Synthesis and characterization of four novel manganese(II) chains formed by 4,4′-azobis(pyridine) and benzoate or nitrobenzoates: Stabilization of unusual ladder structures

Four new manganese(II) coordination polymers: [Mn(4,4′-azpy)(C6H5COO)2](4,4′-azpy)0.5 (1), [Mn(4,4′-azpy)(p-(NO2)C6H4COO)2] (2), [Mn(4,4′-azpy)(m-(NO2)C6H4COO)2] (3) and [Mn(4,4′-azpy)(o-(NO2)C6H4COO)2(H2O)2] (4), where 4,4′-azpy = 4,4′-azobis(pyridine), have been synthesized by self-assembly of MnX2 (X = benzoate, p-, m-, or o-nitrobenzoates) together with 4,4′-azpy. All four complexes were characterized by elemental analyses, IR spectroscopy, thermal analyses, single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. The structural analyses reveal that complexes 1, 2 and 3 feature a 1D molecular ladder formed by syn–syn (complex 1) or syn–anti (complexes 2 and 3) carboxylate-bridged dimeric Mn(II) units which are joined together by 4,4′-azpy ligands. In complex 1, these ladders assemble with the help of π–π and C–H⋯π interactions to form a nanoporous framework that incorporates non coordinated 4,4′-azpy molecules by exploiting host–guest C–H⋯π and hydrogen bonding interactions. Complex 2 presents a 3D supramolecular framework by π–π and CH⋯π interactions, whereas, complex 3 having a similar ladder structure to 1 and 2, forms a 2D grid through π–π interactions. On the other hand, complex 4 is a 4,4′-azpy bridged fish-bone chain of carboxylate-coordinated mononuclear manganese(II) units, which are linked together by strong hydrogen bonds to form a 2D structure. Variable-temperature (2–300 K) magnetic susceptibility measurements show the presence of weak antiferromagnetic interactions within the discrete Mn–(OCO)2–Mn dimers for complexes 1, 2 and 3 that have been fitted with a S = 5/2 dimer model (J = −0.8, −0.5 and −0.4 cm−1 respectively). The magnetic data of complex 4 can be reproduced with a S = 5/2 monomer model including a Zero Field Splitting (|D| = 1.7 cm−1).

Mn(II) and 4,4′-azobis(pyridine) react to form novel ladder structures with benzoate and its p- and m-nitro derivatives, whereas the o-derivative yields a fish-bone chain. Variable-temperature (2–300 K) magnetic susceptibility measurements show the presence of weak antiferromagnetic interactions within the discrete Mn–(OCO)2–Mn dimers for benzoate and its p- and m-nitro derivatives that have been fitted with a S = 5/2 dimer model and with a S = 5/2 monomer model including a Zero Field Splitting for the o-derivative.Figure optionsDownload as PowerPoint slide