Oligomeric Sulfur Nitrides. 2. Synthesis and Structure of l, 7-Di-4-tolyltetrasulfurtrinitrogen Chloride

Bis(trimethylsilyl)sulfur diimide reacts with p-tolyl-or p-chlorophenylsulfenyl chloride to yield the corresponding 1, 7-diaryltetrasulfurtrinitrogen cation. The course of the reaction is best explained by two consecutive additions of a sulfur-chlorine bond to a sulfur-nitrogen double bond, followed by the elimination of nitrogen gas and a diaryl disulfide. The crystal and molecular structure of one of the compounds, l, 7-di-4-tolyltetrasulfurtrinitrogen chloride, has been determined from three-dimensional X-ray counter data. The material crystallizes in the triclinic space group P&& with two formula units in a cell of dimensions [formula omitted] Least-squares refinement has led to a conventional R factor of 0.061. The seven-membered SN chain assumes a cis, trans, trans, cis geometry, apparently to maximize the electrostatic interactions between itself and the chloride counterions. The values of the various S-N bond lengths indicate appreciable delocalization of charge over the entire chain. © 1978, American Chemical Society. All rights reserved.