Abstract: A series of aromatic and heteroaromatic fused pentathiepins has been prepared by several methods. The X-ray structure analysis of several of these compounds has been obtained along with other useful characterization data (laser Raman, UV, etc.). Certain benzopentathiepins can be made to disproportionate into sulfur and benzotrithioles. In one case (6-(trifluoromethyl) benzopentathiepin, Sc), an apparent equilibrium is established ...