Crystal Structure and Phase Transition of 4-Aminopyridinium Tetrabromoantimonate(III) as Studied by Bromine and Antimony NQR, Proton NMR, and Single Crystal X-Ray Diffraction

Abstract

The crystal structure of the room temperature phase (RTP) of the title compound was determined at 297 K (monoclinic, space group C2/c, a = 1384.2(2), b = 1377.8(3), c = 755.5(2) pm, β = 121.58(1)°). A complicated disorder was found for the cation. A phase transition from the low-temperature phase (LTP) to the RTP was found at (224 ±1) K (Tc). The 1H NMR spectra showed a sharp motional narrowing at ca. T=Tc , indicating the occurrence of a reorientational motion of the cation in the RTP in accord with the disorder. It was found that another reorientational motion is excited in the LTP. Four 81Br NQR lines (132.71, 115.38, 61.54 and 59.31 MHz at 77 K) and two Sb NQR lines (53.78 and 33.76 MHz at 77 K) were found in the LTP, while a single 81Br NQR line was observed at T> 276 K (ca. 121.80 MHz at 300 K). Crystal dynamics are discussed on the basis of the temperature dependence of the NQR, 1H NMR line width, and 1H NMR T1.