Crystal engineering: a unique cyclic assembly of a 40 membered module composed from two alternating units each of benzenehexacarboxylic acid (mellitic acid, MA) and 2,5-bis-(4-pyridyl)-1,3,4-oxadiazole (4-BPO): assembly of modules to macromolecules by intermolecular hydrogen bonding

Abstract

Individually prepared, equivalent amounts of 2,5-bis-(4-pyridyl)-1,3,4-oxadiazole (4-BPO) and benzenehexacarboxylic acid (mellitic acid, MA) when mixed, deposited long rods, whose X-ray structure showed a unique assembly of 40 membered planar modules composed from two alternating units each of MA and 4-BPO, rather than the anticipated helical profile. Several novel features of complexes of MA with organic molecules are seen here. In almost all cases the intermolecular hydrogen bonding between MA anions is so stable that the MA anions and the complementary cations lie in separate planes. This barrier is overcome in the present case. The basic module associates to form quartets by very simple hydrogen bonding of the carboxylic groups of MA. The quartet assembly is characterized by the rotation of the left hand pair compared to the right hand pair. The mode of the macromolecular assembly is clear, that is, they are layered in alternating planes. Space group: P21/c with a = 9.181(1) Å, b = 9.624(1) Å, c = 29.390(2) Å, and β= 94.626(4)°. The modules are embedded in an extensively hydrogen bonded MA network. The assembly profile of MA and 4-BPO is unique and should be a harbinger for the design of novel functional assemblies. The 40-membered module mimics the self-assemblies of peptides and can be important in the design of "Haptens" from simple molecules.