Chemistry of silicon‐nitrogen compounds. 165. On the crystalline products from the reaction of silicon tetrachloride with nitrogen in a glow discharge. Single crystal X‐ray structure determination of N(SiCl₃)₃ and Cl₃SiN(SiCl₂)₂NSiCl₃

Abstract

Abstract Of the two crystalline products obtained by reacting a silicon tetrachloride/nitrogen mixture in a glow discharge tube, the more volatile (m. p. 78°C) has been confirmed to be tris(trichlorosilyl)amine NSi 3 Cl 9 whereas the less volatile component (m. p. 66°C) has been identified as N,N′‐bis(trichlorosilyl)‐Si,Si′‐tetrachloro‐cyclodisildiazane N 2 Si 4 Cl 10 . These conclusions are supported by mass and vibrational spectroscopy and single crystal X‐ray structures. NSi 3 Cl 9 possesses a nearly planar NSi 3 skeleton with average NSi distances of 1.734(2) Å. The N 2 Si 4 fragment of N 2 Si 4 Cl 10 is roughly planar with endocyclic NSiN and SiNSi angles of 89.2(1) and 90.8(1)°, respectively, and mean NSi distances of 1.731(3) (endocyclic) and 1.687(3) Å (exocyclic).