Systematic Exploration of Structural Topologies in Hydrogen-Bonded Supramolecular Assemblies of Citric Acid with Different Heterocyclic Compounds

[Image: see text] Hydrogen-bonded supramolecular assemblies of citric acid, CA, with some heterocyclic compounds (N-donor and N-oxide)—acridine (acr), phenazine (phenz), 1,10-phenanthroline (110phen), 1,7-phenanthroline (17phen), 4,7-phenanthroline (47phen), 1,4-diazabicyclo[2.2.2]octane (dabco), and 4,4′-bipyridyl-N,N′-dioxide (bpydo)—have been reported. Among these, only the N-donors phenz and N-oxide (bpydo) form neutral co-crystals, while the others form salts owing to the deprotonation of −COOH. Thus, depending on the nature of the aggregate (salt/co-crystal), recognition between the co-formers is established through O–H···N/N(+)–H···O/N(+)H···O(–)heteromeric hydrogen bonding. Additionally, CA molecules establish homomeric interactions mediated by O–H···O hydrogen bonds. Moreover, CA forms a cyclic network with the co-formers or on its own, with a noteworthy feature of formation of host–guest networks in the assemblies with acr and phenz (solvated). In the assembly of acr, the CA molecules form a host network and captivate acr molecules as guest species, while in the case of phenz assembly, both the co-formers together encapsulate the solvent in the channels. However, the observed cyclic networks in the other structures form three-dimensional topologies in the form of ladders, a sandwich, lamellar layers, and interpenetrated networks. The structural features of the ensembles are evaluated unequivocally by the single-crystal X-ray diffraction method, while the homogeneity and phase purity are evaluated by using the powder X-ray diffraction method and differential scanning calorimetry. Further, conformational analysis of CA molecules reveals three types of conformations—T-shape (type I), syn–anti (type II), and syn (type III) as also observed in the literature for other CA co-crystals. In addition, the strength of the intermolecular interactions is quantified by performing Hirshfeld analysis.