Li3Mn(CoO3)2 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 one O(1), two equivalent O(2), and three equivalent O(3) 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(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with five equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. In the second Li site, Li(2) is bonded to two equivalent O(2) 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(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 are 10°. Mn(1) 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 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 1-9°. Co(1) is bonded to one O(2), two 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,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Co(1)O6 octahedra, and edges with five equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. 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), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share corners with three equivalent O(3)Li3Co3 octahedra, corners with three equivalent O(1)Li3MnCo2 octahedra, edges with three equivalent O(3)Li3Co3 octahedra, edges with three equivalent O(1)Li3MnCo2 octahedra, and edges with six equivalent O(2)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-6°. 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(3)Li3Co3 octahedra, corners with three equivalent O(2)Li3Mn2Co octahedra, edges with three equivalent O(3)Li3Co3 octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, and edges with six equivalent O(1)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to three equivalent Li(1) and three equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(2)Li3Mn2Co octahedra, corners with three equivalent O(1)Li3MnCo2 octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, edges with three equivalent O(1)Li3MnCo2 octahedra, and edges with six equivalent O(3)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 5-8°.
Li3Mn(CoO3)2 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 one O(1), two equivalent O(2), and three equivalent O(3) 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(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with five equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-9°. The Li(1)-O(1) bond length is 2.35 Å. Both Li(1)-O(2) bond lengths are 2.29 Å. There are two shorter (2.03 Å) and one longer (2.10 Å) Li(1)-O(3) bond length. In the second Li site, Li(2) is bonded to two equivalent O(2) 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(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 are 10°. Both Li(2)-O(2) bond lengths are 2.13 Å. All Li(2)-O(1) bond lengths are 2.13 Å. Mn(1) 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 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 1-9°. Both Mn(1)-O(1) bond lengths are 1.94 Å. All Mn(1)-O(2) bond lengths are 1.96 Å. Co(1) is bonded to one O(2), two 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,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Co(1)O6 octahedra, and edges with five equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-10°. The Co(1)-O(2) bond length is 2.16 Å. Both Co(1)-O(1) bond lengths are 2.07 Å. There are two shorter (2.04 Å) and one longer (2.05 Å) Co(1)-O(3) bond length. 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), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share corners with three equivalent O(3)Li3Co3 octahedra, corners with three equivalent O(1)Li3MnCo2 octahedra, edges with three equivalent O(3)Li3Co3 octahedra, edges with three equivalent O(1)Li3MnCo2 octahedra, and edges with six equivalent O(2)Li3Mn2Co octahedra. The corner-sharing octahedral tilt angles range from 0-6°. 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(3)Li3Co3 octahedra, corners with three equivalent O(2)Li3Mn2Co octahedra, edges with three equivalent O(3)Li3Co3 octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, and edges with six equivalent O(1)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to three equivalent Li(1) and three equivalent Co(1) atoms to form OLi3Co3 octahedra that share corners with three equivalent O(2)Li3Mn2Co octahedra, corners with three equivalent O(1)Li3MnCo2 octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, edges with three equivalent O(1)Li3MnCo2 octahedra, and edges with six equivalent O(3)Li3Co3 octahedra. The corner-sharing octahedral tilt angles range from 5-8°.