Mn4CoO8 is beta indium sulfide-derived structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form distorted MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. In the second Mn site, Mn(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. Co(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CoO6 octahedra that share edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Mn(3) and one Co(1) atom. In the second O site, O(2) is bonded in a see-saw-like geometry to one Mn(1), one Mn(2), one Mn(3), and one Co(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms.
Mn4CoO8 is beta indium sulfide-derived structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form distorted MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. Both Mn(1)-O(3) bond lengths are 2.19 Å. All Mn(1)-O(2) bond lengths are 2.18 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. Both Mn(2)-O(3) bond lengths are 2.18 Å. All Mn(2)-O(2) bond lengths are 2.04 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form MnO6 octahedra that share edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, edges with two equivalent Mn(3)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. Both Mn(3)-O(1) bond lengths are 1.95 Å. Both Mn(3)-O(2) bond lengths are 1.95 Å. Both Mn(3)-O(3) bond lengths are 1.94 Å. Co(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form CoO6 octahedra that share edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Mn(3)O6 octahedra. Both Co(1)-O(1) bond lengths are 1.96 Å. All Co(1)-O(2) bond lengths are 1.94 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Mn(3) and one Co(1) atom. In the second O site, O(2) is bonded in a see-saw-like geometry to one Mn(1), one Mn(2), one Mn(3), and one Co(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Mn(1), one Mn(2), and two equivalent Mn(3) atoms.