(Z)-2-(5-Methyl-2-oxoindolin-3-yl­idene)-N-phenyl­hydrazinecarbothio­amide

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

doi:10.1107/S1600536811049154

. 2011 Nov 30;67(Pt 12):o3476–o3477. doi: 10.1107/S1600536811049154

(Z)-2-(5-Methyl-2-oxoindolin-3-ylidene)-N-phenylhydrazinecarbothioamide

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

PMCID: PMC3239102 PMID: 22199950

Abstract

In the title compound, C₁₆H₁₄N₄OS, the dihedral angle between the nine-membered 5-methylindolin-2-one ring system and the benzene ring is 10.21 (7)°. Intramolecular cyclic N—H⋯O and C—H⋯S hydrogen-bonding interactions [graph set S(6)] are present within the N—N—C—N chain between the ring systems. In the crystal, molecules form centrosymmetric cyclic dimers through pairs of N—H⋯O hydrogen bonds [graph set R ₂ ²(8)].

Related literature

For related structures, see: Qasem Ali et al. (2011 ▶); Ferrari et al. (2002 ▶); Pervez et al. (2010 ▶); Ramzan et al. (2010 ▶). For the biological activity of Schiff bases, see: Bhandari et al. (2008 ▶); Bhardwaj et al. (2010 ▶); Pandeya et al. (1999 ▶); Sridhar et al. (2002 ▶); Suryavanshi & Pai (2006 ▶). For the cytotoxic and anticancer activiy of isatin and its derivatives, see: Vine et al. (2009 ▶). For bond-length data, see; Allen et al. (1987 ▶). For graph-set analysis, see Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₁₄N₄OS
M _r = 310.37
Monoclinic,
a = 5.6875 (3) Å
b = 17.9405 (8) Å
c = 14.5658 (6) Å
β = 91.105 (3)°
V = 1485.97 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.37 × 0.14 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.921, T _max = 0.980
25266 measured reflections
4645 independent reflections
3565 reflections with I > 2σ(I)
R _int = 0.080

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.123
S = 1.06
4645 reflections
212 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.30 e Å⁻³

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/S1600536811049154/zs2160sup1.cif

e-67-o3476-sup1.cif^{(19KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049154/zs2160Isup2.hkl

e-67-o3476-Isup2.hkl^{(227.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811049154/zs2160Isup3.cml

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—H1N1⋯O1ⁱ	0.89 (2)	1.96 (2)	2.848 (2)	173 (2)
N3—H1N3⋯O1	0.91 (2)	2.04 (2)	2.7595 (17)	135.8 (19)
C11—H11A⋯S1	0.95	2.63	3.2712 (18)	125

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia for the RU research grant (1001/PKIMIA/815067). NEE thanks Universiti Sains Malaysia for a post-doctoral fellowship and the International University of Africa (Sudan) for providing research leave. 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 and offer protection against certain types of infections, such as antibacterial (Suryavanshi & Pai, 2006) antifungal, 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-phenylhydrazinecarbothioamide (Qasem Ali et al., 2011). In the present paper we describe the single-crystal X-ray diffraction study of title compound, C₁₆H₁₄N₄OS.

In this compound (Fig. 1), the dihedral angle between the nine-membered 5-methylindolin-2-one ring system and the benzene ring is 10.21 (7)°. The atoms C8 in the 5-methylindolin-2-one ring and C10 in the benzene ring are connected by a chain of four atoms (N2/N3/C9/N4)) giving a torsion angle of 7.3 (2)°, while the torsion angles (C8/N2/N3/C9) and (C10/N4/C9/N3) are 173.20 (15)° and -177.56 (16)°, respectively. These values are very close to those in the previously mentioned analogous structure (Qasem Ali et al., 2011). The essentially planar conformation of the molecule is maintained by cyclic intramolecular N3—H···O1 and C11—H···S1 hydrogen-bonding interactions [graph set S(6) (Bernstein et al., 1995)] (Table 1) together with an S(5) N4—H···N2 interaction.

In the crystal the molecules form centrosymmetric cyclic dimers through intermolecular N1—H···O1ⁱ hydrogen bonds [graph set R²₂(8)] (Table 1) (Fig. 2). Weak C—H···π interactions are also present: C5—H5A···Cg3ⁱⁱ = 3.6506 (19) Å; C12—H12A···Cg2ⁱⁱⁱ = 3.6600 (19) Å. [Cg3ⁱⁱ is the centroid of the C10—C15 ring; Cg2ⁱⁱⁱ is the centroid of the C1—C6 ring: symmetry code: (ii) = -x + 1, y + 1/2, -z + 1/2; (iii) = -x, y - 1/2, -z + 1/2].

Experimental

The title compound was synthesized by refluxing the reaction mixture of 4-phenyl-3-thiosemicarbazide (0.01 mol) and 5-methylisatin (0.01 mol) in 60 ml of ethanol for 2 hrs. The precipitate formed during reflux was filtered, washed with cold EtOH and recrystallized from hot EtOH: yield 80%. The orange crystals (m.p. 511.8–512.3 K) were grown in acetone-DMF (3:1) by slow evaporation at room temperature.