Nine Supramolecular Adducts of 4-dimethylaminopyridine and Carboxylic acids Assembled by Classical Hydrogen Bonds and Other Noncovalent Intermolecular Interactions

Abstract Cocrystallization of the widely available 4-dimethylaminopyridine, with a series of carboxylic acids gave nine molecular adducts 4-dimethylaminopyridinium trifluoroacetate (1), 4-dimethylaminopyridinium glycolate glycolic acid (2), 4-dimethylaminopyridinium 2-furoate dihydrate (3), tri(4-dimethylaminopyridinium) tri(o-chlorobenzoate) tetrahydrate (4), 4-dimethylaminopyridinium 4-bromobenzoate 4-bromobenzoic acid (5), 4-dimethylaminopyridinium 4-formylbenzoate 4-formylbenzoic acid (6), 4-dimethylaminopyridinium 2,4-dichlorobenzoate (7), 4-dimethylaminopyridinium 2-aminobenzoate 2-aminobenzoic acid (8) and bis(4-dimethylaminopyridinium) 5-nitroisophthalate 5-nitroisophthalic acid methanol solvate (9). The nine adducts have been characterised by X-ray diffraction, IR and elemental analysis, the melting points were also reported. Their structural and supramolecular aspects are fully analyzed. The result reveals that among the nine investigated crystals only the ring Ns in the 4-dimethylaminopyridine moieties are protonated when the carboxylic acids are deprotonated. The crystal packing is interpreted by the strong charge-assisted N-H⋯O hydrogen bond between the NH+ and the deprotonated acidic groups. Except the N-H⋯O hydrogen bonds, the charge assisted or neutral O-H•••O hydrogen bonds were also found at 2-6, 8 and 9. The COOH•••COO−synthon has been at 2, 5-6 and 8-9. Further analysis of the crystal packing indicated that a different family of additional CH-O/CH2-O/CH3-O, F-F, Br-Br, CH-Cl, CH3-Cl, CH-π/CH3-π, C-H•••Cπ, C-π, Cl-O, O-C, O-π and π-π contacts contribute to the stabilization and expansion of the total high-dimensional (2D-3D) framework structures. For the synergism of the various nonbonding contacts there created homo/hetero supramolecular synthons or both.