Abstract Fragmentation of 1,2,3-thiadiazoles (1) leads to the compounds 5 - 8 with an increasing proportion of sulphur. Numerous structural possibilities exist for the products 7 with the general formula (R2C2)2S3. The number of proposals can be reduced by spectroscopic techniques, but the final structure determination is accomplished by an X-ray analysis of the title compound 7a. 7a crystallizes in the space group P21/c (Z = 4) with cell parameters of a = 9.714(1), b = 16.188(8), c = 9.149(2) Å and β = 98.93(1)°. The structure is solved by direct methods and refined to R = 0.053 with 1955 diffractometer data (I ≥ 2σ(I)). The trithiolane ring has a puckered conformation and the whole molecule shows nearly perfect C2-symmetry, which is not required crystallographically.