pH-Dependent reversible crystal transformation of 1-carboxymethyl-1-methyl-pyrrolidinium bromides and their spectroscopic fingerprint

In this work, two 1-carboxymethyl-1-methyl-pyrrolidinium bromides (N-methylpyrrolidine betaine hydrobromides) with the stoichiometry of betaine:hydrobromic acid as 1:1 and 2:1, denoted as CMPRHBr-I and CMPRHBr-II, respectively, were prepared and crystallographically determined. The large difference in these two structures is the type of hydrogen bonds, resulting in the different thermal stability. A strong OH⋯Br hydrogen bond was observed in CMPRHBr-I, whereas O⋯H⋯O hydrogen bond in CMPRHBr-II. Both these two crystals can mutually transform by changing the pH value of the aqueous solution. Vibrational spectroscopic studies shows that these two structures can be easily distinguished by the characteristic bands such as νCO stretching vibration and the D-type bands. Our studies indicate that it should be cautious of the structural change as this type of organic salts was purified and recrystallized.