The crystal structure of the orthorhombic modification of Me₃Sn·S·CS·NMe₂ has been determined by single-crystal X-ray diffraction. The unit-cell dimensions are a= 21·61 ± 0·02, b= 14·13 ± 0·03, c= 7·62 ± 0·02 Å; Z= 8. Statistical tests based on the generalised ‘R index’ have established the space group to be Pba2 rather than the centrosymmetric Pbam, and have enabled an absolute configuration to be assigned to the particular crystal studied. There are two crystallographically independent molecules in the unit-cell; both have approximately planar SnSC(S)N skeletons with short intramolecular Sn ⋯ S(2) contacts of 3·16 ± 0·03 and 3·33 ± 0·01 Å respectively. The other bond lengths are very similar in the two molecules; the mean values are Sn–S(1)= 2·47 ± 0·01, Sn–C = 2·21 ± 0·03, S(1)–C = 1·79 ± 0·02; C–S(2)= 1·71 ± 0·03; C(1)–N = 1·34 ± 0·03, and N–C(5,6)= 1·43 ± 0·03 Å.