(Z)-2-(5-Chloro-2-oxoindolin-3-yl­idene)-N-methyl­hydrazinecarbothio­amide

Amna Qasem Ali; Naser Eltaher Eltayeb; Siang Guan Teoh; Abdussalam Salhin; Hoong-Kun Fun

doi:10.1107/S1600536812007386

. 2012 Mar 7;68(Pt 4):o964–o965. doi: 10.1107/S1600536812007386

(Z)-2-(5-Chloro-2-oxoindolin-3-ylidene)-N-methylhydrazinecarbothioamide

Amna Qasem Ali ^a,^b, Naser Eltaher Eltayeb ^c,^‡, Siang Guan Teoh ^a,^*, Abdussalam Salhin ^a, Hoong-Kun Fun ^d,^§

PMCID: PMC3354764 PMID: 22606200

Abstract

In the title compound, C₁₀H₉ClN₄OS, an intramolecular N—H⋯O hydrogen-bonding interaction and an N—H⋯N interaction generate ring motifs [graph sets S(6) and S(5), respectively]. In the crystal, molecules form a chain through N—H⋯O hydrogen bonds, and these are extended by N—H⋯S hydrogen-bonding interactions into an infinite three-dimensional network. The crystal structure also exhibits weak C—H⋯π interactions.

Related literature

For related structures, see: Qasem Ali et al. (2012 ▶, 2011a ▶,b ▶); Ali et al. (2012 ▶). For various biological activities of Schiff bases, see: Bhandari et al. (2008 ▶); Bhardwaj et al. (2010 ▶); Pandeya et al. (1999 ▶); Sridhar et al. (2002 ▶); Suryavanshi & Pai (2006 ▶). For cytotoxic and anticancer activities of isatin and its derivatives, see: Vine et al. (2009 ▶). For graph-set analysis, see Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₉ClN₄OS
M _r = 268.72
Orthorhombic,
a = 6.2558 (1) Å
b = 10.1449 (1) Å
c = 18.5682 (2) Å
V = 1178.42 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 100 K
0.34 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.853, T _max = 0.961
16807 measured reflections
4886 independent reflections
4072 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.078
S = 1.05
4886 reflections
167 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ▶), 2074 Friedel pairs
Flack parameter: 0.01 (5)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812007386/zs2177sup1.cif

e-68-0o964-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007386/zs2177Isup2.hkl

e-68-0o964-Isup2.hkl^{(239.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812007386/zs2177Isup3.cml

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

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

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯N2	0.88 (2)	2.27 (2)	2.6416 (18)	105.6 (15)
N4—H1N4⋯S1ⁱ	0.88 (2)	2.70 (2)	3.4972 (13)	152.2 (16)
N3—H1N3⋯O1	0.86 (2)	2.086 (19)	2.7526 (16)	134.3 (17)
N1—H1N1⋯O1ⁱⁱ	0.81 (2)	2.01 (2)	2.8161 (16)	175 (2)
C3—H3A⋯Cg2ⁱⁱⁱ	0.95	2.59	3.38	141

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia for the RU research grant (No. 1001/PKIMIA/815067). AQA thanks the Ministry of Higher Education and the University of Sabha (Libya) for a scholarship.

supplementary crystallographic information

Comment

Isatin (2,3-dioxindole) is an endogenous compound identified in humans, and its effect has been studied in a variety of systems. Biological properties of isatin and its derivatives include a range of actions in the brain, offer protection against bacterial (Suryavanshi & Pai, 2006) and fungal infections and possess anticonvulsant, anti-HIV (Pandeya et al., 1999), anti-depressant and anti-inflammatory activities (Bhandari et al., 2008). Recently, we reported the crystal structure of (Z)-2-(5-chloro-2-oxoindolin-3-ylidene)-N-methylhydrazinecarbothioamide (Qasem Ali et al., 2012). In the present paper we describe the single-crystal X-ray diffraction study of title compound, C₁₀H₉ClN₄OS (Fig. 1).

In this compound, the chain N2/N3/C9/S1/N4/C10 is connected to the nine-membered 5-chloroindolin-2-one ring system at C7. In this chain C7—N2—N3—C9 and C10—N4—C9—S1 torsion angles are -177.77 (13)° and 2.7 (2)°, respectively. The essentially planar conformation of the molecule is maintained by the cyclic intramolecular N3—H1N3···O1 hydrogen-bonding interaction together with the N4—H1N4···N2 interaction [graph sets S(6) and S(5), respectively (Bernstein et al., 1995)] (Table 1).

In the crystal the molecules form chain substructures through intermolecular N1—H1N1···O1 hydrogen bonds and these are extended by N4—H1N4···S1 hydrogen-bonding interactions into an infinite a three-dimensional network (Table 1, Fig. 2). Weak C—H···π interactions are also present [C3—H···Cg2ⁱⁱⁱ = 3.38 Å], where Cg2 is the centroid of the C1—C6 ring. For symmetry code (iii), see Table 1.

Experimental

The Schiff base has been synthesized by refluxing the reaction mixture of a hot ethanolic solution (30 ml) of 5-methyl-3-thiosemicarbazide (0.01 mol) and a hot ethanolic solution (30 ml) of 5-chloroisatin (0.01 mol) for 2 hr. The precipitate formed during reflux was filtered, washed with cold ethanol and recrystallized from hot ethanol. Yield (m.p.): 85% (568.4–569.0 K). The yellow crystals were grown in ethylacetate–DMF (3:1) by slow evaporation at room temperature.