1-(5-Bromo-2-oxoindolin-3-yl­idene)thio­semicarbazone

Katlen C T Bandeira; Leandro Bresolin; Christian Näther; Inke Jess; Adriano B Oliveira

doi:10.1107/S1600536813018564

. 2013 Jul 13;69(Pt 8):o1251–o1252. doi: 10.1107/S1600536813018564

1-(5-Bromo-2-oxoindolin-3-ylidene)thiosemicarbazone

Katlen C T Bandeira ^a, Leandro Bresolin ^a, Christian Näther ^b, Inke Jess ^b, Adriano B Oliveira ^c,^*

PMCID: PMC3793752 PMID: 24109339

Abstract

The title molecule, C₉H₇BrN₄OS, is essentially planar [r.m.s. deviation = 0.066 (2) Å], the maximum deviation from the mean plane through the non-H atoms being 0.190 (3) Å for the terminal amine N atom. In the crystal, molecules are linked through N—H⋯O and N—H⋯S interactions, generating infinite chains along the b-axis direction. In turn, the chains are stacked along the a axis via π–π interactions [centroid–centroid distance = 3.470 (2) Å] and further connected by N—H⋯Br interactions into a three-dimensional network. An intramolecular N—H⋯O hydrogen bond is also observed.

Related literature

For the pharmacological properties of isatin-thiosemicarbazone derivatives against cruzain, falcipain-2 and rhodesain, see: Chiyanzu et al. (2003 ▶). For the synthesis of 5-bromoisatin-3-thiosemicarbazone, see: Campaigne & Archer (1952 ▶). For the crystal structure of 1-(5-bromo-2-oxoindolin-3-ylidene)thiosemicarbazide acetonitrile monosolvate, see: Pederzolli et al. (2011 ▶). graphic file with name e-69-o1251-scheme1.jpg

Experimental

Crystal data

C₉H₇BrN₄OS
M _r = 299.16
Orthorhombic,
a = 4.0185 (2) Å
b = 14.6418 (8) Å
c = 18.8276 (11) Å
V = 1107.78 (10) Å³
Z = 4
Mo Kα radiation
μ = 3.88 mm⁻¹
T = 293 K
0.10 × 0.06 × 0.04 mm

Data collection

Stoe IPDS-1 diffractometer
7791 measured reflections
2405 independent reflections
2106 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.091
S = 1.02
2405 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.55 e Å⁻³
Absolute structure: Flack (1983 ▶), 951 Friedel pairs
Absolute structure parameter: −0.015 (13)

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S1600536813018564/lr2109sup1.cif

e-69-o1251-sup1.cif^{(16.1KB, cif)}

Structure factors: contains datablock(s) platon_shelxl. DOI: 10.1107/S1600536813018564/lr2109Isup2.hkl

e-69-o1251-Isup2.hkl^{(118.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.86	2.82	3.507 (3)	139
N3—H3⋯O1	0.86	2.04	2.726 (4)	135
N4—H2N4⋯Br1ⁱⁱ	0.83	2.91	3.665 (4)	152
N4—H1N4⋯O1ⁱⁱⁱ	0.87	1.99	2.851 (4)	167

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We gratefully acknowledge financial support by the State of Schleswig–Holstein, Germany. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities. We gratefully acknowledge financial support through the DECIT/SCTIE-MS-CNPq-FAPERGS-Pronem-# 11/2029–1 and PRONEX-CNPq-FAPERGS projects. KCTB thanks FAPEAM for the award of a scholarship and ABO acknowledges financial support through the FAPITEC/SE/FUNTEC/CNPq PPP 04/2011 program.

supplementary crystallographic information

Comment

Thiosemicarbazone derivatives have a wide range of biological properties. For example, isatin-based synthetic thiosemicarbazones show pharmacological activity against cruzain, falcipain-2 and rhodesain (Chiyanzu et al., 2003). As part of our study of thiosemicarbazone derivatives, we report herein the crystal structure of 5-bromoisatin-3-thiosemicarbazone (Campaigne & Archer, 1952). In the title compound, in which the molecular structure matches the asymmetric unit, the maximal deviation from the least squares plane through all non-hydrogen atoms amount to 0.1896 (32) Å for N4.The molecule shows an E conformation for the atoms about the N2—N3 bond (Fig. 1). The E conformation for the thiosemicarbazone fragment is also observed in the crystal structure of the 5-bromoisatin-3-thiosemicarbazone acetonitrile monosolvate (Pederzolli et al., 2011) and is related with the intramolecular N—H···O H-interaction (Table 1). The mean deviations from the least squares planes for the C1—C8/Br1/N1 and C9/N2—N4/S1 fragments amount to 0.0568 (26) Å for O1 and 0.0394 (27) Å for N3, respectively, and the dihedral angle between the two planes is 9.01 (12)°. The molecules are connected via centrosymmetric pairs of N—H···S and N—H···O interactions and additionally by N—H···Br interactions (Fig. 2 and Table 1) forming a three-dimensional hydrogen-bonded network, which stabilizes the crystal packing. Additionally, π–π-interactions are observed, with C···C distances = 3.396 (6) Å. The molecules are arranged in layers and are stacked into the crystallographic a-axis direction (Fig. 3).

Experimental

Starting materials were commercially available and were used without further purification. The 5-bromoisatine-3-thiosemicarbazone synthesis was adapted from a procedure reported previously (Campaigne & Archer, 1952). A mixture of of 5-bromoisatin (8,83 mmol) and thiosemicarbazide (8,83 mmol) in ethanol (50 ml) in the presence of a catalytic amount of hydrochloric acid was refluxed for 6 h. After cooling and filtering, the title compound was obtained. Crystals suitable for X-ray diffraction of 5-bromoisatine-3-thiosemicarbazone were obtained unexpectedly from an unsuccessful reaction of SnCl₂ dihydrate with the title compound in methanol and dichloromethane by the slow evaporation of the solvents. Elemental analysis(%): Calc. 36.01 C, 2.69 H, 18.67 N, 10.68 S; found 35.95 C, 2.25 H, 18.67 N, 10.60 S.