Different inter-molecular inter-actions in solvated and unsolvated isatin-based di-thio-carbazate imine derivatives.

The syntheses and structures of 2-fluoro-benzyl (Z)-2-(2-oxoindolin-3-yl-idene)hydrazine-1-carbodi-thio-ate dimethyl sulfoxide monosolvate, C16H12FN3OS2·C2H6OS (1) and 2-fluoro-benzyl (Z)-2-(5-bromo-2-oxoindolin-3-yl-idene)hydrazine-1-carbodi-thio-ate, C16H11BrFN3OS2 (2) are reported. Both structures feature a Z-configuration with respect to the C=N bond and the fluoro-benzyl ring is approximately orthogonal to the isatin moiety. For 1, the crystal packing features weak Car-H⋯S (ar = aromatic) hydrogen bonds that link adjacent mol-ecules in a C(10) fashion to form pleated chains propagating along [001] and short S⋯O contacts between dimethyl sulfoxide solvent mol-ecules forming chains along [010]. The N-H hydrogen bond donors in 1 form either intra-molecular or discrete N-H⋯O(DMSO) hydrogen bonds. In 2, alternating R 2 2(8)-type pairwise N-H⋯O hydrogen bonds and short F⋯Br contacts link the mol-ecules into chains propagating along [210]. The later unsolvated structure is of notably poorer quality and exhibits disorder in its o-fluoro-benzyl group, with a 180° flip and a small twist around the S-C bond. These findings are consistent with the results of Hirshfeld surface analyses.