Self-assembly between perchlorate salts of Cu(II), Zn(II) and Cd(II) with tri-substituted N-propionic acid functionalized 1,4,7-triazacyclononane (H 3 L 1 ) or the mono-substituted one (HL 2 ) results in the formation of four novel complexes [Cu 5 (H 3) and [Cd(L 2 )]ClO 4 $CH 3 OH (4) with different aggregation modes. All these complexes were structurally characterized by solid state X-ray diffraction measurement. Complex 1 belongs to a homometallic 2D polymer, where each [Cu(L 1 )] À complex entity acts as a three-connected node joined to three Cu(II) ions through m 2 bridged propionate arms to afford a puckered honeycomb framework. In complex 2, two face-to-face arranged [Zn(L 1 )] À moieties clip three Zn(II) ions by virtue of pendant propionate arms generating a macrotricyclic metallacryptate. Two such metallacryptates are fused via co-sharing one lateral Zn(II) ion into an unprecedented nonazinc cluster with a doublecage architecture. Complex 3 exhibits a discrete centrosymmetric dinuclear unit [Cd 2 (H 2 L 1 ) 2 ] 2+ consisting of two pendant propionate groups linked to a [Cd 2 O 2 ] core. Complex 4 reveals Cd(II) centers are associated through the unique propionate bridge of the L 2 À ligand leading to an infinite 1D zig-zag polymeric chain of [Cd(L 2 )] + cations. Deduced from the structural investigations, the linkage patterns of the selected macrocyclic ligands towards metal centers may be exquisitely tuned according to the type of metals and the number of the coordinating pendant arms present in the macrocyclic ligands, and then the architectural variation of these metal-organic coordination species is achieved. In addition, magnetic studies for complex 1 show a weak Cu/Cu antiferromagnetic coupling in the 2D honeycomb layer with a Weiss temperature of À4.31 K.
In the title half-sandwich compound, [Ni(C6H15N3)(H2O)3]Br(NO3), the central NiII ion, lying on a threefold rotation axis, is six-coordinated by three amine N atoms from the face-capping triaza macrocycle and three water O atoms in a slightly distorted octahedral geometry. In the crystal, O—H⋯O hydrogen bonding and weak O—H⋯Br interactions associate the NiII cations and the counter-ions into a three-dimensional supramolecular network.
In the title compound, [Cu(C3H5N)3(C12H18N6)](ClO4)2·2H2O, the CuII atom lies on a threefold rotation axis and is coordinated in a distorted N6 octahedral environment by three tertiary amines from the tridentate chelating azamacrocyclic ligand and three propionitrile molecules. Intermolecular non-classical C—H⋯N hydrogen bonding interlinks the [Cu(C3H5N)3(C12H18N6)]2+ cations into a two-dimensional supramolecular sheet extending along the ab plane. The crystal packing also exhibits weak C—H⋯O interactions.
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