Zn3N2 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one N(1) and three equivalent N(2) atoms to form a mixture of corner and edge-sharing ZnN4 tetrahedra. In the second Zn site, Zn(2) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. In the third Zn site, Zn(3) is bonded to one N(1) and three equivalent N(2) atoms to form a mixture of corner and edge-sharing ZnN4 tetrahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Zn(1), one Zn(3), and three equivalent Zn(2) atoms to form NZn5 trigonal bipyramids that share corners with six equivalent N(2)Zn6 octahedra and corners with six equivalent N(1)Zn5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 61-67°. In the second N site, N(2) is bonded to three equivalent Zn(1) and three equivalent Zn(3) atoms to form distorted NZn6 octahedra that share corners with six equivalent N(1)Zn5 trigonal bipyramids and edges with six equivalent N(2)Zn6 octahedra.
Zn3N2 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one N(1) and three equivalent N(2) atoms to form a mixture of corner and edge-sharing ZnN4 tetrahedra. The Zn(1)-N(1) bond length is 2.05 Å. There are two shorter (2.17 Å) and one longer (2.21 Å) Zn(1)-N(2) bond length. In the second Zn site, Zn(2) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. All Zn(2)-N(1) bond lengths are 1.97 Å. In the third Zn site, Zn(3) is bonded to one N(1) and three equivalent N(2) atoms to form a mixture of corner and edge-sharing ZnN4 tetrahedra. The Zn(3)-N(1) bond length is 2.06 Å. There is one shorter (2.16 Å) and two longer (2.20 Å) Zn(3)-N(2) bond lengths. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Zn(1), one Zn(3), and three equivalent Zn(2) atoms to form NZn5 trigonal bipyramids that share corners with six equivalent N(2)Zn6 octahedra and corners with six equivalent N(1)Zn5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 61-67°. In the second N site, N(2) is bonded to three equivalent Zn(1) and three equivalent Zn(3) atoms to form distorted NZn6 octahedra that share corners with six equivalent N(1)Zn5 trigonal bipyramids and edges with six equivalent N(2)Zn6 octahedra.