Abstract
Peculiarities of the atomic structure of N,N-diphenylguanidium (1+) hexabromotellurate (IV), (C13H14N3)2[TeBr6], which has reversible thermochromic properties, have been studied by X-ray single crystal method at different temperatures. It has been revealed that temperature-dependent distortions of the geometry of the thermochrom compound are not expressed anyhow substantially; therefore, the temperature behavior of thermal parameters of Br atoms was studied in detail. For the first time the interrelation between the thermochromic properties of the complex and peculiarities of atomic thermal vibrations has been disclosed: abnormally great increase in the deflection angle of the axis σ3 of the ellipsoid of thermal vibrations of apical bromine atoms from Te-Br bond direction under the temperature reduction reflects the decrease of vibronic interaction between the ground and the first excited state of Te(IV) (the display of Jahn-Teller dynamic effect of the second order) and, correspondingly, results in asymmetry lessening of the band A in the absorption spectrum and causes the change in compound color determined by it. There has been revealed the presence of C-H…Br hydrogen bond via hydrogen atoms of phenyl rings of diphenylguanidium. Basing on the analysis of atomic thermal parameters, it has been established that the apical atom Br(4) having the shortest distance in the octahedron is linked with the central atom relatively weaker than other atoms.
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Original Russian Text Copyright © 2005 by B. V. Bukvetskii and A. G. Mirochnik
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Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 4, pp.694–704, July–August, 2005.
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Bukvetskii, B.V., Mirochnik, A.G. X-ray single crystal study of reversible thermochromism and the pecularities of atomic thermal motion in n, n-diphenylguanidinium(1+) hexabromotellurate (IV). J Struct Chem 46, 672–682 (2005). https://doi.org/10.1007/s10947-006-0186-y
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DOI: https://doi.org/10.1007/s10947-006-0186-y