Mn3(CoN)8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a square co-planar geometry to two equivalent N(3) and two equivalent N(4) atoms. In the second Mn site, Mn(2) is bonded in a 3-coordinate geometry to one N(1), one N(2), and one N(3) atom. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded in a 5-coordinate geometry to one N(2), two equivalent N(1), and two equivalent N(4) atoms. In the second Co site, Co(2) is bonded to one N(3), one N(4), and three equivalent N(2) atoms to form a mixture of edge and corner-sharing CoN5 square pyramids. In the third Co site, Co(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form a mixture of edge and corner-sharing CoN5 square pyramids. In the fourth Co site, Co(4) is bonded in a square co-planar geometry to one N(1), one N(2), and two equivalent N(3) atoms. There are four inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Mn(2), one Co(4), two equivalent Co(1), and two equivalent Co(3) atoms. In the second N site, N(2) is bonded to one Mn(2), one Co(1), one Co(4), and three equivalent Co(2) atoms to form NMnCo5 octahedra that share  a cornercorner with one N(4)MnCo5 octahedra, corners with two equivalent N(2)MnCo5 octahedra, edges with two equivalent N(2)MnCo5 octahedra, edges with two equivalent N(4)MnCo5 octahedra, and edges with three equivalent N(3)Mn2Co4 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the third N site, N(3) is bonded to one Mn(1), one Mn(2), one Co(2), one Co(3), and two equivalent Co(4) atoms to form NMn2Co4 octahedra that share  a cornercorner with one N(4)MnCo5 octahedra, corners with three equivalent N(3)Mn2Co4 octahedra, edges with two equivalent N(4)MnCo5 octahedra, and edges with three equivalent N(2)MnCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth N site, N(4) is bonded to one Mn(1), one Co(2), two equivalent Co(1), and two equivalent Co(3) atoms to form NMnCo5 octahedra that share  a cornercorner with one N(3)Mn2Co4 octahedra,  a cornercorner with one N(2)MnCo5 octahedra, corners with three equivalent N(4)MnCo5 octahedra,  an edgeedge with one N(4)MnCo5 octahedra, edges with two equivalent N(3)Mn2Co4 octahedra, and edges with two equivalent N(2)MnCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-18°.
Mn3(CoN)8 crystallizes in the monoclinic C2/m space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a square co-planar geometry to two equivalent N(3) and two equivalent N(4) atoms. Both Mn(1)-N(3) bond lengths are 2.05 Å. Both Mn(1)-N(4) bond lengths are 2.04 Å. In the second Mn site, Mn(2) is bonded in a 3-coordinate geometry to one N(1), one N(2), and one N(3) atom. The Mn(2)-N(1) bond length is 1.81 Å. The Mn(2)-N(2) bond length is 1.79 Å. The Mn(2)-N(3) bond length is 1.86 Å. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded in a 5-coordinate geometry to one N(2), two equivalent N(1), and two equivalent N(4) atoms. The Co(1)-N(2) bond length is 2.16 Å. There is one shorter (1.85 Å) and one longer (2.45 Å) Co(1)-N(1) bond length. Both Co(1)-N(4) bond lengths are 2.00 Å. In the second Co site, Co(2) is bonded to one N(3), one N(4), and three equivalent N(2) atoms to form a mixture of edge and corner-sharing CoN5 square pyramids. The Co(2)-N(3) bond length is 2.07 Å. The Co(2)-N(4) bond length is 1.88 Å. There are two shorter (1.98 Å) and one longer (2.01 Å) Co(2)-N(2) bond length. In the third Co site, Co(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form a mixture of edge and corner-sharing CoN5 square pyramids. The Co(3)-N(3) bond length is 2.06 Å. Both Co(3)-N(1) bond lengths are 2.01 Å. There is one shorter (1.99 Å) and one longer (2.00 Å) Co(3)-N(4) bond length. In the fourth Co site, Co(4) is bonded in a square co-planar geometry to one N(1), one N(2), and two equivalent N(3) atoms. The Co(4)-N(1) bond length is 1.88 Å. The Co(4)-N(2) bond length is 1.96 Å. Both Co(4)-N(3) bond lengths are 1.98 Å. There are four inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to one Mn(2), one Co(4), two equivalent Co(1), and two equivalent Co(3) atoms. In the second N site, N(2) is bonded to one Mn(2), one Co(1), one Co(4), and three equivalent Co(2) atoms to form NMnCo5 octahedra that share  a cornercorner with one N(4)MnCo5 octahedra, corners with two equivalent N(2)MnCo5 octahedra, edges with two equivalent N(2)MnCo5 octahedra, edges with two equivalent N(4)MnCo5 octahedra, and edges with three equivalent N(3)Mn2Co4 octahedra. The corner-sharing octahedral tilt angles range from 3-9°. In the third N site, N(3) is bonded to one Mn(1), one Mn(2), one Co(2), one Co(3), and two equivalent Co(4) atoms to form NMn2Co4 octahedra that share  a cornercorner with one N(4)MnCo5 octahedra, corners with three equivalent N(3)Mn2Co4 octahedra, edges with two equivalent N(4)MnCo5 octahedra, and edges with three equivalent N(2)MnCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the fourth N site, N(4) is bonded to one Mn(1), one Co(2), two equivalent Co(1), and two equivalent Co(3) atoms to form NMnCo5 octahedra that share  a cornercorner with one N(3)Mn2Co4 octahedra,  a cornercorner with one N(2)MnCo5 octahedra, corners with three equivalent N(4)MnCo5 octahedra,  an edgeedge with one N(4)MnCo5 octahedra, edges with two equivalent N(3)Mn2Co4 octahedra, and edges with two equivalent N(2)MnCo5 octahedra. The corner-sharing octahedral tilt angles range from 0-18°.