Optimum yields of heterocyclic products are obtained when the reaction of 4-XC(6)H(4)CN(2)(SiMe(3))(3) (X = Br, CF(3)) with PhSCl in a 1:3 molar ratio in CH(2)Cl(2) is carried out at -100 degrees C followed by the mixture being warmed to -70 degrees C for 16 h. Under these conditions the eight-membered rings (4-XC(6)H(4))(2)C(2)N(4)S(2)Ph(2) (1b, X = Br; 1c, X = CF(3)) are obtained in 64 and 80% yields, respectively, in addition to the purple diazenes Z,E,Z-PhSN(4-XC(6)H(4))CN=NC(C(6)H(4)X-4)NSPh (2b, 8%; 2c, 19%) and, in the case of X = Br, the sixteen-membered ring (4-BrC(6)H(4))(4)C(4)N(8)S(4)Ph(4) (3) (8%). With a reaction time of 40 h the yield of 3 is increased to 25%. By contrast, the reaction of 3-BrC(6)H(4)CN(2)(SiMe(3))(3) with 3 equiv of PhSCl at -70 degrees C gives Z,E,Z-PhSN(3-BrC(6)H(4))CN=NC(3-BrC(6)H(4))NSPh in 75% yield. A possible pathway for the formation of cyclic products is proposed. The solid-state structures of 1b, 1c, and 3 were determined by X-ray crystallography. The eight-membered rings 1b and 1c adopt long boat conformations with the phenyl groups (attached to S) in equatorial positions. Density functional theory (DFT) calculations for the model ring system (HC)(2)N(4)(SH)(2) reveal that the observed C(2)(v)() geometry is the result of a second-order Jahn-Teller distortion of the planar (D(2)(h)()) structure. The chair conformer (C(2)(h)()) is only ca. 10 kJ mol(-)(1) higher in energy than the boat conformer. The hypothetical dianion (HC)(2)N(4)(SH)(2)(2)(-) is predicted to have a transannular S.S contact of about 2.5 Å. The sixteen-membered ring 3 has a cradle-like structure with S(4) symmetry.