Further structural motifs from the reactions of thioamides with diiodine and the interhalogens iodine monobromide and iodine monochloride: an FT-Raman and crystallographic study
Pd. Boyle et al., Further structural motifs from the reactions of thioamides with diiodine and the interhalogens iodine monobromide and iodine monochloride: an FT-Raman and crystallographic study, J CHEM S DA, (18), 2000, pp. 3106-3112
Citations number
57
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
The reactions of the thioamides thiourea, tu, 1-ethyl-2-thiourea, etu, 1,3-
dimethyl-2-thiourea, dmtu, 1,3-diethyl-2-thiourea, detu, 3-methylbenzothiaz
ole-2-thione, mbtt and 3-methylrhodanine, mrh, with one equivalent of diiod
ine have been studied; attempts have been made to characterise the resultan
t 1:1 addition products using FT-Raman spectroscopy. It has been shown that
these materials lie on a CT-ionic borderline. The crystal structure of dmt
u . I-2 has been determined and is shown to be ionic and of the form [(dmtu
)(2)I]I-+(3)-, an arrangement previously only rarely found in crystallograp
hic reports. The reactions of etu and dmtu with iodine monobromide and iodi
ne monochloride and of mbtt with iodine monobromide give 1:1 interhalogen a
ddition products; initial FT-Raman investigations point to these adopting a
CT 'spoke' structure. The reaction of tu with two equivalents of diiodine
to give a bulk material of stoichiometry tu . I-4 has been studied in detai
l and shown to lead to a variety of novel polyiodide arrangements, the crys
tal structures of two of which are reported, (tu)(2)(I-2)(3) and (tu)(3)(I-
2)(5), and compared to each other, the previously reported (tu)(2)I-2 and t
o tu itself. These two structures represent further, previously unreported,
structural motifs available for these highly complicated systems.