Ca5(CrN3)2 crystallizes in the monoclinic Pm space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2), one N(4), one N(5), and two equivalent N(1) atoms to form distorted CaN5 square pyramids that share  a cornercorner with one Ca(4)N5 square pyramid, corners with two equivalent Ca(1)N5 square pyramids, corners with two equivalent Ca(5)N4 trigonal pyramids,  an edgeedge with one Ca(4)N5 square pyramid, and edges with two equivalent Ca(2)N5 square pyramids. In the second Ca site, Ca(2) is bonded to one N(1), one N(3), one N(6), and two equivalent N(2) atoms to form distorted CaN5 square pyramids that share corners with two equivalent Ca(2)N5 square pyramids, edges with two equivalent Ca(1)N5 square pyramids, edges with two equivalent Ca(4)N5 square pyramids, and  an edgeedge with one Ca(5)N4 trigonal pyramid. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one N(1), one N(3), one N(6), and two equivalent N(4) atoms. In the fourth Ca site, Ca(4) is bonded to one N(2), one N(4), one N(5), and two equivalent N(3) atoms to form CaN5 square pyramids that share  a cornercorner with one Ca(1)N5 square pyramid, corners with two equivalent Ca(4)N5 square pyramids,  an edgeedge with one Ca(1)N5 square pyramid, edges with two equivalent Ca(2)N5 square pyramids, and edges with two equivalent Ca(5)N4 trigonal pyramids. In the fifth Ca site, Ca(5) is bonded to one N(3), one N(6), and two equivalent N(5) atoms to form distorted CaN4 trigonal pyramids that share corners with two equivalent Ca(1)N5 square pyramids, corners with two equivalent Ca(5)N4 trigonal pyramids,  an edgeedge with one Ca(2)N5 square pyramid, and edges with two equivalent Ca(4)N5 square pyramids. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a trigonal planar geometry to one N(1), one N(3), and one N(6) atom. In the second Cr site, Cr(2) is bonded in a trigonal planar geometry to one N(2), one N(4), and one N(5) atom. There are six inequivalent N sites. In the first N site, N(1) is bonded in a 1-coordinate geometry to one Ca(2), one Ca(3), two equivalent Ca(1), and one Cr(1) atom. In the second N site, N(2) is bonded to one Ca(1), one Ca(4), two equivalent Ca(2), and one Cr(2) atom to form NCa4Cr square pyramids that share  a cornercorner with one N(5)Ca4Cr square pyramid, corners with two equivalent N(2)Ca4Cr square pyramids,  a cornercorner with one N(4)Ca4Cr trigonal bipyramid, edges with two equivalent N(3)Ca5Cr octahedra,  an edgeedge with one N(5)Ca4Cr square pyramid, and  an edgeedge with one N(4)Ca4Cr trigonal bipyramid. In the third N site, N(3) is bonded to one Ca(2), one Ca(3), one Ca(5), two equivalent Ca(4), and one Cr(1) atom to form NCa5Cr octahedra that share corners with two equivalent N(3)Ca5Cr octahedra, edges with two equivalent N(2)Ca4Cr square pyramids, edges with two equivalent N(5)Ca4Cr square pyramids, and edges with two equivalent N(4)Ca4Cr trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°. In the fourth N site, N(4) is bonded to one Ca(1), one Ca(4), two equivalent Ca(3), and one Cr(2) atom to form distorted NCa4Cr trigonal bipyramids that share  a cornercorner with one N(2)Ca4Cr square pyramid, corners with three equivalent N(5)Ca4Cr square pyramids, corners with two equivalent N(4)Ca4Cr trigonal bipyramids, edges with two equivalent N(3)Ca5Cr octahedra, and  an edgeedge with one N(2)Ca4Cr square pyramid. In the fifth N site, N(5) is bonded to one Ca(1), one Ca(4), two equivalent Ca(5), and one Cr(2) atom to form distorted NCa4Cr square pyramids that share  a cornercorner with one N(2)Ca4Cr square pyramid, corners with two equivalent N(5)Ca4Cr square pyramids, corners with three equivalent N(4)Ca4Cr trigonal bipyramids, edges with two equivalent N(3)Ca5Cr octahedra, and  an edgeedge with one N(2)Ca4Cr square pyramid. In the sixth N site, N(6) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one Ca(5), and one Cr(1) atom.
Ca5(CrN3)2 crystallizes in the monoclinic Pm space group. There are five inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2), one N(4), one N(5), and two equivalent N(1) atoms to form distorted CaN5 square pyramids that share  a cornercorner with one Ca(4)N5 square pyramid, corners with two equivalent Ca(1)N5 square pyramids, corners with two equivalent Ca(5)N4 trigonal pyramids,  an edgeedge with one Ca(4)N5 square pyramid, and edges with two equivalent Ca(2)N5 square pyramids. The Ca(1)-N(2) bond length is 2.47 Å. The Ca(1)-N(4) bond length is 2.41 Å. The Ca(1)-N(5) bond length is 2.62 Å. Both Ca(1)-N(1) bond lengths are 2.51 Å. In the second Ca site, Ca(2) is bonded to one N(1), one N(3), one N(6), and two equivalent N(2) atoms to form distorted CaN5 square pyramids that share corners with two equivalent Ca(2)N5 square pyramids, edges with two equivalent Ca(1)N5 square pyramids, edges with two equivalent Ca(4)N5 square pyramids, and  an edgeedge with one Ca(5)N4 trigonal pyramid. The Ca(2)-N(1) bond length is 2.78 Å. The Ca(2)-N(3) bond length is 2.46 Å. The Ca(2)-N(6) bond length is 2.41 Å. Both Ca(2)-N(2) bond lengths are 2.52 Å. In the third Ca site, Ca(3) is bonded in a 5-coordinate geometry to one N(1), one N(3), one N(6), and two equivalent N(4) atoms. The Ca(3)-N(1) bond length is 2.55 Å. The Ca(3)-N(3) bond length is 2.39 Å. The Ca(3)-N(6) bond length is 2.81 Å. Both Ca(3)-N(4) bond lengths are 2.52 Å. In the fourth Ca site, Ca(4) is bonded to one N(2), one N(4), one N(5), and two equivalent N(3) atoms to form CaN5 square pyramids that share  a cornercorner with one Ca(1)N5 square pyramid, corners with two equivalent Ca(4)N5 square pyramids,  an edgeedge with one Ca(1)N5 square pyramid, edges with two equivalent Ca(2)N5 square pyramids, and edges with two equivalent Ca(5)N4 trigonal pyramids. The Ca(4)-N(2) bond length is 2.48 Å. The Ca(4)-N(4) bond length is 2.57 Å. The Ca(4)-N(5) bond length is 2.62 Å. Both Ca(4)-N(3) bond lengths are 2.51 Å. In the fifth Ca site, Ca(5) is bonded to one N(3), one N(6), and two equivalent N(5) atoms to form distorted CaN4 trigonal pyramids that share corners with two equivalent Ca(1)N5 square pyramids, corners with two equivalent Ca(5)N4 trigonal pyramids,  an edgeedge with one Ca(2)N5 square pyramid, and edges with two equivalent Ca(4)N5 square pyramids. The Ca(5)-N(3) bond length is 2.42 Å. The Ca(5)-N(6) bond length is 2.39 Å. Both Ca(5)-N(5) bond lengths are 2.56 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a trigonal planar geometry to one N(1), one N(3), and one N(6) atom. The Cr(1)-N(1) bond length is 1.75 Å. The Cr(1)-N(3) bond length is 1.79 Å. The Cr(1)-N(6) bond length is 1.68 Å. In the second Cr site, Cr(2) is bonded in a trigonal planar geometry to one N(2), one N(4), and one N(5) atom. The Cr(2)-N(2) bond length is 1.73 Å. The Cr(2)-N(4) bond length is 1.74 Å. The Cr(2)-N(5) bond length is 1.71 Å. There are six inequivalent N sites. In the first N site, N(1) is bonded in a 1-coordinate geometry to one Ca(2), one Ca(3), two equivalent Ca(1), and one Cr(1) atom. In the second N site, N(2) is bonded to one Ca(1), one Ca(4), two equivalent Ca(2), and one Cr(2) atom to form NCa4Cr square pyramids that share  a cornercorner with one N(5)Ca4Cr square pyramid, corners with two equivalent N(2)Ca4Cr square pyramids,  a cornercorner with one N(4)Ca4Cr trigonal bipyramid, edges with two equivalent N(3)Ca5Cr octahedra,  an edgeedge with one N(5)Ca4Cr square pyramid, and  an edgeedge with one N(4)Ca4Cr trigonal bipyramid. In the third N site, N(3) is bonded to one Ca(2), one Ca(3), one Ca(5), two equivalent Ca(4), and one Cr(1) atom to form NCa5Cr octahedra that share corners with two equivalent N(3)Ca5Cr octahedra, edges with two equivalent N(2)Ca4Cr square pyramids, edges with two equivalent N(5)Ca4Cr square pyramids, and edges with two equivalent N(4)Ca4Cr trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°. In the fourth N site, N(4) is bonded to one Ca(1), one Ca(4), two equivalent Ca(3), and one Cr(2) atom to form distorted NCa4Cr trigonal bipyramids that share  a cornercorner with one N(2)Ca4Cr square pyramid, corners with three equivalent N(5)Ca4Cr square pyramids, corners with two equivalent N(4)Ca4Cr trigonal bipyramids, edges with two equivalent N(3)Ca5Cr octahedra, and  an edgeedge with one N(2)Ca4Cr square pyramid. In the fifth N site, N(5) is bonded to one Ca(1), one Ca(4), two equivalent Ca(5), and one Cr(2) atom to form distorted NCa4Cr square pyramids that share  a cornercorner with one N(2)Ca4Cr square pyramid, corners with two equivalent N(5)Ca4Cr square pyramids, corners with three equivalent N(4)Ca4Cr trigonal bipyramids, edges with two equivalent N(3)Ca5Cr octahedra, and  an edgeedge with one N(2)Ca4Cr square pyramid. In the sixth N site, N(6) is bonded in a 4-coordinate geometry to one Ca(2), one Ca(3), one Ca(5), and one Cr(1) atom.