Cr3N2 crystallizes in the monoclinic C2/m space group. There are five inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one N(3), two equivalent N(1), and two equivalent N(2) atoms to form distorted CrN5 trigonal bipyramids that share corners with five equivalent Cr(2)N4 tetrahedra,  an edgeedge with one Cr(2)N4 tetrahedra, and edges with two equivalent Cr(1)N5 trigonal bipyramids. In the second Cr site, Cr(2) is bonded to one N(3) and three equivalent N(2) atoms to form distorted CrN4 tetrahedra that share corners with two equivalent Cr(2)N4 tetrahedra, corners with five equivalent Cr(1)N5 trigonal bipyramids, edges with two equivalent Cr(2)N4 tetrahedra, and  an edgeedge with one Cr(1)N5 trigonal bipyramid. In the third Cr site, Cr(3) is bonded in a 3-coordinate geometry to one N(2) and two equivalent N(1) atoms. In the fourth Cr site, Cr(4) is bonded in a rectangular see-saw-like geometry to two equivalent N(1) and two equivalent N(3) atoms. In the fifth Cr site, Cr(5) is bonded in a square co-planar geometry to four equivalent N(3) atoms. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to two equivalent Cr(1), two equivalent Cr(3), and two equivalent Cr(4) atoms. In the second N site, N(2) is bonded to one Cr(3), two equivalent Cr(1), and three equivalent Cr(2) atoms to form a mixture of distorted corner and edge-sharing NCr6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 50-64°. In the third N site, N(3) is bonded to one Cr(1), one Cr(2), two equivalent Cr(4), and two equivalent Cr(5) atoms to form a mixture of corner and edge-sharing NCr6 octahedra. The corner-sharing octahedra are not tilted.
Cr3N2 crystallizes in the monoclinic C2/m space group. There are five inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one N(3), two equivalent N(1), and two equivalent N(2) atoms to form distorted CrN5 trigonal bipyramids that share corners with five equivalent Cr(2)N4 tetrahedra,  an edgeedge with one Cr(2)N4 tetrahedra, and edges with two equivalent Cr(1)N5 trigonal bipyramids. The Cr(1)-N(3) bond length is 2.02 Å. Both Cr(1)-N(1) bond lengths are 2.07 Å. Both Cr(1)-N(2) bond lengths are 2.04 Å. In the second Cr site, Cr(2) is bonded to one N(3) and three equivalent N(2) atoms to form distorted CrN4 tetrahedra that share corners with two equivalent Cr(2)N4 tetrahedra, corners with five equivalent Cr(1)N5 trigonal bipyramids, edges with two equivalent Cr(2)N4 tetrahedra, and  an edgeedge with one Cr(1)N5 trigonal bipyramid. The Cr(2)-N(3) bond length is 1.96 Å. There is one shorter (1.96 Å) and two longer (2.04 Å) Cr(2)-N(2) bond lengths. In the third Cr site, Cr(3) is bonded in a 3-coordinate geometry to one N(2) and two equivalent N(1) atoms. The Cr(3)-N(2) bond length is 1.97 Å. Both Cr(3)-N(1) bond lengths are 1.96 Å. In the fourth Cr site, Cr(4) is bonded in a rectangular see-saw-like geometry to two equivalent N(1) and two equivalent N(3) atoms. There is one shorter (1.93 Å) and one longer (2.13 Å) Cr(4)-N(1) bond length. Both Cr(4)-N(3) bond lengths are 1.92 Å. In the fifth Cr site, Cr(5) is bonded in a square co-planar geometry to four equivalent N(3) atoms. All Cr(5)-N(3) bond lengths are 1.97 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a 6-coordinate geometry to two equivalent Cr(1), two equivalent Cr(3), and two equivalent Cr(4) atoms. In the second N site, N(2) is bonded to one Cr(3), two equivalent Cr(1), and three equivalent Cr(2) atoms to form a mixture of distorted corner and edge-sharing NCr6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 50-64°. In the third N site, N(3) is bonded to one Cr(1), one Cr(2), two equivalent Cr(4), and two equivalent Cr(5) atoms to form a mixture of corner and edge-sharing NCr6 octahedra. The corner-sharing octahedra are not tilted.