Crystal structures of Zn(cyclam)I(2) (second monoclinic polymorph) and Zn(cyclam)I(I(3))

The asymmetric unit of the first title compound iodido­(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ(4) N (1),N (4),N (8),N (11))zinc(II) iodide, [ZnI(C(10)H(24)N(4))]I, 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-tetra­aza­cyclo­tetra­decane-κ(4) N (1),N (4),N (8),N (11))zinc(II) triiodide, [ZnI(C(10)H(24)N(4))]I(3), II, consists of half of the centrosymmetric macrocyclic cation, in which the Zn(II) 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 N,N,N,N-tetra­dentate macrocyclic ligand is present in the most energetically favored trans-III conformation. In the crystals of I, the [Zn(C(10)H(24)N(4))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 II are built up from infinite chains of the five-coordinate macrocyclic units arranged along the b-axis direction and perpendicular sheets formed of the triiodide counter-ions without significant hydrogen bonding between them.