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.
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