Abstract
The asymmetric units of the title compounds, trans-di-aqua-(3-benzyl-1,3,5,8,12-penta-aza-cyclo-tetra-decane-κ4 N 1,N 5,N 8,N 12)copper(II) isophthalate monohydrate, [Cu(C16H29N5)(H2O)2](C8H4O4)·H2O, (I), and trans-di-aqua-[3-(pyridin-3-ylmeth-yl)-1,3,5,8,12-penta-aza-cyclo-tetra-decane-κ4 N 1,N 5,N 8,N 12]copper(II) iso-phthalate 0.9-hydrate, [Cu(C15H28N6)(H2O)2](C8H4O4)·0.9H2O, (II) consist of one di-aqua macrocyclic cation, one di-carboxyl-ate anion and uncoordinated water mol-ecule(s). In each compound, the metal ion is coordinated by the four secondary N atoms of the macrocyclic ligand and the mutually trans O atoms of the water mol-ecules in a tetra-gonally distorted octa-hedral geometry. The average equatorial Cu-N bond lengths are significantly shorter than the average axial Cu-O bond lengths [2.020 (9) versus 2.495 (12) Å and 2.015 (4) versus 2.507 (7) Å for (I) and (II), respectively]. The coordinated macrocyclic ligand in the cations of both compounds adopts the most energetically favorable trans-III conformation. In the crystals, the complex cations and counter-anions are connected via hydrogen-bonding inter-actions between the N-H groups of the macrocycles and the O-H groups of coordinated water mol-ecules as the proton donors and the O atoms of the carboxyl-ate as the proton acceptors. Additionally, as a result of O-H⋯O hydrogen bonding with the coordinated and water mol-ecules of crystallization, the isophthalate dianions form layers lying parallel to the (01) and (100) planes in (I) and (II), respectively.
Highlights
Though the isophthalate (1,3-benzenedicarboxylate) dianion is often used as bridging ligand in the construction of metal–organic frameworks (MOFs), a very limited number of its compounds with azamacrocyclic cations have been described to date and all they are complexes of the NiII ion
The average equatorial Cu—N bond lengths are significantly shorter than the average axial Cu—O bond lengths [2.020 (9) versus 2.495 (12) Aand 2.015 (4) versus 2.507 (7) Afor (I) and (II), respectively]
The complex cations and counter-anions are connected via hydrogen-bonding interactions between the N—H groups of the macrocycles and the O—H groups of coordinated water molecules as the proton donors and the O atoms of the carboxylate as the proton acceptors
Summary
2. Structural commentary Each CuII ion in the complex cations in the title compounds (I) and (II) is coordinated in the equatorial plane by four secondary amine N atoms of the azamacrocyclic ligand in a square-planar fashion, and by two O atoms from the water molecules in the axial positions, resulting in a tetragonally distorted octahedral geometry (Table 1, Fig. 1 and Fig. 2). The CuII ions are displaced from the nearly planar (r.m.s. deviations less than 0.01 A ) mean planes of the N4 donor atoms towards the O1W water molecule by 0.024 and 0.033 Ain (I) and (II), respectively Both coordinated macrocyclic ligands adopt the most energetically favourable trans-III (R,R,S,S) conformation (Bosnich et al, 1965) with the five-membered chelate rings in gauche [bite angles 86.28 (1) for (I) and 86.30 (7) for (II)] and six-membered chelate rings in chair [bite angles 93.7 (2) for (I) and 93.7 (9) for (II)] conformations. Because of their low partial population, these were not considered further in the analysis of the hydrogen-bonding network
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