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Structure, Optical and Magnetic Properties of Two Isomeric 2-Bromomethylpyridine Cu(II) Complexes
Fatma Garci1,2, Hammouda Chebbi1,3, Nahal Rouzbeh4
1University of Tunis El Manar, Faculty of Sciences of Tunis Laboratory of Materials, Crystal Chemistry and Applied Thermodynamics, El Manar II, Tunis 2092, Tunisia.
Abstract:
Two isomeric 2-bromomethylpyridine Cu(II) complexes [Cu(C6H9NBr)2(NO3)2] with 2-bromo-5-methylpyridine (L1) and 2-bromo-4-methylpyridine (L2) were synthesized as air-stable blue materials in good yields. The crystal structures were different with [Cu(L1)2(NO3)2] (CuL) crystallizing in the monoclinic space group P21/c, while the 4-methyl derivative CuL was solved and refined in triclinic P1¯. The orientation of the Br substituents in the molecular structure (anti (CuL) vs. syn (CuL) conformations) and the geometry around Cu(II) in an overall 4 + 2 distorted coordination was very different with two secondary (axially elongated) Cu-O bonds on each side of the CuN2O2 basal plane in CuL or both on one side in CuL. The two Br substituents in CuL come quite close to the Cu(II) centers and to each other (Br⋯Br ~3.7 Å). Regardless of these differences, the thermal behavior (TG/DTA) of both materials is very similar with decomposition starting at around 160 °C and CuO as the final product. In contrast to this, FT-IR and Raman frequencies are markedly different for the two isomers and the UV-vis absorption spectra in solution show marked differences in the π-π* absorptions at 263 (CuL) or 270 (CuL) nm and in the ligand-to-metal charge transfer bands at around 320 nm which are pronounced for CuL with the higher symmetry at the Cu(II) center, but very weak for CuL. The T-dependent susceptibility measurements also show very similar results (µeff = 1.98 µB for CuL and 2.00 µB for CuL and very small Curie-Weiss constants of about -1. The EPR spectra of both complexes show axial symmetry, very similar averaged g values of 2.123 and 2.125, respectively, and no hyper-fine splitting.
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