NQR and X-ray Studies of [N(CH3)4]3M2X9 and (CH3NH3)3M2X9 (M = Sb,Bi; X = Cl,Br)

Abstract

Abstract35Cl, 81Br, 121Sb, and 209Bi NQR of the title compounds was observed. According to the results of the temperature dependences of NQR frequencies and the DTA measurements, phase transitions take place in [N(CH3)4]3Bi2Br9 (Ttr=183K), [N(CH3)4]3Bi2Cl9 (Ttr = 155K), and (CH3NH3)3Bi2Cl3 (Ttr = 200 and 249 K). 2D NMR spectra for partially deuterated (CH3ND3)3Bi,Br9 showed that the phase transitions in this compound are related to the motion of the methylammonium cations. Single-crystal X-ray work at room temperature shows that the space group for [N(CH3)4]3Sb2Cl9 is P63/mmc with a = 925.1 pm, c = 2173.4 pm, Z = 2. For (CH3NH3 ) 3Sb2Br9 the space group is P3ml with a = 818.8 pm, c = 992.7 pm, Z = 1; in both cases the cations show dynamical disorder. The Rietveld analysis of the powder X-ray diffraction for (CH3NH3)3Bi2Br9 reveals the space group P3ml with a = 821.0, c - 1000.4 pm, Z = 1 at room temperature; the compound is isomorphous with (CH3NH3 )3Sb2Br9 . The crystal symmetries of the low-temperature phases of (CH3NH3)3Bi2Br9 and [N(CH3)4]3Bi2Br9 were deduced from the results of the NQR spectroscopy