Ca3CrN3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2) and four equivalent N(1) atoms to form a mixture of distorted corner and edge-sharing CaN5 square pyramids. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and three equivalent N(2) atoms to form a mixture of corner and edge-sharing CaN5 square pyramids. Cr(1) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(1) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(2), four equivalent Ca(1), and one Cr(1) atom to form a mixture of distorted corner and edge-sharing NCa5Cr octahedra. The corner-sharing octahedral tilt angles range from 9-46°. In the second N site, N(2) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one Cr(1) atom to form a mixture of corner and edge-sharing NCa5Cr octahedra. The corner-sharing octahedral tilt angles are 9°.
Ca3CrN3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to one N(2) and four equivalent N(1) atoms to form a mixture of distorted corner and edge-sharing CaN5 square pyramids. The Ca(1)-N(2) bond length is 2.41 Å. There are three shorter (2.52 Å) and one longer (2.73 Å) Ca(1)-N(1) bond length. In the second Ca site, Ca(2) is bonded to two equivalent N(1) and three equivalent N(2) atoms to form a mixture of corner and edge-sharing CaN5 square pyramids. Both Ca(2)-N(1) bond lengths are 2.61 Å. There is one shorter (2.38 Å) and two longer (2.52 Å) Ca(2)-N(2) bond lengths. Cr(1) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(1) atoms. The Cr(1)-N(2) bond length is 1.84 Å. Both Cr(1)-N(1) bond lengths are 1.76 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(2), four equivalent Ca(1), and one Cr(1) atom to form a mixture of distorted corner and edge-sharing NCa5Cr octahedra. The corner-sharing octahedral tilt angles range from 9-46°. In the second N site, N(2) is bonded to two equivalent Ca(1), three equivalent Ca(2), and one Cr(1) atom to form a mixture of corner and edge-sharing NCa5Cr octahedra. The corner-sharing octahedral tilt angles are 9°.