The 1,2,5,6-tetrathiocins (C 6 X 4 S 2 ) 2 (3a, X = F; 3b, X = Cl) are obtained in high yields by the oxidation of the dithiols 1,2-C 6 X 4 (SH) 2 (X = F, Cl) with I 2 or SO 2 Cl 2 , respectively. In the solid state 3a has the C 2h (chair) conformation and crystallizes in two different phases: alpha-(C 6 F 4 S 2 ) 2 , monoclinic, P2 1 /a, a = 9.351(2), b = 6.465(2), and c = 11.546(2) Å, ß = 95.60(1)°, V = 694.6(2) Å 3 , Z = 2; and ß-(C 6 F 4 S 2 ) 2 , monoclinic, P2 1 /c, a = 4.825(2), b = 11.302(2), and c = 12.453(2) Å, ß = 91.45(3)°, V = 678.8(3) Å 3 , Z = 2. By contrast, 3b displays a D 2 (twist-boat) structure and crystallizes in the C2/c space group with a = 15.243(3), b = 8.703(2), and c = 27.010(14) Å, ß = 92.81(4)°, V = 3578(1) Å 3 , and Z = 8. The derivative 3a exists as an equilibrium mixture of two conformational isomers in toluene solution. The VT 19 F NMR data afford the thermodynamic parameters H° = 9.9 ± 0.4 kJ mol -1 and S° = 14 ± 1 J K -1 mol -1 . Density functional theory calculations for 3a indicate that the D 2 conformation is lower in energy than the C 2h isomer by 4.6 kJ mol -1 . The photolysis of 3a in benzene promotes a transannular sulfur migration to give the 1,2,3,6-tetrathiocin, C 6 F 4 SSSC 6 F 4 S (6), which exists in a chair conformation with respect to antipodal sulfur atoms. Crystal structure of 6: orthorhombic, space group Pnma, a = 8.652(6), b = 19.084(4), and c = 8.301(6) Å, V = 1370.6(14) Å 3 , and Z = 4. The isomers 3a and 6 were also characterized by EI mass spectrometry, 19 F NMR, FTIR, and Raman spectroscopies.Key words: tetrathiocins, conformational isomers, photoisomerization.