35Cl NQR and Crystal Structure Studies of Salts of Chlorodifluoro- and Dichloroacetic Acid

Abstract

AbstractThe 35Cl NQR spectra of several chlorodifluoroacetates were studied as a function of temperature, including the acid ClF2CCOOH. The cations were: Ammonium, guanidinium, paramethylanilinium. Also some acid salts M⊕ClF2CCOO⊖ • n - ClF2CCOOH ( n > l ) were studied by 35Cl NQR. The bleaching temperatures of the NQR signals were determined. In the para-methylanilinium salt and in the guanidinium salt a phase transition has been observed. The crystal structure of guanidinium chlorodifluoroacetate has been determined at room temperature (a = 1089 pm, 6 = 845 pm, c = 832 pm, space group Pnma, Z = 4). For comparison, guanidinium dichloroacetate was studied by 35Cl NQR and by X-ray diffraction, too: P21/c, Z = 4 , a = 804pm, b = 1202 pm, c = 1080 pm, ß = 131.58°. For guanidinium chlorodifluoroacetate and chlorodifluoroacetic acid, the 35Cl spin lattice relaxation time T1 and the line width have been followed up as a function of temperature. Therefrom, the activation energies of the reorientation motion of the group -CF2C1 have been determined to be 14 kJ • mol-1 (from T1) and 12.5 kJ • mol- 1 (from Δv) for the pure acid and 9.2 kJ • mol-1 and 8.8 kJ • mol-1 , respectively, for the guanidinium salt.