Ca3(CrN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to one N(1) and three equivalent N(2) atoms. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form edge-sharing CrN4 tetrahedra. In the second Cr site, Cr(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing CrN4 tetrahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one Cr(1), and one Cr(2) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(2), three equivalent Ca(1), one Cr(1), and one Cr(2) atom.
Ca3(CrN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 4-coordinate geometry to one N(1) and three equivalent N(2) atoms. The Ca(1)-N(1) bond length is 2.39 Å. There are a spread of Ca(1)-N(2) bond distances ranging from 2.39-2.57 Å. In the second Ca site, Ca(2) is bonded in a 6-coordinate geometry to two equivalent N(2) and four equivalent N(1) atoms. Both Ca(2)-N(2) bond lengths are 2.75 Å. There are two shorter (2.57 Å) and two longer (2.59 Å) Ca(2)-N(1) bond lengths. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form edge-sharing CrN4 tetrahedra. Both Cr(1)-N(1) bond lengths are 1.87 Å. Both Cr(1)-N(2) bond lengths are 1.86 Å. In the second Cr site, Cr(2) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted edge-sharing CrN4 tetrahedra. Both Cr(2)-N(1) bond lengths are 1.93 Å. Both Cr(2)-N(2) bond lengths are 1.93 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 5-coordinate geometry to one Ca(1), two equivalent Ca(2), one Cr(1), and one Cr(2) atom. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(2), three equivalent Ca(1), one Cr(1), and one Cr(2) atom.