phenanthroline (Me2phen) with some acceptors such as chloranil (Chl), picric acid (HPA) Charge-transfer (CT) complexes formed in the reactions of 2,9-dimethyl-1,10-Charge-transfer (CT) complexes formed in the reactions of 2,9-dimethyl-1,10-Charge-transfer (CT) complexes formed in the reactions of 2,9-dimethyl-1,10-and chloranilic acid (H2CA) have been studied in the defined solvent at room temperature. Based on elemental analysis and infrared spectra of the solid CT-complexes along with the photometric titration curves for the reactions, obtained data indicate the formation of 1:1 charge-transfer complexes [(Me2phen)(Chl)] (1), [(Me2phenH)(PA)] (2) and [(Me2phenH)(HCA)] (3), respectively, was proposed. In the three complexes, infrared and 1H NMR spectroscopic data indicate a charge-transfer interaction and as far as complexes 2 and 3 are concerned this interaction is associated with a hydrogen bonding. The formation constants for the complexes (KC) were shown to be dependent upon the nature of the electron acceptors used. The X-ray structure of complex 3 indicate the formation of dimeric units [Me2phenH]2[(HCA)2] in which the two anions (HCA)− are connected by two O–H⋯O hydrogen bonds whereas the cations and anions are joined together by strong three-center (bifurcated) N–H⋯O hydrogen bonds. Furthermore, the cations are arranged in a π–π stackin