The Counterion Effect on the Assembly of Coordination Networks of Cationic (η3‐Allyl)palladium Complexes Containing 3,5‐Dimethyl‐4‐nitro‐1H‐pyrazole |
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Authors: | Mercedes Cano JosV Heras MLuz Gallego Josefina Perles Caridad Ruiz‐Valero Elena Pinilla MRosario Torres |
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Institution: | Mercedes Cano,José?V. Heras,M.?Luz Gallego,Josefina Perles,Caridad Ruiz‐Valero,Elena Pinilla,M.?Rosario Torres |
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Abstract: | Two new (η3‐allyl)palladium complexes containing the ligand 3,5‐dimethyl‐4‐nitro‐1H‐pyrazole (Hdmnpz) were synthesized and characterized as Pd(η3‐C3H5)(Hdmnpz)2]BF4 ( 1 ) and Pd(η3‐C3H5)(Hdmnpz)2]NO3 ( 2 ). The structures of these compounds were determined by single‐crystal X‐ray diffraction to evaluate the intermolecular assembly. Each complex exhibits similar coordination behavior consistent with cationic entities comprised of two pyrazole ligands coordinated with the Pd(η3‐C3H5)]+ fragment in an almost square‐planar coordination geometry. In 1 , the cationic entities are propagated through strong intermolecular H‐bonds formed between the pyrazole NH groups and BF ions in one‐dimensional polymer chains along the a axis. These chains are extended into two‐dimensional sheet networks via bifurcated H‐bonds. New intermolecular interactions established between NO2 and Me substituents at the pyrazole ligand of neighboring sheets give rise to a three‐dimensional network. By contrast, compound 2 presents molecular cyclic dimers formed through N? H???O H‐bonds between two NO counterions and the pyrazole NH groups of two cationic entities. The dimers are also connected to each other through C? H???O H‐bonds between the remaining O‐atom of each NO ion and the allyl CH2 H‐atom. Those interactions expand in a layer which lies parallel to the face (101). |
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