Ca11(CoN5)2 is Orthorhombic Perovskite-like structured and crystallizes in the tetragonal P4_2/mnm space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(4) and four equivalent N(1) atoms to form CaN6 octahedra that share corners with four equivalent Ca(3)N6 octahedra, edges with two equivalent Ca(1)N6 octahedra, edges with two equivalent Ca(3)N6 octahedra, and edges with eight equivalent Ca(2)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 1°. In the second Ca site, Ca(2) is bonded to one N(1), two equivalent N(2), and two equivalent N(4) atoms to form distorted CaN5 trigonal bipyramids that share corners with three equivalent Ca(2)N5 trigonal bipyramids, edges with two equivalent Ca(1)N6 octahedra, edges with two equivalent Ca(3)N6 octahedra, and edges with three equivalent Ca(2)N5 trigonal bipyramids. In the third Ca site, Ca(3) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form distorted CaN6 octahedra that share corners with two equivalent Ca(1)N6 octahedra,  an edgeedge with one Ca(1)N6 octahedra, edges with two equivalent Ca(3)N6 octahedra, and edges with four equivalent Ca(2)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 1°. In the fourth Ca site, Ca(4) is bonded in a 4-coordinate geometry to one N(3) and three equivalent N(2) atoms. Co(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 to two equivalent Ca(3), two equivalent Ca(4), and one Co(1) atom to form distorted NCa4Co trigonal bipyramids that share  a cornercorner with one N(4)Ca5Co octahedra, corners with two equivalent N(1)Ca6 octahedra, corners with two equivalent N(3)Ca4Co trigonal bipyramids, and  an edgeedge with one N(1)Ca6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second N site, N(4) is bonded to one Ca(1), four equivalent Ca(2), and one Co(1) atom to form distorted NCa5Co octahedra that share  a cornercorner with one N(4)Ca5Co octahedra,  a cornercorner with one N(3)Ca4Co trigonal bipyramid, edges with two equivalent N(4)Ca5Co octahedra, and edges with four equivalent N(1)Ca6 octahedra. The corner-sharing octahedra are not tilted. In the third N site, N(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Ca(3) atoms to form NCa6 octahedra that share corners with two equivalent N(1)Ca6 octahedra, corners with two equivalent N(3)Ca4Co trigonal bipyramids, edges with three equivalent N(1)Ca6 octahedra, edges with four equivalent N(4)Ca5Co octahedra, and  an edgeedge with one N(3)Ca4Co trigonal bipyramid. The corner-sharing octahedra are not tilted. In the fourth N site, N(2) is bonded in a 6-coordinate geometry to one Ca(3), two equivalent Ca(2), and three equivalent Ca(4) atoms.
Ca11(CoN5)2 is Orthorhombic Perovskite-like structured and crystallizes in the tetragonal P4_2/mnm space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent N(4) and four equivalent N(1) atoms to form CaN6 octahedra that share corners with four equivalent Ca(3)N6 octahedra, edges with two equivalent Ca(1)N6 octahedra, edges with two equivalent Ca(3)N6 octahedra, and edges with eight equivalent Ca(2)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 1°. Both Ca(1)-N(4) bond lengths are 2.43 Å. All Ca(1)-N(1) bond lengths are 2.49 Å. In the second Ca site, Ca(2) is bonded to one N(1), two equivalent N(2), and two equivalent N(4) atoms to form distorted CaN5 trigonal bipyramids that share corners with three equivalent Ca(2)N5 trigonal bipyramids, edges with two equivalent Ca(1)N6 octahedra, edges with two equivalent Ca(3)N6 octahedra, and edges with three equivalent Ca(2)N5 trigonal bipyramids. The Ca(2)-N(1) bond length is 2.45 Å. Both Ca(2)-N(2) bond lengths are 2.53 Å. Both Ca(2)-N(4) bond lengths are 2.60 Å. In the third Ca site, Ca(3) is bonded to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms to form distorted CaN6 octahedra that share corners with two equivalent Ca(1)N6 octahedra,  an edgeedge with one Ca(1)N6 octahedra, edges with two equivalent Ca(3)N6 octahedra, and edges with four equivalent Ca(2)N5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 1°. Both Ca(3)-N(1) bond lengths are 2.46 Å. Both Ca(3)-N(2) bond lengths are 3.02 Å. Both Ca(3)-N(3) bond lengths are 2.32 Å. In the fourth Ca site, Ca(4) is bonded in a 4-coordinate geometry to one N(3) and three equivalent N(2) atoms. The Ca(4)-N(3) bond length is 2.84 Å. There are two shorter (2.41 Å) and one longer (2.51 Å) Ca(4)-N(2) bond length. Co(1) is bonded in a linear geometry to one N(3) and one N(4) atom. The Co(1)-N(3) bond length is 1.63 Å. The Co(1)-N(4) bond length is 1.66 Å. There are four inequivalent N sites. In the first N site, N(3) is bonded to two equivalent Ca(3), two equivalent Ca(4), and one Co(1) atom to form distorted NCa4Co trigonal bipyramids that share  a cornercorner with one N(4)Ca5Co octahedra, corners with two equivalent N(1)Ca6 octahedra, corners with two equivalent N(3)Ca4Co trigonal bipyramids, and  an edgeedge with one N(1)Ca6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second N site, N(4) is bonded to one Ca(1), four equivalent Ca(2), and one Co(1) atom to form distorted NCa5Co octahedra that share  a cornercorner with one N(4)Ca5Co octahedra,  a cornercorner with one N(3)Ca4Co trigonal bipyramid, edges with two equivalent N(4)Ca5Co octahedra, and edges with four equivalent N(1)Ca6 octahedra. The corner-sharing octahedra are not tilted. In the third N site, N(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), and two equivalent Ca(3) atoms to form NCa6 octahedra that share corners with two equivalent N(1)Ca6 octahedra, corners with two equivalent N(3)Ca4Co trigonal bipyramids, edges with three equivalent N(1)Ca6 octahedra, edges with four equivalent N(4)Ca5Co octahedra, and  an edgeedge with one N(3)Ca4Co trigonal bipyramid. The corner-sharing octahedra are not tilted. In the fourth N site, N(2) is bonded in a 6-coordinate geometry to one Ca(3), two equivalent Ca(2), and three equivalent Ca(4) atoms.