Structural, Magnetic and Spectroscopic Characterization of Novel Di-μ-carboxylato-Bridged Binuclear Copper(II) Complexes with 1,10-Phenanthroline

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Abstract
Bis(μ-carboxylato-O,O′)-diaquabis(1,10-phenanthroline)dicopper(II) dinitrate tetrahydrates, [Cu(RCOO)(phen)(H2O)]2(NO3)2·4H2O, where R=H, CH3, and (CH3)3C, were prepared and characterized by elemental analyses, electronic spectra, magnetic susceptibilities, and X-ray structure analysis. The magnetic susceptibility data conform to the usual dimer equation. The −2J values are 125 cm−1 for formate, 86 cm−1 for acetate, and 99 cm−1 for 2,2-dimethylpropanoate. The crystal structures of [Cu(HCOO)(phen)(H2O)]2(NO3)2·4H2O (1) and [Cu(CH3COO)(phen)(H2O)]2(NO3)2·4H2O (2) were determined by the single-crystal X-ray diffraction method. The crystallographic data are: Compound 1, monoclinic, I2⁄a, a=18.850(2), b=9.775(2), c=17.752(2) Å, β=99.03(1)°, V=3230.4(8) Å3, Z=4, R=0.055 for 2511 observed unique reflections; Compound 2, monoclinic, C2⁄c, a=18.563(4), b=14.272(5), c=14.126(3) Å, β=106.72(2)°, V=3584(2) Å3, Z=4, R=0.082 for 2092 reflections. The complexes consist of dimeric [Cu(RCOO)(phen)(H2O)]22+)] cations with five-coordinated copper ions linked by two carboxylato ions in a syn-syn bridging arrangement. The Cu···Cu distances are 3.103(2) Å for 1 and 3.063(3) Å for 2.

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