Über bismut-haltige heterocyclen: I. Methylierte und phenylierte bismocane,intra- und intermolekulare koordinationserhöhung an bismut(III)

Methyl and phenyl oxadithia and trithiabismocanes have been synthesized from methyl or phenyl diethoxybismutane and the respective dithiol. The light-sensitive compounds have been investigated by mass, vibrational and ¹³C NMR spectra: ν(BiMe) 470–460, ν(BiS₂) 300–240 cm^?1; δ(¹³Me) ?12 ppm. The crystal structure of 5-phenyl-1,4,6,5-oxadithiabismocane has been determined (R = 0.056). The eight-membered ring has the chair-chair conformation. Besides three direct bonds (BiPh 225(2), BiS 256.0(2) and 260.2(3) pm) there are one transannular (Bi?O 297(1) and two intermolecular contacts (Bi ?S 344.0(3) and 350.9(3) pm) to bismuth in resulting a ψ-monocapped octahedral sphere of coordination. These polyhedra are connected in sharing two different edges, and the crystal structure exhibits double chains of molecules.