Li3MnCoO5 is Caswellsilverite-derived structured and 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(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(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 are 11°. In the second Li site, Li(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. In the third Li site, Li(3) is bonded to one O(4), two equivalent O(2), and three equivalent O(5) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. In the fourth Li site, Li(4) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form a mixture of edge and corner-sharing LiO6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. Mn(1) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-13°. Co(1) is bonded in a 6-coordinate geometry to one O(2), 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 to one Li(1), two equivalent Li(2), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra,  a cornercorner with one O(3)Li3MnCo2 octahedra, corners with two equivalent O(2)Li3Mn2Co octahedra, corners with two equivalent O(4)Li5Co octahedra,  an edgeedge with one O(4)Li5Co octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), two equivalent Mn(1), and one Co(1) atom to form distorted OLi3Mn2Co octahedra that share  a cornercorner with one O(3)Li3MnCo2 octahedra,  a cornercorner with one O(4)Li5Co octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(5)Li4Co2 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3MnCo2 octahedra, edges with two equivalent O(4)Li5Co octahedra, edges with three equivalent O(1)Li3Mn3 octahedra, and edges with three equivalent O(5)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share  a cornercorner with one O(2)Li3Mn2Co octahedra,  a cornercorner with one O(1)Li3Mn3 octahedra, corners with two equivalent O(3)Li3MnCo2 octahedra, corners with two equivalent O(5)Li4Co2 octahedra,  an edgeedge with one O(5)Li4Co2 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(4)Li5Co octahedra, edges with three equivalent O(3)Li3MnCo2 octahedra, and edges with four equivalent O(1)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(2), two equivalent Li(4), and one Co(1) atom to form OLi5Co octahedra that share  a cornercorner with one O(2)Li3Mn2Co octahedra,  a cornercorner with one O(5)Li4Co2 octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(4)Li5Co octahedra,  an edgeedge with one O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3MnCo2 octahedra, edges with three equivalent O(4)Li5Co octahedra, and edges with four equivalent O(5)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the fifth O site, O(5) is bonded to one Li(4), three equivalent Li(3), and two equivalent Co(1) atoms to form OLi4Co2 octahedra that share  a cornercorner with one O(5)Li4Co2 octahedra,  a cornercorner with one O(4)Li5Co octahedra, corners with two equivalent O(2)Li3Mn2Co octahedra, corners with two equivalent O(3)Li3MnCo2 octahedra,  an edgeedge with one O(3)Li3MnCo2 octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, edges with four equivalent O(5)Li4Co2 octahedra, and edges with four equivalent O(4)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-17°.
Li3MnCoO5 is Caswellsilverite-derived structured and 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(3) atoms to form LiO6 octahedra that share corners with two equivalent Mn(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 are 11°. Both Li(1)-O(1) bond lengths are 2.15 Å. All Li(1)-O(3) bond lengths are 2.14 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-11°. The Li(2)-O(2) bond length is 2.08 Å. The Li(2)-O(3) bond length is 2.25 Å. Both Li(2)-O(1) bond lengths are 2.39 Å. Both Li(2)-O(4) bond lengths are 1.95 Å. In the third Li site, Li(3) is bonded to one O(4), two equivalent O(2), and three equivalent O(5) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(4)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. The Li(3)-O(4) bond length is 2.13 Å. Both Li(3)-O(2) bond lengths are 2.44 Å. There are two shorter (2.07 Å) and one longer (2.08 Å) Li(3)-O(5) bond length. In the fourth Li site, Li(4) is bonded to two equivalent O(5) and four equivalent O(4) atoms to form a mixture of edge and corner-sharing LiO6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. Both Li(4)-O(5) bond lengths are 2.12 Å. All Li(4)-O(4) bond lengths are 2.15 Å. Mn(1) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-13°. The Mn(1)-O(3) bond length is 1.86 Å. Both Mn(1)-O(2) bond lengths are 1.93 Å. There are two shorter (2.00 Å) and one longer (2.02 Å) Mn(1)-O(1) bond length. Co(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms. The Co(1)-O(2) bond length is 2.29 Å. The Co(1)-O(4) bond length is 1.80 Å. Both Co(1)-O(3) bond lengths are 2.19 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 to one Li(1), two equivalent Li(2), and three equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share  a cornercorner with one O(1)Li3Mn3 octahedra,  a cornercorner with one O(3)Li3MnCo2 octahedra, corners with two equivalent O(2)Li3Mn2Co octahedra, corners with two equivalent O(4)Li5Co octahedra,  an edgeedge with one O(4)Li5Co octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, edges with four equivalent O(1)Li3Mn3 octahedra, and edges with four equivalent O(3)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), two equivalent Mn(1), and one Co(1) atom to form distorted OLi3Mn2Co octahedra that share  a cornercorner with one O(3)Li3MnCo2 octahedra,  a cornercorner with one O(4)Li5Co octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(5)Li4Co2 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3MnCo2 octahedra, edges with two equivalent O(4)Li5Co octahedra, edges with three equivalent O(1)Li3Mn3 octahedra, and edges with three equivalent O(5)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), one Mn(1), and two equivalent Co(1) atoms to form OLi3MnCo2 octahedra that share  a cornercorner with one O(2)Li3Mn2Co octahedra,  a cornercorner with one O(1)Li3Mn3 octahedra, corners with two equivalent O(3)Li3MnCo2 octahedra, corners with two equivalent O(5)Li4Co2 octahedra,  an edgeedge with one O(5)Li4Co2 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(4)Li5Co octahedra, edges with three equivalent O(3)Li3MnCo2 octahedra, and edges with four equivalent O(1)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(2), two equivalent Li(4), and one Co(1) atom to form OLi5Co octahedra that share  a cornercorner with one O(2)Li3Mn2Co octahedra,  a cornercorner with one O(5)Li4Co2 octahedra, corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent O(4)Li5Co octahedra,  an edgeedge with one O(1)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3MnCo2 octahedra, edges with three equivalent O(4)Li5Co octahedra, and edges with four equivalent O(5)Li4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the fifth O site, O(5) is bonded to one Li(4), three equivalent Li(3), and two equivalent Co(1) atoms to form OLi4Co2 octahedra that share  a cornercorner with one O(5)Li4Co2 octahedra,  a cornercorner with one O(4)Li5Co octahedra, corners with two equivalent O(2)Li3Mn2Co octahedra, corners with two equivalent O(3)Li3MnCo2 octahedra,  an edgeedge with one O(3)Li3MnCo2 octahedra, edges with three equivalent O(2)Li3Mn2Co octahedra, edges with four equivalent O(5)Li4Co2 octahedra, and edges with four equivalent O(4)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 0-17°.