Li4MnCo3O8 is Caswellsilverite-derived structured and crystallizes in the monoclinic P2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Co(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Co(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, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)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(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the third Li site, Li(3) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. 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 Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. In the second Co site, Co(2) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Co(2), and two equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(1)Li3Co3 octahedra, corners with three equivalent O(3)Li3MnCo2 octahedra,  an edgeedge with one O(3)Li3MnCo2 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with three equivalent O(1)Li3Co3 octahedra, and edges with six equivalent O(4)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with three equivalent O(4)Li3Co3 octahedra, corners with three equivalent O(2)Li3Mn2Co octahedra,  an edgeedge with one O(4)Li3Co3 octahedra, edges with two equivalent O(1)Li3Co3 octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, and edges with six equivalent O(3)Li3MnCo2 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), one Mn(1), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share corners with three equivalent O(1)Li3Co3 octahedra, corners with three equivalent O(3)Li3MnCo2 octahedra,  an edgeedge with one O(1)Li3Co3 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with three equivalent O(3)Li3MnCo2 octahedra, and edges with six equivalent O(2)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(1), one Co(1), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(4)Li3Co3 octahedra, corners with three equivalent O(2)Li3Mn2Co octahedra,  an edgeedge with one O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3MnCo2 octahedra, edges with three equivalent O(4)Li3Co3 octahedra, and edges with six equivalent O(1)Li3Co3 octahedra. The corner-sharing octahedra are not tilted.
Li4MnCo3O8 is Caswellsilverite-derived structured and crystallizes in the monoclinic P2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Co(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Co(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, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. The Li(1)-O(1) bond length is 2.26 Å. The Li(1)-O(3) bond length is 2.18 Å. Both Li(1)-O(2) bond lengths are 2.11 Å. Both Li(1)-O(4) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)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(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. Both Li(2)-O(2) bond lengths are 2.21 Å. All Li(2)-O(3) bond lengths are 2.15 Å. In the third Li site, Li(3) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Co(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles are 5°. Both Li(3)-O(4) bond lengths are 2.22 Å. All Li(3)-O(1) bond lengths are 2.13 Å. 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 Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both Mn(1)-O(3) bond lengths are 2.25 Å. All Mn(1)-O(2) bond lengths are 1.96 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Li(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-6°. The Co(1)-O(2) bond length is 2.27 Å. The Co(1)-O(4) bond length is 2.17 Å. Both Co(1)-O(1) bond lengths are 1.94 Å. Both Co(1)-O(3) bond lengths are 1.93 Å. In the second Co site, Co(2) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. Both Co(2)-O(1) bond lengths are 2.19 Å. All Co(2)-O(4) bond lengths are 1.96 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Co(2), and two equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(1)Li3Co3 octahedra, corners with three equivalent O(3)Li3MnCo2 octahedra,  an edgeedge with one O(3)Li3MnCo2 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with three equivalent O(1)Li3Co3 octahedra, and edges with six equivalent O(4)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with three equivalent O(4)Li3Co3 octahedra, corners with three equivalent O(2)Li3Mn2Co octahedra,  an edgeedge with one O(4)Li3Co3 octahedra, edges with two equivalent O(1)Li3Co3 octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, and edges with six equivalent O(3)Li3MnCo2 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), one Mn(1), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share corners with three equivalent O(1)Li3Co3 octahedra, corners with three equivalent O(3)Li3MnCo2 octahedra,  an edgeedge with one O(1)Li3Co3 octahedra, edges with two equivalent O(4)Li3Co3 octahedra, edges with three equivalent O(3)Li3MnCo2 octahedra, and edges with six equivalent O(2)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(1), one Co(1), and two equivalent Co(2) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(4)Li3Co3 octahedra, corners with three equivalent O(2)Li3Mn2Co octahedra,  an edgeedge with one O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3MnCo2 octahedra, edges with three equivalent O(4)Li3Co3 octahedra, and edges with six equivalent O(1)Li3Co3 octahedra. The corner-sharing octahedra are not tilted.