Li4MnCo3O8 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), two equivalent O(1), 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(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. In the second Li site, Li(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Co(1)O6 octahedra, corners with three equivalent Co(2)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. Mn(1) is bonded to two equivalent O(2) and four equivalent O(4) 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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form CoO6 octahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second Co site, Co(2) is bonded to two equivalent O(4) and four equivalent O(2) 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 Co(2)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 6-11°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and three equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(3)Li3Co3 octahedra, corners with three equivalent O(4)Li3Mn2Co octahedra,  an edgeedge with one O(4)Li3Mn2Co octahedra, edges with two equivalent O(2)Li3MnCo2 octahedra, edges with four equivalent O(1)Li3Co3 octahedra, and edges with five equivalent O(3)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Mn(1), and two equivalent Co(2) atoms to form OLi3MnCo2 octahedra that share corners with three equivalent O(3)Li3Co3 octahedra, corners with three equivalent O(2)Li3MnCo2 octahedra,  an edgeedge with one O(3)Li3Co3 octahedra, edges with two equivalent O(1)Li3Co3 octahedra, edges with three equivalent O(2)Li3MnCo2 octahedra, and edges with six equivalent O(4)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), and three equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(1)Li3Co3 octahedra, corners with three equivalent O(2)Li3MnCo2 octahedra,  an edgeedge with one O(2)Li3MnCo2 octahedra, edges with two equivalent O(4)Li3Mn2Co octahedra, edges with four equivalent O(3)Li3Co3 octahedra, and edges with five equivalent O(1)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(1), and one Co(2) atom to form OLi3Mn2Co octahedra that share corners with three equivalent O(1)Li3Co3 octahedra, corners with three equivalent O(4)Li3Mn2Co octahedra,  an edgeedge with one O(1)Li3Co3 octahedra, edges with two equivalent O(3)Li3Co3 octahedra, edges with three equivalent O(4)Li3Mn2Co octahedra, and edges with six equivalent O(2)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
Li4MnCo3O8 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), two equivalent O(1), 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(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. The Li(1)-O(2) bond length is 2.13 Å. The Li(1)-O(3) bond length is 2.13 Å. There is one shorter (2.12 Å) and one longer (2.18 Å) Li(1)-O(1) bond length. There is one shorter (2.09 Å) and one longer (2.14 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Co(1)O6 octahedra, corners with three equivalent Co(2)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Li(2)-O(1) bond length is 2.08 Å. The Li(2)-O(4) bond length is 2.20 Å. There is one shorter (2.15 Å) and one longer (2.34 Å) Li(2)-O(2) bond length. There is one shorter (2.08 Å) and one longer (2.12 Å) Li(2)-O(3) bond length. Mn(1) is bonded to two equivalent O(2) and four equivalent O(4) 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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-10°. Both Mn(1)-O(2) bond lengths are 2.00 Å. There are two shorter (1.93 Å) and two longer (2.17 Å) Mn(1)-O(4) bond lengths. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form CoO6 octahedra that share corners with three equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. There are a spread of Co(1)-O(1) bond distances ranging from 1.98-2.10 Å. There are a spread of Co(1)-O(3) bond distances ranging from 1.98-2.09 Å. In the second Co site, Co(2) is bonded to two equivalent O(4) and four equivalent O(2) 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 Co(2)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 6-11°. Both Co(2)-O(4) bond lengths are 1.96 Å. There are two shorter (1.96 Å) and two longer (1.97 Å) Co(2)-O(2) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), and three equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(3)Li3Co3 octahedra, corners with three equivalent O(4)Li3Mn2Co octahedra,  an edgeedge with one O(4)Li3Mn2Co octahedra, edges with two equivalent O(2)Li3MnCo2 octahedra, edges with four equivalent O(1)Li3Co3 octahedra, and edges with five equivalent O(3)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Mn(1), and two equivalent Co(2) atoms to form OLi3MnCo2 octahedra that share corners with three equivalent O(3)Li3Co3 octahedra, corners with three equivalent O(2)Li3MnCo2 octahedra,  an edgeedge with one O(3)Li3Co3 octahedra, edges with two equivalent O(1)Li3Co3 octahedra, edges with three equivalent O(2)Li3MnCo2 octahedra, and edges with six equivalent O(4)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), and three equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(1)Li3Co3 octahedra, corners with three equivalent O(2)Li3MnCo2 octahedra,  an edgeedge with one O(2)Li3MnCo2 octahedra, edges with two equivalent O(4)Li3Mn2Co octahedra, edges with four equivalent O(3)Li3Co3 octahedra, and edges with five equivalent O(1)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), two equivalent Mn(1), and one Co(2) atom to form OLi3Mn2Co octahedra that share corners with three equivalent O(1)Li3Co3 octahedra, corners with three equivalent O(4)Li3Mn2Co octahedra,  an edgeedge with one O(1)Li3Co3 octahedra, edges with two equivalent O(3)Li3Co3 octahedra, edges with three equivalent O(4)Li3Mn2Co octahedra, and edges with six equivalent O(2)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.