Synthesis and structural characterization of the dichloride complex formed by carb-oxy-functionalized Cu(di-aza-cyclam)(2+) cation and its heterometallic coordination polymer with CdCl(2).

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(4) N (1),N (5),N (8),N (12)]di-chlorido-copper(II), [CuCl(2)(C(16)H(34)N(6)O(4))] or [Cu(H(2) L)Cl(2)] (I), consists of a centrosymmetric macrocyclic Cu(II) dication and a chloride anion. The components of the heterometallic compound poly[[aqua-[μ(3)-3,10-bis-(3-carb-oxy-prop-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-dec-ane-κ(4) N (1),N (5),N (8),N (12):κ(2) O,O':κ(2) O'',O''']-μ-chlorido--copper(II)cadmium(II] 1.25-hydrate], {[CuCd(C(16)H(32)N(6)O(4))Cl(2)(H(2)O)]·1.25H(2)O} (n) or {[CuCd(L)(H(2)O)Cl(2)]·1.25H(2)O} (n) (II) are [Cu(L)(H(2)O)] moieties coordinated to CdCl(2) units via the deprotonated carb-oxy-lic groups of the macrocycle, and four water mol-ecules of crystallization with partial occupancies. In each compound, the Cu(II) ion coord-inates in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable trans-III conformation, and two mutually trans axial ligands in tetra-gonally elongated trans-CuN(4)Cl(2) and trans-CuN(4)(H(2)O)Cl octa-hedral geometries in I and II, respectively. The coordination environment of the Cd(II) ion in II is a CdO(4)Cl(2) 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(2)-bridging function between the Cu(II) and Cd(II) 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 I 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 II, polymeric chains running along the [101] direction are joined into layers parallel to the (101) plane via 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 II is based on the weak C-H⋯O and C-H⋯Cl contacts.