Li3MnCoO5 crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms. In the third Li site, Li(3) is bonded to two equivalent O(5) and three equivalent O(4) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Li(4)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with four equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles are 13°. In the fourth Li site, Li(4) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form LiO6 octahedra that share corners with four equivalent Li(3)O5 square pyramids, edges with two equivalent Li(4)O6 octahedra, and edges with six equivalent Li(3)O5 square pyramids. Mn(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. Co(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), two equivalent Li(2), two equivalent Mn(1), and one Co(1) atom. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(5)Li4Co2 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, and edges with five equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Li(2), one Mn(1), and two equivalent Co(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(4), three equivalent Li(3), and one Co(1) atom to form OLi5Co octahedra that share corners with two equivalent O(5)Li4Co2 octahedra, corners with two equivalent O(4)Li5Co octahedra, edges with five equivalent O(5)Li4Co2 octahedra, and edges with five equivalent O(4)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), two equivalent Li(3), and two equivalent Co(1) atoms to form distorted OLi4Co2 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li4Co2 octahedra, corners with two equivalent O(4)Li5Co octahedra, edges with two equivalent O(5)Li4Co2 octahedra, and edges with five equivalent O(4)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-17°.
Li3MnCoO5 crystallizes in the monoclinic C2/m space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with six equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. Both Li(1)-O(1) bond lengths are 2.07 Å. All Li(1)-O(2) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms. The Li(2)-O(2) bond length is 2.49 Å. The Li(2)-O(5) bond length is 1.95 Å. Both Li(2)-O(1) bond lengths are 2.29 Å. Both Li(2)-O(3) bond lengths are 2.07 Å. In the third Li site, Li(3) is bonded to two equivalent O(5) and three equivalent O(4) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Li(4)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with four equivalent Li(3)O5 square pyramids. The corner-sharing octahedral tilt angles are 13°. Both Li(3)-O(5) bond lengths are 2.13 Å. There is one shorter (2.04 Å) and two longer (2.07 Å) Li(3)-O(4) bond lengths. In the fourth Li site, Li(4) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form LiO6 octahedra that share corners with four equivalent Li(3)O5 square pyramids, edges with two equivalent Li(4)O6 octahedra, and edges with six equivalent Li(3)O5 square pyramids. Both Li(4)-O(5) bond lengths are 2.20 Å. All Li(4)-O(4) bond lengths are 2.12 Å. Mn(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. The Mn(1)-O(3) bond length is 1.87 Å. Both Mn(1)-O(1) bond lengths are 1.92 Å. There are two shorter (1.98 Å) and one longer (2.07 Å) Mn(1)-O(2) bond length. Co(1) is bonded in a 6-coordinate geometry to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms. The Co(1)-O(1) bond length is 2.57 Å. The Co(1)-O(4) bond length is 1.77 Å. Both Co(1)-O(3) bond lengths are 2.15 Å. Both Co(1)-O(5) bond lengths are 1.97 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(1), two equivalent Li(2), two equivalent Mn(1), and one Co(1) atom. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(5)Li4Co2 octahedra, corners with two equivalent O(2)Li3Mn3 octahedra, and edges with five equivalent O(2)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Li(2), one Mn(1), and two equivalent Co(1) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(4), three equivalent Li(3), and one Co(1) atom to form OLi5Co octahedra that share corners with two equivalent O(5)Li4Co2 octahedra, corners with two equivalent O(4)Li5Co octahedra, edges with five equivalent O(5)Li4Co2 octahedra, and edges with five equivalent O(4)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), two equivalent Li(3), and two equivalent Co(1) atoms to form distorted OLi4Co2 octahedra that share  a cornercorner with one O(2)Li3Mn3 octahedra,  a cornercorner with one O(5)Li4Co2 octahedra, corners with two equivalent O(4)Li5Co octahedra, edges with two equivalent O(5)Li4Co2 octahedra, and edges with five equivalent O(4)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-17°.