Li5Mn2CoO8 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), two equivalent O(3), 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 Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. In the second Li site, Li(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form LiO6 octahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. In the third Li site, Li(3) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. Mn(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form MnO6 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 Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. Co(1) is bonded to two equivalent O(2) 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(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with three equivalent O(3)Li3Mn3 octahedra, corners with three equivalent O(2)Li5Co octahedra,  an edgeedge with one O(2)Li5Co octahedra, edges with two equivalent O(4)Li4Co2 octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with five equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Co(1) atom to form distorted OLi5Co octahedra that share corners with three equivalent O(1)Li3Mn3 octahedra, corners with three equivalent O(2)Li5Co octahedra,  an edgeedge with one O(1)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with three equivalent O(2)Li5Co octahedra, and edges with six equivalent O(4)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with three equivalent O(1)Li3Mn3 octahedra, corners with three equivalent O(4)Li4Co2 octahedra,  an edgeedge with one O(4)Li4Co2 octahedra, edges with two equivalent O(2)Li5Co octahedra, edges with four equivalent O(3)Li3Mn3 octahedra, and edges with five equivalent O(1)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Co(1) atoms to form OLi4Co2 octahedra that share corners with three equivalent O(3)Li3Mn3 octahedra, corners with three equivalent O(4)Li4Co2 octahedra,  an edgeedge with one O(3)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with three equivalent O(4)Li4Co2 octahedra, and edges with six equivalent O(2)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
Li5Mn2CoO8 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), two equivalent O(3), 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 Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. The Li(1)-O(1) bond length is 2.16 Å. The Li(1)-O(2) bond length is 2.37 Å. Both Li(1)-O(3) bond lengths are 2.19 Å. Both Li(1)-O(4) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form LiO6 octahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Mn(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. The Li(2)-O(3) bond length is 2.16 Å. The Li(2)-O(4) bond length is 2.02 Å. Both Li(2)-O(1) bond lengths are 2.25 Å. Both Li(2)-O(2) bond lengths are 2.01 Å. In the third Li site, Li(3) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. Both Li(3)-O(4) bond lengths are 2.14 Å. All Li(3)-O(2) bond lengths are 2.10 Å. Mn(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form MnO6 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 Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. There are two shorter (1.96 Å) and one longer (2.21 Å) Mn(1)-O(1) bond length. There are two shorter (1.97 Å) and one longer (2.24 Å) Mn(1)-O(3) bond length. Co(1) is bonded to two equivalent O(2) 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(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. Both Co(1)-O(2) bond lengths are 1.81 Å. All Co(1)-O(4) bond lengths are 1.95 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with three equivalent O(3)Li3Mn3 octahedra, corners with three equivalent O(2)Li5Co octahedra,  an edgeedge with one O(2)Li5Co octahedra, edges with two equivalent O(4)Li4Co2 octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with five equivalent O(3)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Co(1) atom to form distorted OLi5Co octahedra that share corners with three equivalent O(1)Li3Mn3 octahedra, corners with three equivalent O(2)Li5Co octahedra,  an edgeedge with one O(1)Li3Mn3 octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with three equivalent O(2)Li5Co octahedra, and edges with six equivalent O(4)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with three equivalent O(1)Li3Mn3 octahedra, corners with three equivalent O(4)Li4Co2 octahedra,  an edgeedge with one O(4)Li4Co2 octahedra, edges with two equivalent O(2)Li5Co octahedra, edges with four equivalent O(3)Li3Mn3 octahedra, and edges with five equivalent O(1)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-3°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent Co(1) atoms to form OLi4Co2 octahedra that share corners with three equivalent O(3)Li3Mn3 octahedra, corners with three equivalent O(4)Li4Co2 octahedra,  an edgeedge with one O(3)Li3Mn3 octahedra, edges with two equivalent O(1)Li3Mn3 octahedra, edges with three equivalent O(4)Li4Co2 octahedra, and edges with six equivalent O(2)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-3°.