Crystal Structures and Solution Studies of Two Novel Zinc(II) Complexes of a Proton Transfer Compound Obtained from 2, 6‐Pyridinedicarboxylic Acid and 1, 10‐Phenanthroline: Observation of Strong Intermolecular Hydrogen Bonds

Abstract

AbstractThe proton transfer compound LH2, (phenH+)2(pydc2—), has been prepared from 1, 10‐phenanthroline, phen, and 2, 6‐pyridinedicarboxylic acid, (dipicolinic acid), pydcH2. Characterization was performed using solution and solid phase CP/MAS 13C NMR and IR spectroscopy. The reactions of this adduct with ZnSO4·7H2O and Zn(NO3)2·4H2O give the complexes, [Zn(pydc)2][Zn(phen)2(H2O)2]·7H2O (1) and [Zn(phen)3]4(H(Hpydc)2)(NO3)7·26H2O (2), respectively. These complexes were characterized by 1H and 13C NMR spectroscopy and single crystal X‐ray analysis. The complexes crystallize in the triclinic space group P1 with Z = 2. The unit cell dimensions for complex 1 and 2 are: a = 9.9838(9) Å, b = 14.7483(13) Å, c = 14.8365(13) Å and a = 12.640(4) Å, b = 15.855(5) Å, c = 21.830(7) Å, respectively. In complex 1 (pydc2—) and phen, are tri‐ and bidentate ligands, respectively, and an anionic [Zn(pydc)2]2— and cationic [Zn(phen)2(H2O)2]2+ complex are formed simultaneously. In complex 2, three phen participate in complexation leaving hydrogen‐bis(pyridine‐2‐carboxylate), (H(Hpydc)2)— as a supramolecular anion. The fragments (H(Hpydc)2)—, 7 NO3—, and 26 H2O in complex 2 are joined together by extensive and strong H‐bonding; therefore, the structure is composed of [Zn(phen)3]48+, and an anionic hydrogen bond supramolecular assembly with the formula, {(H(Hpydc)2(NO3)7)8—·26H2O}n. The anionic species (H(Hpydc)2)— has a special position at the inversion center, as well as one of the NO3— anions, which is disordered over the inversion center. Most of the hydrogen bonds in complex 2 represent strong H‐bonding. The protonation constants of the building blocks of the pydc‐phen adduct, the equilibrium constants for the reaction of (pydc2—) with phenanthroline and the stoichiometry and stability of the ZnII complex with LH2 on aqueous solution were determined by potentiometric pH titration. The solution study results support self‐association between (pydc2—) and (phenH+) with a stoichiometry for the Zn(II) complex similar to that observed for the isolated crystalline complex.