Pressure-induced phase transition of 4-aminobenzonitrile: the formation and enhancement of N–H⋯N weak hydrogen bonds

A reversible pressure-induced structural phase transition of 4-aminobenzonitrile was found at about 0.3 GPa by conducting in situ high-pressure synchrotron angle-dispersive X-ray diffraction (ADXRD) experiments. The discontinuous changes of Raman modes at 0.2 GPa confirmed the occurrence of phase transition. In situ high-pressure Raman spectra indicated that the molecular arrangement and intermolecular interactions changed abruptly. The process of this phase transition continued up to about 1.0 GPa. When the pressure reached 1.1 GPa, the initial N–H⋯N interaction transformed into a new weak hydrogen bond, which was enhanced by further compression. The ab initio calculations and Hirshfeld surfaces were used to illustrate the above views. This study gives an example that demonstrates that the pressure can induce the formation of hydrogen bonds, which contributes to the development of supramolecular chemistry.