Аннотация
New H‐bonded supramolecular assembliesare obtained using the polyfluorobiphenyl H‐donor derivatives and 18‐crown‐6 ether. Cocrystals of octafluorobenzidine with 18‐crown‐6 of 1:1 stoichiometry belong to the enantiomorphous space groups P 6 5 and P 6 1 . The helical self‐assembly of these achiral molecules is achieved due to the interplanar angle of the bis‐aryl molecule (≈60°), which is fixed by directed N–H ··· O cr H‐bonds between two H amino atoms with two O cr atoms at both ends of the molecule. Cocrystallization of octafluorobiphenol results in the formation of a crystalline hydrate based on the water‐mediated H‐bond Ar‐O‐H···O(H)‐H···O cr . Flexible water linker eliminates the effect of the H‐donor coformer structure and makes this cocrystal achiral. The hydrogen bonding details between octafluorobenzidine and 18‐crown‐6 within a unit cell are investigated through a combination of vibrational spectroscopy and quantum mechanical calculations. An oxygen atom in 18‐crown‐6 is identified as a chiral center, as a result of intermolecular interactions involving this atom and hydrogen atoms bonded to its α and β carbon atoms. The unique interaction patterns of 18‐crown‐6 with acetone and chloroform, along with scanning electron microscopic images, reveal the role of solvent molecules in determining the chirality of the self‐assembly.