Organoimido-Derivatized Hexamolybdates with a Remote Carboxyl Group: Syntheses and Structural Characterizations

Four novel organoimido derivatives of hexamolybdate containing a remote carboxyl group have been synthesized: [Bu4N](2)[Mo6O18(N-C6H4-3-COOH)] (1), [Bu4N](2)[Mo6O18(N-C6H4-2-CH3-4-COOH)] (2), [B4N](2)[Mo6O18(N-C6H4-2-CH3-5-COOH)] (3), and [Bu4N](2)[Mo6O18(N-C6H4-2-CH3-3-COOH)] (4) with 3-aminobenzoic acid, 4-amino-3-methylbenzoic acid, 3-ammo-4-methylbenzoic acid, and 3-amino-2-methylbenzoic acid as the imido-releasing agents, respectively. Their structures have been characterized by IR, UV-vis, H-1 NMR, ESI-MS, and single-crystal X-ray diffraction techniques. Hydrogen bonding interactions play an important role in the supramolecular assemblies of these compounds in the solid state. Although the incorporated organic ligands are similar to each other, their supramolecular assembly behaviors are quite different. For compound 1, the dimer structure is formed via hydrogen bonding between the carboxyl group and the POM cluster of two neighboring cluster anions. For compound 2, the 1D chain structure is formed via hydrogen bonding between the carboxyl groups and the POM clusters of the cluster anions. For compound 3, the 2D plane structure is formed via two types of hydrogen bonding between the aromatic rings and the POM clusters of the cluster anions. For compound 4, the 1D plus 2D structures are formed via three types of hydrogen bonding between the aromatic rings and the POM clusters of the two types of cluster anions with different orientations.