Li4Mn3CoO8 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Co(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 4-9°. In the second Li site, Li(2) is bonded to one O(1), one O(4), 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(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 Mn(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the third Li site, Li(3) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)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 6-7°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(4), 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(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 Mn(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the second Mn site, Mn(2) is bonded to two equivalent O(3) and four equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)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 6-7°. Co(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four 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 4-9°. There are four inequivalent O sites. In the first O site, O(1) 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 corners with two equivalent O(4)Li3Mn3 octahedra, corners with four equivalent O(1)Li3MnCo2 octahedra, edges with four equivalent O(2)Li3Mn2Co octahedra, edges with four equivalent O(3)Li3Mn3 octahedra, and edges with four equivalent O(1)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with two equivalent O(2)Li3Mn2Co octahedra, corners with four equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(4)Li3Mn3 octahedra, and edges with four equivalent O(1)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(3)Li3Mn3 octahedra, corners with four equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(4)Li3Mn3 octahedra, and edges with four equivalent O(1)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(3), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(1)Li3MnCo2 octahedra, corners with four equivalent O(4)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn2Co octahedra, edges with four equivalent O(3)Li3Mn3 octahedra, and edges with four equivalent O(4)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.
Li4Mn3CoO8 is Caswellsilverite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Co(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 4-9°. Both Li(1)-O(3) bond lengths are 2.11 Å. There are two shorter (2.08 Å) and two longer (2.41 Å) Li(1)-O(1) bond lengths. In the second Li site, Li(2) is bonded to one O(1), one O(4), 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(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 Mn(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. The Li(2)-O(1) bond length is 2.10 Å. The Li(2)-O(4) bond length is 2.16 Å. There is one shorter (2.17 Å) and one longer (2.19 Å) Li(2)-O(2) bond length. There is one shorter (2.17 Å) and one longer (2.27 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)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 6-7°. Both Li(3)-O(2) bond lengths are 2.13 Å. There are two shorter (2.17 Å) and two longer (2.23 Å) Li(3)-O(4) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(4), 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(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 Mn(2)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. The Mn(1)-O(1) bond length is 1.94 Å. The Mn(1)-O(4) bond length is 1.95 Å. There is one shorter (1.98 Å) and one longer (2.30 Å) Mn(1)-O(2) bond length. There is one shorter (1.96 Å) and one longer (2.34 Å) Mn(1)-O(3) bond length. In the second Mn site, Mn(2) is bonded to two equivalent O(3) and four equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mn(2)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 6-7°. Both Mn(2)-O(3) bond lengths are 1.96 Å. There are two shorter (1.97 Å) and two longer (2.32 Å) Mn(2)-O(4) bond lengths. Co(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four 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 4-9°. Both Co(1)-O(2) bond lengths are 1.94 Å. There are two shorter (2.06 Å) and two longer (2.13 Å) Co(1)-O(1) bond lengths. There are four inequivalent O sites. In the first O site, O(1) 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 corners with two equivalent O(4)Li3Mn3 octahedra, corners with four equivalent O(1)Li3MnCo2 octahedra, edges with four equivalent O(2)Li3Mn2Co octahedra, edges with four equivalent O(3)Li3Mn3 octahedra, and edges with four equivalent O(1)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), two equivalent Mn(1), and one Co(1) atom to form OLi3Mn2Co octahedra that share corners with two equivalent O(2)Li3Mn2Co octahedra, corners with four equivalent O(3)Li3Mn3 octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(4)Li3Mn3 octahedra, and edges with four equivalent O(1)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), one Mn(2), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(3)Li3Mn3 octahedra, corners with four equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(2)Li3Mn2Co octahedra, edges with two equivalent O(3)Li3Mn3 octahedra, edges with four equivalent O(4)Li3Mn3 octahedra, and edges with four equivalent O(1)Li3MnCo2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(3), one Mn(1), and two equivalent Mn(2) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(1)Li3MnCo2 octahedra, corners with four equivalent O(4)Li3Mn3 octahedra, edges with four equivalent O(2)Li3Mn2Co octahedra, edges with four equivalent O(3)Li3Mn3 octahedra, and edges with four equivalent O(4)Li3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°.