Reversible structural phase transition of pyridinium-4-carboxylic acid perchlorate

Abstract

Pyridinium-4-carboxylic acid perchlorate (C6H6NO2·ClO4) was synthesized and separated as crystals. Differential scanning calorimetry measurement shows that this compound undergoes a reversible phase transition at about 122 K with a heat hysteresis of 1.8 K. A dielectric anomaly observed at 127 K further confirms the phase transition. The low-temperature (LT;T= 103 K) structure has space groupP21/cand cell parametersa= 17.356 (6),b= 13.241 (3),c= 16.161 (7) Å, β = 138.055 (17)°. The high-temperature (HT;T= 298 K) structure has space groupP21/cand cell parametersa= 5.5046 (11),b= 13.574 (3),c= 11.834 (2) Å, β = 99.35 (3)°, but can be re-described using new axesa′ =a,b′ =b,c′ = −2a+c,V′ =Vto give the cella′ = 5.5046 (11),b′ = 13.574 (3),c′ = 17.424 (3) Å, β′ = 137.92 (3)° and space groupP21/c. The associated coordinate transformation isx′ =x+ 2z,y′ =y,z′ =zand the associated reflection index transformation ish′ =h,k′ =k,l′ =l− 2h. The relationship between the two cells is 3a,b,c(HT) approximatesa,b,c(LT). The crystal comprises one-dimensional hydrogen-bonded chains of the pyridinium-4-carboxylic acid cations and perchlorate anions. A precise analysis of the main packing and structural differences as well as the changes in the intermolecular interactions between the HT phase and the LT phase reveals that the disorder–order transition of the perchlorate anions may be the driving force of the transition, and the hydrogen-bonding effect may contribute to the transition as a secondary parameter.