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Studies of Structure and Phase Transition in [C(NH~2~)~3~]HgBr~3~ and [C(NH~2~)~3~]HgI~3~ by Means of Halogen NQR, ^1^H NMR, and Single Crystal X-Ray Diffraction by Hiromitsu Terao; Masao Hashimoto; Shinichi Hashimoto; Yoshihiro Furukawa is a Chemistry article available to read on EtoBox.

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## (T The crystal structure of [C(NH~2~)~3~]HgBr~3~ was determined at room temperature: monoclinic, space group C2/c, Z = 4, a = 775.0(2), b = 1564.6(2), c = 772.7(2) pm, β = 109.12(2)°. In the crystal, almost planar HgBr3^-^ ions are connected via Hg ··· Br bonds, resulting in single chains of trigonal bipyramidal HgBr~5~ units which run along the c direction. [C(NH~2~)~3~]HgI~3~ was found to be isomorphous with the bromide at room temperature. The temperature dependence of the halogen NQR frequencies (77 < 77K < ca. 380) and the DTA measurements evidenced no phase transition for the bromide, but a second-order phase transition at (251 ± 1) K (T~c1~) and a first-order one at (210 ± 1) K for the iodide. The transitions at T~c2~ are accompanied with strong supercooling and significant superheating. The room temperature phase (RTP) and the intermediate temperature phase (ITP) of the iodide are characterized by two ^127^I~(m=1/2↔3/2)~ NQR lines which are assigned to the terminal and the bridging I atoms, respectively. There exist three lines in the lowest temperature phase (LTP), indicating that the resonance line of the bridging atom splits into two. The signal intensities of the ^12

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Author

Hiromitsu Terao; Masao Hashimoto; Shinichi Hashimoto; Yoshihiro Furukawa

Publisher

Walter de Gruyter GmbH

Published

2000

Language

EN

Field

Chemistry (Physical Sciences)