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(3), and four equivalent O(2) atoms to form LiO6 octahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Co(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. In the second Li site, Li(2) 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(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the third Li site, Li(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 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 Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. Mn(1) 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(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Co(1) is bonded to two equivalent O(3) and four equivalent O(2) 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 Li(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-11°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with three equivalent O(3)Li3Mn2Co octahedra, corners with three equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one O(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li3Mn2Co octahedra, and edges with eight equivalent O(2)Li4MnCo octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), one Mn(1), and one Co(1) atom to form OLi4MnCo octahedra that share corners with six equivalent O(2)Li4MnCo octahedra, edges with four equivalent O(3)Li3Mn2Co octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(2)Li4MnCo 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), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with three equivalent O(3)Li3Mn2Co octahedra, corners with three equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one O(3)Li3Mn2Co octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with eight equivalent O(2)Li4MnCo 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(3), and four equivalent O(2) atoms to form LiO6 octahedra that share corners with three equivalent Li(3)O6 octahedra, corners with three equivalent Co(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. The Li(1)-O(1) bond length is 2.07 Å. The Li(1)-O(3) bond length is 2.05 Å. There are two shorter (2.06 Å) and two longer (2.17 Å) Li(1)-O(2) bond lengths. In the second Li site, Li(2) 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(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Both Li(2)-O(1) bond lengths are 2.09 Å. Both Li(2)-O(2) bond lengths are 2.29 Å. Both Li(2)-O(3) bond lengths are 2.16 Å. In the third Li site, Li(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 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 Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-12°. Both Li(3)-O(1) bond lengths are 2.13 Å. All Li(3)-O(2) bond lengths are 2.03 Å. Mn(1) 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(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Both Mn(1)-O(1) bond lengths are 1.95 Å. Both Mn(1)-O(2) bond lengths are 1.94 Å. Both Mn(1)-O(3) bond lengths are 1.94 Å. Co(1) is bonded to two equivalent O(3) and four equivalent O(2) 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 Li(3)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-11°. Both Co(1)-O(3) bond lengths are 2.22 Å. All Co(1)-O(2) bond lengths are 1.91 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with three equivalent O(3)Li3Mn2Co octahedra, corners with three equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one O(1)Li4Mn2 octahedra, edges with three equivalent O(3)Li3Mn2Co octahedra, and edges with eight equivalent O(2)Li4MnCo octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), one Mn(1), and one Co(1) atom to form OLi4MnCo octahedra that share corners with six equivalent O(2)Li4MnCo octahedra, edges with four equivalent O(3)Li3Mn2Co octahedra, edges with four equivalent O(1)Li4Mn2 octahedra, and edges with four equivalent O(2)Li4MnCo 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), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with three equivalent O(3)Li3Mn2Co octahedra, corners with three equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one O(3)Li3Mn2Co octahedra, edges with three equivalent O(1)Li4Mn2 octahedra, and edges with eight equivalent O(2)Li4MnCo octahedra. The corner-sharing octahedral tilt angles range from 0-3°.