Crystal structures of Zn(cyclam)I (second monoclinic polymorph) and Zn(cyclam)I(I).

The asymmetric unit of the first title compound iodido-(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )zinc(II) iodide, [ZnI(CHN)]I, , consists of the zinc-cyclam macrocyclic cation with one iodide anion coordinated to the metal ion [Zn-I = 2.6619 (5) Å] and the second present as a counter-ion. The asymmetric unit of the second title compound iodido-(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ , , , )zinc(II) triiodide, [ZnI(CHN)]I, , consists of half of the centrosymmetric macrocyclic cation, in which the Zn ion coordinated to an iodide anion [Zn-I = 2.766 (2) Å] is disordered over two positions [Zn⋯Zn = 0.810 (3) Å], and of the two halves of the crystallographically non-equivalent, non-coordinated, centrosymmetric triiodide anions. In both compounds, the ,,,-tetra-dentate macrocyclic ligand is present in the most energetically favored -III conformation. In the crystals of , the [Zn(CHN)I] cations and the non-coordinated iodide anions are linked by N-H⋯I and bifurcated N-H⋯(I,I) hydrogen bonds, resulting in the formation of two-dimensional networks lying parallel to the (001) and (101) planes. In contrast, the crystals of are built up from infinite chains of the five-coordinate macrocyclic units arranged along the -axis direction and perpendicular sheets formed of the triiodide counter-ions without significant hydrogen bonding between them.