Proton-transfer compounds of isonipecotamide with the aromatic dicarboxylic acids 4-nitrophthalic, 4,5-dichlorophthalic, 5-nitroisophthalic and terephthalic acid

Abstract

The structures of the 1:1 proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with 4-nitrophthalic acid [4-carbamoylpiperidinium 2-carboxy-4-nitrobenzoate, C6H13N2O8+·C8H4O6-, (I)], 4,5-dichlorophthalic acid [4-carbamoylpiperidinium 2-carboxy-4,5-dichlorobenzoate, C6H13N2O8+·C8H3Cl2O4-, (II)] and 5-nitroisophthalic acid [4-carbamoylpiperidinium 3-carboxy-5-nitrobenzoate, C6H13N2O8+·C8H4O6-, (III)], as well as the 2:1 compound with terephthalic acid [bis(4-carbamoylpiperidinium) benzene-1,2-dicarboxylate dihydrate, 2C6H13N2O8+·C8H4O42-·2H2O, (IV)], have been determined at 200 K. All salts form hydrogen-bonded structures, viz. one-dimensional in (II) and three-dimensional in (I), (III) and (IV). In (I) and (III), the centrosymmetric R22(8) cyclic amide-amide association is found, while in (IV) several different types of water-bridged cyclic associations are present [graph sets R42(8), R43(10), R44(12), R33(18) and R64(22)]. The one-dimensional structure of (I) features the common `planar' hydrogen 4,5-dichlorophthalate anion, together with enlarged cyclic R33(13) and R43(17) associations. In the structures of (I) and (III), the presence of head-to-tail hydrogen phthalate chain substructures is found. In (IV), head-to-tail primary cation-anion associations are extended longitudinally into chains through the water-bridged cation associations, and laterally by piperidinium-carboxylate N-H...O and water-carboxylate O-H...O hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. An additional example of cation-anion association with this cation is also shown in the asymmetric three-centre piperidinium-carboxylate N-H...O,O' interaction in the first-reported structure of a 2:1 isonipecotamide-carboxylate salt.