Zn11(CN5)2 crystallizes in the tetragonal P4_2/mnm space group. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent N(4) and four equivalent N(1) atoms to form edge-sharing ZnN6 octahedra. In the second Zn site, Zn(2) is bonded in a 5-coordinate geometry to one N(1), two equivalent N(2), and two equivalent N(4) atoms. In the third Zn site, Zn(3) is bonded in a square co-planar geometry to two equivalent N(1) and two equivalent N(3) atoms. In the fourth Zn site, Zn(4) is bonded in a distorted trigonal planar geometry to three equivalent N(2) 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(3) is bonded in a 3-coordinate geometry to two equivalent Zn(3) and one C(1) atom. In the second N site, N(4) is bonded in a distorted single-bond geometry to one Zn(1), four equivalent Zn(2), and one C(1) atom. In the third N site, N(1) is bonded to two equivalent Zn(1), two equivalent Zn(2), and two equivalent Zn(3) atoms to form NZn6 octahedra that share corners with two equivalent N(1)Zn6 octahedra, corners with four equivalent N(2)Zn5 square pyramids, and edges with three equivalent N(1)Zn6 octahedra. The corner-sharing octahedra are not tilted. In the fourth N site, N(2) is bonded to two equivalent Zn(2) and three equivalent Zn(4) atoms to form distorted NZn5 square pyramids that share corners with two equivalent N(1)Zn6 octahedra, corners with four equivalent N(2)Zn5 square pyramids, and edges with two equivalent N(2)Zn5 square pyramids. The corner-sharing octahedral tilt angles are 61°.
Zn11(CN5)2 crystallizes in the tetragonal P4_2/mnm space group. There are four inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent N(4) and four equivalent N(1) atoms to form edge-sharing ZnN6 octahedra. Both Zn(1)-N(4) bond lengths are 2.38 Å. All Zn(1)-N(1) bond lengths are 2.21 Å. In the second Zn site, Zn(2) is bonded in a 5-coordinate geometry to one N(1), two equivalent N(2), and two equivalent N(4) atoms. The Zn(2)-N(1) bond length is 2.05 Å. Both Zn(2)-N(2) bond lengths are 2.13 Å. Both Zn(2)-N(4) bond lengths are 2.49 Å. In the third Zn site, Zn(3) is bonded in a square co-planar geometry to two equivalent N(1) and two equivalent N(3) atoms. Both Zn(3)-N(1) bond lengths are 2.13 Å. Both Zn(3)-N(3) bond lengths are 2.10 Å. In the fourth Zn site, Zn(4) is bonded in a distorted trigonal planar geometry to three equivalent N(2) atoms. There is one shorter (1.97 Å) and two longer (2.08 Å) Zn(4)-N(2) bond lengths. 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 1.23 Å. The C(1)-N(4) bond length is 1.23 Å. There are four inequivalent N sites. In the first N site, N(3) is bonded in a 3-coordinate geometry to two equivalent Zn(3) and one C(1) atom. In the second N site, N(4) is bonded in a distorted single-bond geometry to one Zn(1), four equivalent Zn(2), and one C(1) atom. In the third N site, N(1) is bonded to two equivalent Zn(1), two equivalent Zn(2), and two equivalent Zn(3) atoms to form NZn6 octahedra that share corners with two equivalent N(1)Zn6 octahedra, corners with four equivalent N(2)Zn5 square pyramids, and edges with three equivalent N(1)Zn6 octahedra. The corner-sharing octahedra are not tilted. In the fourth N site, N(2) is bonded to two equivalent Zn(2) and three equivalent Zn(4) atoms to form distorted NZn5 square pyramids that share corners with two equivalent N(1)Zn6 octahedra, corners with four equivalent N(2)Zn5 square pyramids, and edges with two equivalent N(2)Zn5 square pyramids. The corner-sharing octahedral tilt angles are 61°.