A series of 21 sulfoester and sulfonamide derivatives comprising two aromatic rings was synthesized to investigate the effect of the presence of either electron-donating (ED) or electron-withdrawing (EW) groups on the intramolecular pi-stacking assembly. The positioning of ED or EW moieties was carried out directly on one of the aromatic rings linked to the sulfonyl or sulfonamide moieties. In contrast, the other aromatic ring (phenyl or pyridine) was connected by a -CH2-CH2- spacer with the sulfonyl or sulfonamide moiety. The purpose of having an ethyl spacer between the two aromatic rings was to achieve conformational flexibility, facilitating the intramolecular pi-stacking assembly between the two aromatic rings. The use of sulfoester/sulfonamide groups allowed more conformational flexibility to attain desired orientations in solids with the interplay of the hydrogen-bonding interactions. Between the two functional groups, sulfonamides offered a more hydrogen-rich environment due to the amine moiety and may exhibit higher H-bonding propensity than the sulfoester moiety. The central idea here was to study the interplay between the hydrogen-bonding and pi & ctdot;pi interactions. The substituent groups chosen were categorized as strong electron-withdrawing (-CF3 and -CN), weak electron-withdrawing (-Cl and -Br), neutral (-H), and good electron-donating (-CH3 and -OCH3) groups. Crystal structure analysis revealed the syn conformation for all the derivatives, enabling intramolecular pi & ctdot;pi interactions between the two aromatic rings, whereas in the sulfonamide derivatives, the molecule takes either midway or anti conformations, except for one pyridine sulfonamide derivative, which showed the syn orientation but lacked intramolecular pi-stacking interactions. The absence of any conventional H-bond forming functional groups in the sulfoester derivatives may have resulted in the syn geometry facilitated by intramolecular pi-stacking interactions. Conversely, H-bond-forming functional groups in the sulfonamide derivatives could have prevented the syn conformation. The conformational analysis carried out employing density functional theory (DFT) calculations confirmed the higher stability of the syn conformation over the midway and anti orientations. The placing of electron-withdrawing and electron-donating groups at the para position of the benzene revealed sulfoesters preferably adopts a syn geometry facilitating the intramolecular pi-stacking, but sulphonamides takes midway or anti-geometry.

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