Influence of nitrogen donor ligands on the coordination modes of copper(II) 2-nitrobenzoate complexes: structures, DFT calculations and magnetic properties

Three novel copper(II) 2-nitrobenzoate complexes, [Cu(γ-pic)2(2-nitrobenzoate)2] 1, [Cu(β-pic)2(2-nitrobenzoate)2(H2O)2] 2 and [Cu2(H2tea)2(2-nitrobenzoate)2]·2(H2O) 3 (where γ-pic = 4-methylpyridine, β-pic = 3-methylpyridine and H2tea = mono deprotonated triethanolamine), were isolated by addition of γ-pic, β-pic and H3tea to the hydrated copper(II) 2-nitrobenzoate, [Cu2(2-nitrobenzoate)4(H2O)2]·2H2O, suspended in a methanol : water (4 : 1) mixture. The newly synthesized complexes have been characterized by elemental analyses, thermogravimetric analysis (TGA), spectroscopic techniques (EPR, IR and UV/Visible), magnetic susceptibility measurements, single crystal X-ray structure determination and DFT study. All compounds crystallize in the monoclinic crystal system with the P21/c space group. X-ray structure determination revealed the presence of monomers in both 1 and 2 and dimer in 3 with the deprotonated oxygen atom of the H2tea ligand bridging two Cu(II) atoms. Two co-crystallized water molecules are also present in 3. The crystal lattice is stabilized by C–H⋯O hydrogen bonding interactions in 1 and O–H⋯O, C–H⋯O hydrogen bonding interactions in 2 and 3. The dimeric complex exhibits relatively strong ferromagnetic exchange with J = −100 cm−1 (corresponding to H = JS1S2). The zero-field splitting parameters (zfs) of the dimer triplet states D and E were derived from HF EPR spectra recorded at moderately low temperatures. The sign of D was determined from low-temperature HF EPR spectra