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The temperature dependence of the  81 Br NQR frequencies of the title compound has revealed the presence of three phases (I, II and III, in the order of decreasing temperature): T cl  (II -1) = (318 ± 10) K and T c2  (III -II) = (202 ± 1) K. The transitions were confirmed by thermal analysis (DTA). Both of the II-I and I-II transitions exhibited strong hysteresis (i. e., superheating and supercooling, respectively). The crystal data, determined by single crystal X-ray diffraction, are: monoclinic, space group P2/a, a = 1384.8(3), b = 934.7(4), c = 1452.0(2) pm, β = 104.10(1)°, Z= 8, R = 0.076. The crystal has two crystallographically independent cations (CH 3 ) 2 NH 2+  and an infinite chain of anions almost in the c-direction. The anion chain is considered to consist of a HgBr 2  molecule and two different HgBr 4  2-  anions which are interconnected via weak intermolecular Hg···Br bonds. The splitting patterns of the  81 Br NQR spectra indicate that rearrangements of the Hg-Br bonds are slight at the III-II transition but serious at the II-I transition. Some of the  81 Br NQR lines show anomalous temperature coefficients, attributable probably to thermal motions of cations.

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Phase Transitions and Crystal Structure of Dimethylammonium Tribromomercurate(II), (CH 3 ) 2 NH 2 HgBr 3  , as Studied by  81 Br NQR and Single Crystal X-ray Diffraction