Co11(CN5)2 crystallizes in the tetragonal P4_2/mnm space group. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent N(4) and four equivalent N(1) atoms to form edge-sharing CoN6 octahedra. In the second Co site, Co(2) is bonded in a 5-coordinate geometry to one N(1), two equivalent N(2), and two equivalent N(4) atoms. In the third Co site, Co(3) is bonded in a rectangular see-saw-like geometry to two equivalent N(1) and two equivalent N(3) atoms. In the fourth Co site, Co(4) is bonded in a distorted trigonal planar geometry to three equivalent N(2) atoms. C(1) is bonded in a linear geometry to one N(3) and one N(4) atom. There are four inequivalent N sites. In the first N site, N(3) is bonded in a 3-coordinate geometry to two equivalent Co(3) and one C(1) atom. In the second N site, N(4) is bonded in a 6-coordinate geometry to one Co(1), four equivalent Co(2), and one C(1) atom. In the third N site, N(1) is bonded to two equivalent Co(1), two equivalent Co(2), and two equivalent Co(3) atoms to form NCo6 octahedra that share corners with two equivalent N(1)Co6 octahedra, corners with four equivalent N(2)Co5 trigonal bipyramids, and edges with three equivalent N(1)Co6 octahedra. The corner-sharing octahedra are not tilted. In the fourth N site, N(2) is bonded to two equivalent Co(2) and three equivalent Co(4) atoms to form distorted NCo5 trigonal bipyramids that share corners with two equivalent N(1)Co6 octahedra, corners with four equivalent N(2)Co5 trigonal bipyramids, and edges with two equivalent N(2)Co5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 62°.
Co11(CN5)2 crystallizes in the tetragonal P4_2/mnm space group. There are four inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent N(4) and four equivalent N(1) atoms to form edge-sharing CoN6 octahedra. Both Co(1)-N(4) bond lengths are 2.14 Å. All Co(1)-N(1) bond lengths are 2.08 Å. In the second Co site, Co(2) is bonded in a 5-coordinate geometry to one N(1), two equivalent N(2), and two equivalent N(4) atoms. The Co(2)-N(1) bond length is 2.03 Å. Both Co(2)-N(2) bond lengths are 1.87 Å. Both Co(2)-N(4) bond lengths are 2.41 Å. In the third Co site, Co(3) is bonded in a rectangular see-saw-like geometry to two equivalent N(1) and two equivalent N(3) atoms. Both Co(3)-N(1) bond lengths are 1.86 Å. Both Co(3)-N(3) bond lengths are 1.98 Å. In the fourth Co site, Co(4) is bonded in a distorted trigonal planar geometry to three equivalent N(2) atoms. There is one shorter (1.87 Å) and two longer (1.89 Å) Co(4)-N(2) bond lengths. C(1) is bonded in a linear geometry to one N(3) and one N(4) atom. The C(1)-N(3) bond length is 1.22 Å. The C(1)-N(4) bond length is 1.25 Å. There are four inequivalent N sites. In the first N site, N(3) is bonded in a 3-coordinate geometry to two equivalent Co(3) and one C(1) atom. In the second N site, N(4) is bonded in a 6-coordinate geometry to one Co(1), four equivalent Co(2), and one C(1) atom. In the third N site, N(1) is bonded to two equivalent Co(1), two equivalent Co(2), and two equivalent Co(3) atoms to form NCo6 octahedra that share corners with two equivalent N(1)Co6 octahedra, corners with four equivalent N(2)Co5 trigonal bipyramids, and edges with three equivalent N(1)Co6 octahedra. The corner-sharing octahedra are not tilted. In the fourth N site, N(2) is bonded to two equivalent Co(2) and three equivalent Co(4) atoms to form distorted NCo5 trigonal bipyramids that share corners with two equivalent N(1)Co6 octahedra, corners with four equivalent N(2)Co5 trigonal bipyramids, and edges with two equivalent N(2)Co5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 62°.