Crown ether inclusion compound 3,4‐difluoroanilinium di(methanesulfonyl)amidate–18‐crown‐6 (1/1) clathrate

In recent years, molecular‐based ferroelectric materials have attracted widespread research interest due to their excellent performance. Among them, host–guest‐type crown ether inclusion compounds composed of organic ammonium cations, crown ether molecules and corresponding anions have become a star component in the design of molecular‐based ferroelectric materials because they are prone to order–disorder phase transitions. Many anions have been studied extensively as counter‐ions, such as bis(trifluoromethanesulfonyl)amidate (TFSA−), PF6− and [FeCl4]−. However, crown ether inclusion compounds with di(methanesulfonyl)amidate (DMSA) as the anion have been rarely investigated. Here, we converted TFSA to DMSA to obtain 3,4‐difluoroanilinium di(methanesulfonyl)amidate–18‐crown‐6 (1/1), C6H6F2N+·C2H6NO4S2−·C12H24O6 or [(3,4‐DFA)(18‐crown‐6)][DMSA]. At both 100 and 300 K, the crystal falls into the space group P21/c. The 3,4‐DFA cation forms three well‐defined N—H…O hydrogen bonds, positioned at the perching position of the crown ether ring. In contrast to the distinct packing configuration observed in the [(3,4‐DFA)(18‐crown‐6)][TFSA] crystals, where TFSA exhibits a disordered structure, the [(3,4‐DFA)(18‐crown‐6)][DMSA] complex features a staggered arrangement, with DMSA existing in an ordered fashion. A new host–guest‐type inclusion compound, 3,4‐difluoroanilinium di(methanesulfonyl)amidate–18‐crown‐6 (1/1) or [(3,4‐DFA)(18‐crown‐6)][DMSA], exhibits isostructural single‐crystal structures at 100 and 300 K.