)Li3Mn3 octahedra, and edges with eight equivalent O(1)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-6°.
Li4Mn3CoO8 is Caswellsilverite-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(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both Li(1)-O(1) bond lengths are 2.19 Å. Both Li(1)-O(2) bond lengths are 2.16 Å. Both Li(1)-O(3) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form LiO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Co(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. The Li(2)-O(2) bond length is 2.12 Å. The Li(2)-O(3) bond length is 2.48 Å. All Li(2)-O(1) bond lengths are 2.13 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. Both Mn(1)-O(2) bond lengths are 2.26 Å. All Mn(1)-O(1) bond lengths are 1.97 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(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both Mn(2)-O(1) bond lengths are 2.26 Å. Both Mn(2)-O(2) bond lengths are 1.97 Å. Both Mn(2)-O(3) bond lengths are 1.98 Å. Co(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Co(1)-O(3) bond lengths are 2.05 Å. All Co(1)-O(1) bond lengths are 2.03 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Mn(1), one Mn(2), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with six equivalent O(1)Li3Mn2Co octahedra, edges with four equivalent O(1)Li3Mn2Co octahedra, edges with four equivalent O(3)Li3Mn2Co octahedra, and edges with four equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share corners with three equivalent O(3)Li3Mn2Co octahedra, corners with three equivalent O(2)Li3Mn3 octahedra,  an edgeedge with one O(2)Li3Mn3 octahedra, edges with three equivalent O(3)Li3Mn2Co octahedra, and edges with eight equivalent O(1)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(2), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with three equivalent O(3)Li3Mn2Co octahedra, corners with three equivalent O(2)Li3Mn3 octahedra,  an edgeedge with one O(3)Li3Mn2Co octahedra, edges with three equivalent O(2)Li3Mn3 octahedra, and edges with eight equivalent O(1)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-6°.