Different hydrogen-bonding patterns in two [Zn(ENTPP)] complexes with water or methanol as ligands

We have synthesized zinc complexes of H2ENTPP (5-(8-ethoxycarbonyl-1-naphthyl)-10,15,20-triphenyl porphyrin) as a model to study hydrogen-bonding interactions. When water or methanol is a ligand, crystals of [Zn(ENTPP)(CH3OH)] or [Zn(ENTPP)(H2O)] · C6H5CH3 were obtained. In both structures, the ligand has hydrogen-bonding interactions, but in different patterns. In [Zn(ENTPP)(CH3OH)], the methanol oxygen and carboxylate oxygen in the naphthyl group form an intermolecular hydrogen bond. In [Zn(ENTPP)(H2O)] · C6H5CH3, there are two independent molecules A and B. In molecule B, there is an intramolecular hydrogen bond between the water oxygen and the carboxylate oxygen, while in molecule A, besides the intramolecular hydrogen bond, there is an intermolecular hydrogen bond between the water oxygen and the carboxylate oxygen. 1H NMR spectra suggest the binding of methanol or water to zinc are equilibrium processes in solution. Equilibrium constant has been determined by UV-Vis measurements, and it suggests the...