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The asymmetric unit of the first title compound iodido-(1,4,8,11-tetra-aza-cyclo-tetra-decane-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-tetra-aza-cyclo-tetra-decane-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 -tetra-dentate 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.

Crystal structures of Zn(cyclam)I2 (second monoclinic polymorph) and Zn(cyclam)I(I3)

Crystal structures of Zn(cyclam)I₂ (second monoclinic polymorph) and Zn(cyclam)I(I₃)