Co4CN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form CoN4 tetrahedra that share corners with four equivalent Co(4)N5 square pyramids, corners with five equivalent Co(2)N5 square pyramids, corners with two equivalent Co(1)N4 tetrahedra, edges with two equivalent Co(3)CN5 octahedra, and  an edgeedge with one Co(2)N5 square pyramid. In the second Co site, Co(2) is bonded to one N(1), two equivalent N(2), and two equivalent N(3) atoms to form CoN5 square pyramids that share corners with four equivalent Co(3)CN5 octahedra, corners with five equivalent Co(1)N4 tetrahedra, edges with two equivalent Co(2)N5 square pyramids, edges with two equivalent Co(4)N5 square pyramids, and  an edgeedge with one Co(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-71°. In the third Co site, Co(3) is bonded to one C(1), one N(2), two equivalent N(1), and two equivalent N(4) atoms to form distorted CoCN5 octahedra that share corners with four equivalent Co(2)N5 square pyramids, corners with four equivalent Co(4)N5 square pyramids,  a cornercorner with one N(3)Co3C tetrahedra, edges with two equivalent Co(3)CN5 octahedra,  an edgeedge with one Co(4)N5 square pyramid, edges with two equivalent Co(1)N4 tetrahedra, and  a faceface with one Co(4)N5 square pyramid. In the fourth Co site, Co(4) is bonded to one N(2), two equivalent N(1), and two equivalent N(4) atoms to form distorted CoN5 square pyramids that share corners with four equivalent Co(3)CN5 octahedra, corners with four equivalent Co(1)N4 tetrahedra,  an edgeedge with one Co(3)CN5 octahedra, edges with two equivalent Co(2)N5 square pyramids, edges with two equivalent Co(4)N5 square pyramids, and  a faceface with one Co(3)CN5 octahedra. The corner-sharing octahedral tilt angles range from 11-50°. C(1) is bonded in a trigonal planar geometry to one Co(3), one N(3), and one N(4) atom. There are four inequivalent N sites. In the first N site, N(4) is bonded in a 5-coordinate geometry to two equivalent Co(3), two equivalent Co(4), and one C(1) atom. In the second N site, N(1) is bonded to one Co(1), one Co(2), two equivalent Co(3), and two equivalent Co(4) atoms to form NCo6 octahedra that share corners with three equivalent N(3)Co3C tetrahedra and edges with two equivalent N(1)Co6 octahedra. In the third N site, N(2) is bonded in a 6-coordinate geometry to one Co(3), one Co(4), two equivalent Co(1), and two equivalent Co(2) atoms. In the fourth N site, N(3) is bonded to one Co(1), two equivalent Co(2), and one C(1) atom to form NCo3C tetrahedra that share  a cornercorner with one Co(3)CN5 octahedra, corners with three equivalent N(1)Co6 octahedra, and corners with two equivalent N(3)Co3C tetrahedra. The corner-sharing octahedral tilt angles range from 59-85°.
Co4CN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form CoN4 tetrahedra that share corners with four equivalent Co(4)N5 square pyramids, corners with five equivalent Co(2)N5 square pyramids, corners with two equivalent Co(1)N4 tetrahedra, edges with two equivalent Co(3)CN5 octahedra, and  an edgeedge with one Co(2)N5 square pyramid. The Co(1)-N(1) bond length is 1.90 Å. The Co(1)-N(3) bond length is 1.93 Å. Both Co(1)-N(2) bond lengths are 1.88 Å. In the second Co site, Co(2) is bonded to one N(1), two equivalent N(2), and two equivalent N(3) atoms to form CoN5 square pyramids that share corners with four equivalent Co(3)CN5 octahedra, corners with five equivalent Co(1)N4 tetrahedra, edges with two equivalent Co(2)N5 square pyramids, edges with two equivalent Co(4)N5 square pyramids, and  an edgeedge with one Co(1)N4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-71°. The Co(2)-N(1) bond length is 1.90 Å. Both Co(2)-N(2) bond lengths are 1.96 Å. Both Co(2)-N(3) bond lengths are 1.98 Å. In the third Co site, Co(3) is bonded to one C(1), one N(2), two equivalent N(1), and two equivalent N(4) atoms to form distorted CoCN5 octahedra that share corners with four equivalent Co(2)N5 square pyramids, corners with four equivalent Co(4)N5 square pyramids,  a cornercorner with one N(3)Co3C tetrahedra, edges with two equivalent Co(3)CN5 octahedra,  an edgeedge with one Co(4)N5 square pyramid, edges with two equivalent Co(1)N4 tetrahedra, and  a faceface with one Co(4)N5 square pyramid. The Co(3)-C(1) bond length is 1.91 Å. The Co(3)-N(2) bond length is 2.29 Å. Both Co(3)-N(1) bond lengths are 2.12 Å. Both Co(3)-N(4) bond lengths are 1.98 Å. In the fourth Co site, Co(4) is bonded to one N(2), two equivalent N(1), and two equivalent N(4) atoms to form distorted CoN5 square pyramids that share corners with four equivalent Co(3)CN5 octahedra, corners with four equivalent Co(1)N4 tetrahedra,  an edgeedge with one Co(3)CN5 octahedra, edges with two equivalent Co(2)N5 square pyramids, edges with two equivalent Co(4)N5 square pyramids, and  a faceface with one Co(3)CN5 octahedra. The corner-sharing octahedral tilt angles range from 11-50°. The Co(4)-N(2) bond length is 2.02 Å. Both Co(4)-N(1) bond lengths are 1.90 Å. Both Co(4)-N(4) bond lengths are 2.17 Å. C(1) is bonded in a trigonal planar geometry to one Co(3), one N(3), and one N(4) atom. The C(1)-N(3) bond length is 1.35 Å. The C(1)-N(4) bond length is 1.35 Å. There are four inequivalent N sites. In the first N site, N(4) is bonded in a 5-coordinate geometry to two equivalent Co(3), two equivalent Co(4), and one C(1) atom. In the second N site, N(1) is bonded to one Co(1), one Co(2), two equivalent Co(3), and two equivalent Co(4) atoms to form NCo6 octahedra that share corners with three equivalent N(3)Co3C tetrahedra and edges with two equivalent N(1)Co6 octahedra. In the third N site, N(2) is bonded in a 6-coordinate geometry to one Co(3), one Co(4), two equivalent Co(1), and two equivalent Co(2) atoms. In the fourth N site, N(3) is bonded to one Co(1), two equivalent Co(2), and one C(1) atom to form NCo3C tetrahedra that share  a cornercorner with one Co(3)CN5 octahedra, corners with three equivalent N(1)Co6 octahedra, and corners with two equivalent N(3)Co3C tetrahedra. The corner-sharing octahedral tilt angles range from 59-85°.