Zn4CN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a distorted trigonal planar geometry to one N(1) and two equivalent N(2) atoms. In the second Zn site, Zn(2) is bonded to two equivalent N(3) and three equivalent N(2) atoms to form a mixture of distorted corner and edge-sharing ZnN5 trigonal bipyramids. In the third Zn site, Zn(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form a mixture of distorted corner and edge-sharing ZnN5 square pyramids. In the fourth Zn site, Zn(4) is bonded in a distorted trigonal planar geometry to one N(2) and two equivalent N(1) atoms. C(1) is bonded in a linear geometry to one N(3) and one N(4) atom. There are four inequivalent N sites. In the first N site, N(4) is bonded in a distorted trigonal planar geometry to two equivalent Zn(3) and one C(1) atom. In the second N site, N(1) is bonded to one Zn(1), two equivalent Zn(3), and two equivalent Zn(4) atoms to form distorted NZn5 square pyramids that share corners with four equivalent N(2)Zn6 octahedra, corners with two equivalent N(3)Zn3C tetrahedra, and edges with two equivalent N(1)Zn5 square pyramids. The corner-sharing octahedral tilt angles range from 50-60°. In the third N site, N(2) is bonded to one Zn(4), two equivalent Zn(1), and three equivalent Zn(2) atoms to form NZn6 octahedra that share corners with four equivalent N(1)Zn5 square pyramids, corners with four equivalent N(3)Zn3C tetrahedra, edges with four equivalent N(2)Zn6 octahedra, and  an edgeedge with one N(3)Zn3C tetrahedra. In the fourth N site, N(3) is bonded to one Zn(3), two equivalent Zn(2), and one C(1) atom to form distorted NZn3C tetrahedra that share corners with four equivalent N(2)Zn6 octahedra, corners with two equivalent N(1)Zn5 square pyramids, corners with two equivalent N(3)Zn3C tetrahedra, and  an edgeedge with one N(2)Zn6 octahedra. The corner-sharing octahedral tilt angles range from 26-73°.
Zn4CN4 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a distorted trigonal planar geometry to one N(1) and two equivalent N(2) atoms. The Zn(1)-N(1) bond length is 1.94 Å. Both Zn(1)-N(2) bond lengths are 2.06 Å. In the second Zn site, Zn(2) is bonded to two equivalent N(3) and three equivalent N(2) atoms to form a mixture of distorted corner and edge-sharing ZnN5 trigonal bipyramids. Both Zn(2)-N(3) bond lengths are 2.20 Å. There is one shorter (2.14 Å) and two longer (2.26 Å) Zn(2)-N(2) bond lengths. In the third Zn site, Zn(3) is bonded to one N(3), two equivalent N(1), and two equivalent N(4) atoms to form a mixture of distorted corner and edge-sharing ZnN5 square pyramids. The Zn(3)-N(3) bond length is 2.22 Å. Both Zn(3)-N(1) bond lengths are 2.19 Å. Both Zn(3)-N(4) bond lengths are 2.14 Å. In the fourth Zn site, Zn(4) is bonded in a distorted trigonal planar geometry to one N(2) and two equivalent N(1) atoms. The Zn(4)-N(2) bond length is 2.04 Å. Both Zn(4)-N(1) bond lengths are 2.02 Å. C(1) is bonded in a linear geometry to one N(3) and one N(4) atom. The C(1)-N(3) bond length is 1.25 Å. The C(1)-N(4) bond length is 1.22 Å. There are four inequivalent N sites. In the first N site, N(4) is bonded in a distorted trigonal planar geometry to two equivalent Zn(3) and one C(1) atom. In the second N site, N(1) is bonded to one Zn(1), two equivalent Zn(3), and two equivalent Zn(4) atoms to form distorted NZn5 square pyramids that share corners with four equivalent N(2)Zn6 octahedra, corners with two equivalent N(3)Zn3C tetrahedra, and edges with two equivalent N(1)Zn5 square pyramids. The corner-sharing octahedral tilt angles range from 50-60°. In the third N site, N(2) is bonded to one Zn(4), two equivalent Zn(1), and three equivalent Zn(2) atoms to form NZn6 octahedra that share corners with four equivalent N(1)Zn5 square pyramids, corners with four equivalent N(3)Zn3C tetrahedra, edges with four equivalent N(2)Zn6 octahedra, and  an edgeedge with one N(3)Zn3C tetrahedra. In the fourth N site, N(3) is bonded to one Zn(3), two equivalent Zn(2), and one C(1) atom to form distorted NZn3C tetrahedra that share corners with four equivalent N(2)Zn6 octahedra, corners with two equivalent N(1)Zn5 square pyramids, corners with two equivalent N(3)Zn3C tetrahedra, and  an edgeedge with one N(2)Zn6 octahedra. The corner-sharing octahedral tilt angles range from 26-73°.