ISSN:
1573-9171
Keywords:
organic metals
;
bis(ethylenedithio)tetrathiafulvalene = ET
;
x-ray diffraction analysis
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract The compositions and structures of two new organic metals based on ET [where ET = bis(ethylenedithio)tetrathiafulvalene], viz., (ET)2[Hg(SCN)Cl2], with a metal-dielectric transition temperature (Tm-d) of 35°K, and (ET)2[Hg(SCN)2Br], with Tm-d = 140°K, were established by x-ray diffraction analysis. The crystal structures of the investigated compounds are similar to the structure of the previously studied organic metal (ET)2[Hg(SCN)2Cl] with Tm-d = 50°K. The principal crystallographic data for (ET)2[Hg(SCN)Cl2] are as follows: a = 36.64(1), b = 8.300(4), c = 11.798(1) Å, β = 89.91(3)°, V = 3588.1(9) Å3, space group Cc, Z = 4, dcalc = 2.05 g/cm3. The principal crystallographic data for (ET)2[Hg(SCN)2Br] are as follows: a = 37.088(14), b = 8.338(3), c = 11.738(5) Å, β = 89.71(3)°, V = 3629.6(8) Å3, space group C2/c, Z = 8, dcalc = 2.15 g/cm3. A characteristic feature of the crystal structure of the investigated compounds is alternation of the anion and cation layers along the a axis of the crystal. In the cation layer of the k type the ET are interconnected by shortened S...S intermolecular contacts (3.39–3.58 Å). The [Hg(SCN)3−nXn]− anions (X = Cl, Br; n = 1, 2) form polymeric chains with one or two bridged SCN groups. A tendency for a decrease in the metal-dielectric transition temperature with a decrease in the volume of the anion is detected in the (ET)2[Hg(SCN)3−nXn] salts, where X = Cl and Br, and n = 1 and 2.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00863816
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