Influence of the Crystallization Solvent on the Molecular Structures of Copper(ii) Saccharinato Complexes with Pyridazine: Synthesis, X-Ray Crystallography, Spectroscopy, Photoluminescence, and Thermal Properties
Veysel T. Yilmaz A D , Evrim Senel B and Canan Kazak CA Department of Chemistry, Faculty of Arts and Sciences, Uludag University, 16059 Gorukle, Bursa, Turkey.
B Department of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayis University, 55139 Kurupelit, Samsun, Turkey.
C Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayis University, 55139 Kurupelit, Samsun, Turkey.
D Corresponding author. Email: vtyilmaz@uludag.edu.tr
Australian Journal of Chemistry 61(8) 634-639 https://doi.org/10.1071/CH08254
Submitted: 11 June 2008 Accepted: 10 July 2008 Published: 15 August 2008
Abstract
X-Ray structural analysis has shown that the products of the reaction of [Cu(sac)2(H2O)4]·2H2O (sac = saccharinate) with pyridazine (pydz) are markedly dependent on the solvent used in the crystallization. The mononuclear complex [Cu(sac)2(H2O)(pydz)2] is obtained by slow evaporation of a 1:2 H2O/methanol solution at room temperature, whereas liquid-phase diffusion of diethyl ether into the same reaction solution produces the polymeric complex [Cu(μ-OH)(μ-sac)(μ-pydz)]n. The individual molecules of [Cu(sac)2(H2O)(pydz)2] are doubly bridged into dimers by O–H…O hydrogen bonds. All ligands in [Cu(sac)2(H2O)(pydz)2] are monodentate, whereas copper(ii) ions in [Cu(μ-OH)(μ-sac)(μ-pydz)]n are triply bridged by all ligands, leading to a one-dimensional chain structure, which is further assembled to form a three-dimensional framework by non-covalent π–π and CH–π stacking interactions. Complex [Cu(sac)2(H2O)(pydz)2] is paramagnetic, whereas complex [Cu(μ-OH)(μ-sac)(μ-pydz)]n exhibits a significantly low μeffective value due to very strong exchange coupling between the copper atoms with a relatively short Cu–Cu distance of 3.360(3) Å. In addition, the full spectroscopic, luminescence, and thermal properties of the complexes are reported.
Acknowledgements
We thank Dr O. Z. Yesilel and Dr B. Karabulut for their assistance in obtaining DTA-TG curves and ESR spectra, respectively.
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