ISSN:
0044-2313
Keywords:
Thallium(I) thiolates
;
syntheses
;
crystal structure
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Thallium(I) Thiolates: Synthesis, Structure, and Properties of TlSC6H5, TlS-t-C4H9, and TlSC7H7By reaction of thallium(I) salts with sodium thiolates in organic solvents it is possible to synthesize and crystallize polymeric and oligomeric neutral thallium(I) thiolate complexes. The polymeric crystal structure of yellow benzenethiolato thallium(I) TlSC6H5 (space group P213, a = 19.943(3) Å at 143 K) is built up by the two novel structure units [Tl7(SC6H5)6]+ and [Tl5(SC6H5)6]-. Yellow tert.-butanethiolato thallium(I) TlS-t-C4H9 (space group P1, a = 11.490(3), b = 11.490(3), c = 12.698(4) Å, α = 108.31(3), β = 91.21(2), σ = 116.99(3)° at 143 K) consists of [Tl8(S-t-C4H9)8] molecules, the thallium atoms being either in trigonal pyramidal or ψ-trigonal bipyramidal coordination. Yellow phenylmethanethiolato thallium(I) TlSC7H7 crystallizes as thin plates (space group: Pbcn, a = 31.215(9), b = 7.173(2), c = 7.184(2) Å at 293 K). The crystal structure contains chains of fourmembered Tl2S2 rings which are linked through trans edges to form a ladder-like arrangement. Each thallium atom is coordinated trigonal-pyramidally by three sulfur atoms. The vibrational spectra of the compounds are reported.
Notes:
Durch Umsetzung von Thallium(I)-Salzen mit Natriumthiolaten in organischen Lösungsmitteln gelang die Synthese und Kristallisation von polymeren und oligomeren neutralen TlI-Thiolat-Komplexen. Das gelbe Benzolthiolatothallium(I) TlSC6H5 (Raumgruppe P213, a = 19,943(3) Å bei 143 K) enthält in der polymeren Kristallstruktur die zwei neuartigen Strukturelemente [Tl7(SC6H5)6]+ und [Tl5(SC6H5)6]-. Die Thallium-Atome sind entweder trigonal-pyramidal oder ψ-trigonal-bipyramidal koordiniert. Das gelbe tert.-Butanthiolato-thallium(I) TlS-t-C4H9 (Raumgruppe P1, a = 11,490(3), b = 11,490(3), c = 12,698(4) Å, α = 108,31(3), β = 91,21(2), σ = 116,99(3)° bei 143 K) wird aus [Tl8(S-t-C4H9)8]-Molekülen aufgebaut, wobei die Thallium-Atome wieder trigonal-pyramidal und ψ-trigonal-bipyramidal koordiniert sind. Phenylmethanthiolato-thallium(I) TlSC7H7 kristallisiert in Form dünner gelber Plättchen (Raumgruppe: Pbcn, a = 31,215(9), b = 7,173(2), c = 7,184(2) Å bei 293 K). Die Kristallstruktur enthält Thallium-Thiolat-Ketten, die strickleiterartig aus trans-verknüpften Tl2S2-Vierringen bestehen. Jedes Thallium-Atom ist trigonal-pyramidal von drei Schwefel-Atomen koordiniert. Über schwingungsspektroskopische Untersuchungen wird berichtet.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19915950116
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