Abstract: | The crystal structures of octaisopropylcyclotetrasilane [i-Pr2Si]4 (1) and octakis(trimethylsilylmethyl)cyclotetrasilane [(Me3SiCH2)2Si]4 (2) have been determined by means of X-ray diffraction analysis. Various crystallographic and structural data for the two compounds were recorded. The Si4 rings of the compounds are nonplanar with quite large dihedral angles of 37.1° in (1) and 36.6° in (2), being comparable to that (36.8)° for [t-BuMeSi]4 reported previously and other characteristic features in the structures of (1) and (2) were described. Some structural properties of the cyclic catenation systems, [R1R2Si]n (n = 3–6), including (1) and (2) were also discussed from a comparative viewpoint with respect to the ring shape and the relationship between ring size and Si-Si bond length. |