Li3Mn(CoO3)2 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(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, edges with two equivalent Co(2)O6 octahedra, and edges with four equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)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 two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, and edges with three equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the second Co site, Co(2) is bonded to one O(5), one O(6), two equivalent O(2), and two equivalent O(4) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Mn(1), and two equivalent Co(1) atoms to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one Mn(1), and two equivalent Co(2) atoms to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the third O site, O(3) is bonded to one Li(1), one Li(3), one Li(4), one Mn(1), and two equivalent Co(1) atoms to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), one Mn(1), and two equivalent Co(2) atoms to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(3), one Mn(1), one Co(1), and one Co(2) atom to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Li(4), one Mn(1), one Co(1), and one Co(2) atom to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
Li3Mn(CoO3)2 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. Both Li(1)-O(2) bond lengths are 2.12 Å. Both Li(1)-O(3) bond lengths are 2.21 Å. Both Li(1)-O(5) bond lengths are 2.18 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(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, edges with two equivalent Co(2)O6 octahedra, and edges with four equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Li(2)-O(1) bond lengths are 2.12 Å. Both Li(2)-O(4) bond lengths are 2.26 Å. Both Li(2)-O(6) bond lengths are 2.14 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. The Li(3)-O(1) bond length is 2.18 Å. The Li(3)-O(2) bond length is 2.10 Å. The Li(3)-O(3) bond length is 2.21 Å. The Li(3)-O(4) bond length is 2.10 Å. There is one shorter (2.12 Å) and one longer (2.19 Å) Li(3)-O(5) bond length. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)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 two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. The Li(4)-O(1) bond length is 2.20 Å. The Li(4)-O(2) bond length is 2.16 Å. The Li(4)-O(3) bond length is 2.06 Å. The Li(4)-O(4) bond length is 2.07 Å. There is one shorter (2.15 Å) and one longer (2.29 Å) Li(4)-O(6) bond length. Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form MnO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, and edges with three equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. The Mn(1)-O(1) bond length is 2.25 Å. The Mn(1)-O(2) bond length is 2.20 Å. The Mn(1)-O(3) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 1.93 Å. The Mn(1)-O(5) bond length is 2.00 Å. The Mn(1)-O(6) bond length is 1.99 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. The Co(1)-O(5) bond length is 2.22 Å. The Co(1)-O(6) bond length is 1.92 Å. There is one shorter (1.91 Å) and one longer (1.94 Å) Co(1)-O(1) bond length. There is one shorter (1.95 Å) and one longer (2.22 Å) Co(1)-O(3) bond length. In the second Co site, Co(2) is bonded to one O(5), one O(6), two equivalent O(2), and two equivalent O(4) atoms to form CoO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with three equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-7°. The Co(2)-O(5) bond length is 1.95 Å. The Co(2)-O(6) bond length is 2.16 Å. There is one shorter (1.88 Å) and one longer (2.07 Å) Co(2)-O(2) bond length. There is one shorter (2.06 Å) and one longer (2.15 Å) Co(2)-O(4) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Mn(1), and two equivalent Co(1) atoms to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one Mn(1), and two equivalent Co(2) atoms to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the third O site, O(3) is bonded to one Li(1), one Li(3), one Li(4), one Mn(1), and two equivalent Co(1) atoms to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), one Mn(1), and two equivalent Co(2) atoms to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(3), one Mn(1), one Co(1), and one Co(2) atom to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Li(4), one Mn(1), one Co(1), and one Co(2) atom to form a mixture of edge and corner-sharing OLi3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.