Methyl 2-[(Z)-5-bromo-2-oxoindolin-3-ylidene]hydrazinecarbodithioate

The crystal structure of a new S-methyl-substituted dithiocarbazate imine containing the 5-bromoisatin moiety is described.

The title compound, C 10 H 8 BrN 3 OS 2 , a brominated dithiocarbazate imine derivative, was obtained from the condensation reaction of S-methyldithiocarbazate (SMDTC) and 5-bromoisatin.The essentially planar molecule exhibits a Z configuration, with the dithiocarbazate and 5-bromoisatin fragments located on the same sides of the C N azomethine bond, which allows for the formation of an intramolecular N-H� � �O b (b = bromoisatin) hydrogen bond generating an S(6) ring motif.In the crystal, adjacent molecules are linked by pairs of N-H� � �O hydrogen bonds, forming dimers characterized by an R 2 2 (8) loop motif.In the extended structure, molecules are linked into a threedimensional network by C-H� � �S and C-H� � �Br hydrogen bonds, C-Br� � �S halogen bonds and aromatic �-� stacking.

Structure description
Isatin-derived dithiocarbazate imines have been reported to exhibit a broad spectrum of physiological properties (Yekke-ghasemi et al., 2020;Ramilo-Gomes et al., 2021).In particular, the S-methyl-substituted derivatives have received considerable attention in the field of organic transformations for the preparation of carbothiohydrazones, carbothiohydrazides and various aza-heterocyclic compounds such as pyrazoles, 1,2,4-triazoles and 1,3,4-thiadiazoles (Lin et al., 2013;Moustafa et al., 2021;Bekircan et al., 2022;Malakar et al., 2023, Geoghegan et al., 2024).Recent study has revealed that the imine obtained from the condensation reaction of isatin and S-methyldithiocarbazate can be directly transformed into the spiro-fused 1,3,4-thiadiazole compound in a straightforward synthetic protocol (Moustafa et al., 2021).This approach opens a new avenue in accessing isatin-based spirocycle molecules.We are concerned with developing new dithiocarbazate imines containing isatin derivatives and continue research work to explore their potential applications (Abdul Manan et al., 2024).Therefore, as part of our ongoing research and structural studies on such molecules, we now report the synthesis and crystal structure of the title compound.

Synthesis and crystallization
The dithiocarbazate precursor, SMDTC was prepared by the literature method (Das & Livingstone, 1976).The title compound was prepared by adding 5-bromoisatin (2.26 g, 10.0 mmol, 1.0 eq) dissolved in hot ethanol (20 ml) to a solution of the precursor, SMDTC (1.22 g, 10.0 mmol, 1.0 eq) in hot ethanol (35 ml).The mixture was heated (80 � C) with continuous stirring for 15 min and later allowed to stand about 20 min at room temperature until a precipitate was formed, which was then filtered and dried over silica gel, yielding orange crystals on recrystallization from ethanol solution (yield: 2.74 g, 83%).m.p. 259-260 � C; 1 H NMR ( 400 The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Figure 3
View showing both the weak hydrogen bonds and halogen bonds connecting the hydrogen-bonded dimers in three-dimensions.

Special details
Geometry.All esds (except the esd in the dihedral angle between two l.s.planes) are estimated using the full covariance matrix.The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry.An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s.planes.Refinement.Refined as a 2-component twin with HKLF5 generated by TWINROTMAT running in PLATON.NH hydrogen atoms were identifed from F map and refined with N-H restrained to 0.98 Å.

Table 2
Experimental details.