Hydrogen bonding and pi-pi interactions in 1-benzofuran-2,3-dicarboxylic acid and its 1:1 cocrystals with pyridine, phenazine and 1,4-phenylenediamine

The structure of 1-benzofuran-2,3-dicarboxylic acid (BFDC), C(10)H(6)O(5), (I), exhibits an intramolecular hydrogen bond between one -COOH group and the other, while the second carboxyl function is involved in intermolecular hydrogen bonding to neighbouring species. The latter results in the formation of flat one-dimensional hydrogen-bonded chains in the crystal structure, which are pi-pi stacked along the normal to the plane of the molecular framework, forming a layered structure. 1:1 Cocrystallization of BFDC with pyridine, phenazine and 1,4-phenylenediamine is associated with H-atom transfer from BFDC to the base and charge-assisted hydrogen bonding between the BFDC(-) monoanion and the corresponding ammonium species, while preserving, in all cases, the intramolecular hydrogen bond between the carboxyl and carboxylate functions. The pyridinium 2-carboxylato-1-benzofuran-3-carboxylic acid, C(5)H(6)N(+)center dot C(10)H(5)O(5)(-), (II), and phenazinium 3-carboxylato-1-benzofuran-2-carboxylic acid, C(12)H(9)N(2)(+)center dot C(10)H(5)O(5)(-), (III), adducts form discrete hydrogen-bonded ion-pair entities. In the corresponding crystal structures, the two components are arranged in either segregated or mixed pi-pi stacks, respectively. On the other hand, the structure of 4-aminoanilinium 2-carboxylato-1-benzofuran-3-carboxylic acid, C(6)H(9)N(2)(+)center dot C(10)H(5)O(5)(-), (IV), exhibits an intermolecular hydrogen- bonding network with three-dimensional connectivity. Moreover, this fourth structure exhibits induction of supramolecular chirality by the extended hydrogen bonding, leading to a helical arrangement of the interacting moieties around 21 screw axes. The significance of this study is that it presents the first crystallographic characterization of pure BFDC, and manifestation of its cocrystallization with a variety of weakly basic amine molecules. It confirms the tendency of BFDC to preserve its intramolecular hydrogen bond and to prefer a monoanionic form in supramolecular association with other components. The aromaticity of the flat benzofuran residue plays an important role in directing either homo-or heteromolecular pi-pi stacking in the first three structures, while the occurrence of a chiral architecture directed by multiple hydrogen bonding is the dominant feature in the fourth.