Three novel copper(II) 2-nitrobenzoate complexes, [Cu(g-pic) 2 (2-nitrobenzoate) 2 ] 1, [Cu(b-pic) 2 (2-nitrobenzoate) 2 (H 2 O) 2 ] 2 and [Cu 2 (H 2 tea) 2 (2-nitrobenzoate) 2 ]Á2(H 2 O) 3 (where g-pic = 4-methylpyridine, b-pic = 3-methylpyridine and H 2 tea = mono deprotonated triethanolamine), were isolated by addition of g-pic, b-pic and H 3 tea to the hydrated copper(II) 2-nitrobenzoate, [Cu 2 (2-nitrobenzoate) 4 (H 2 O) 2 ]Á2H 2 O, 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 P2 1 /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 H 2 tea ligand bridging two Cu(II) atoms. Two co-crystallized water molecules are also present in 3. The crystal lattice is stabilized by C-HÁ Á ÁO hydrogen bonding interactions in 1 and O-HÁ Á ÁO, C-HÁ Á ÁO hydrogen bonding interactions in 2 and 3. The dimeric complex exhibits relatively strong ferromagnetic exchange with J = À100 cm À1 (corresponding to H = JS 1 S 2). 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.