Synthesis and structural characterization of the dichloride complex formed by carb-oxy-functionalized Cu(di-aza-cyclam) cation and its heterometallic coordination polymer with CdCl.

The asymmetric unit of the complex [3,10-bis-(3-carb-oxy-prop-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-decane-κ , , , ]di-chlorido-copper(II), [CuCl(CHNO)] or [Cu(H )Cl] (), consists of a centrosymmetric macrocyclic Cu dication and a chloride anion. The components of the heterometallic compound poly[[aqua-[μ-3,10-bis-(3-carb-oxy-prop-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-dec-ane-κ , , , :κ ,':κ '',''']-μ-chlorido--copper(II)cadmium(II] 1.25-hydrate], {[CuCd(CHNO)Cl(HO)]·1.25HO} or {[CuCd()(HO)Cl]·1.25HO} () are [Cu()(HO)] moieties coordinated to CdCl units the deprotonated carb-oxy-lic groups of the macrocycle, and four water mol-ecules of crystallization with partial occupancies. In each compound, the Cu ion coord-inates in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable -III conformation, and two mutually axial ligands in tetra-gonally elongated -CuNCl and -CuN(HO)Cl octa-hedral geometries in and , respectively. The coordination environment of the Cd ion in is a CdOCl distorted octa-hedron formed by two bidentately coordinated deprotonated carb-oxy-lic groups of different macrocycles and two chloride anions, one of which displays a μ-bridging function between the Cu and Cd ions. The extended structures of both complexes are distinctly lamellar. In particular, due to hydrogen-bonding inter-actions with participation of carb-oxy-lic groups, chloride atoms and secondary amino groups of the macrocycle, the electro-neutral mol-ecules in crystal of are arranged in chains running in the [101] direction; hydrogen bonding between the chains leads to layers parallel to the (101) plane. In crystal of , polymeric chains running along the [101] direction are joined into layers parallel to the (101) plane formation of Cu-Cl bonds and inter-chain hydrogen bonds. There are no hydrogen-bonding inter-actions between the layers and the three-dimensional structure of is based on the weak C-H⋯O and C-H⋯Cl contacts.