Crystal Structure and Phase Transition of the C–HF–H-Bonded Supramolecular Compound with 4-Nitroanilinium Based on 18-Crown-6

A novel inorganic-organic hybrid supramolecular macrocyclic compound, (4-nitroanilinium) (18-crown-6)(PF6)(1), was synthesized and characterized by infrared spectroscopy, thermogravimetric analysis, elemental analysis, differential scanning calorimetry (DSC), and single-crystal X-ray diffraction. Crystal 1 is found to comprise 1D C–H···F–P hydrogen-bonded chains of (4-nitroanilinium+) (18-crown-6) supramolecular cations and PF6 anions. DSC measurements confirm that 1 undergoes a reversible phase transition at 255 K with a hysteresis width of 6 K. A strong dielectric response is observed above 250 K at a low frequency (500 Hz), suggesting the occurrence of proton transfer in the C–H···F–P hydrogen bonds. A precise analysis on the main packing and structural differences, as well as the changes in the intermolecular interaction between the lowand high-temperature phases, reveals that C–H···F–P hydrogen bonds are the main factors affecting phase transition and dielectric behavior.