(Z)-2-(2-Oxoindolin-3-yl­idene)-N-phenylhydrazinecarbothio­amide

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

doi:10.1107/S160053681200400X

. 2012 Mar 7;68(Pt 4):o962–o963. doi: 10.1107/S160053681200400X

(Z)-2-(2-Oxoindolin-3-ylidene)-N-phenylhydrazinecarbothioamide

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

PMCID: PMC3343940 PMID: 22590021

Abstract

In the title compound, C₁₅H₁₂N₄OS, the dihedral angle between the nine-membered indolin-2-one ring system and the phenyl ring is 2.72 (7)°. Intramolecular cyclic N—H⋯O and C—H⋯S hydrogen-bonding interactions [graph set S(6)] are present, as are weak N—H⋯N interactions [graph set S(5)]. In the crystal, molecules form centrosymmetric cyclic dimers through pairs of N—H⋯O hydrogen bonds [graph set R ₂ ²(8)] and these are extended by C—H⋯S interactions. The crystal structure also features weak C—H⋯π interactions.

Related literature

For related crystal structures, see: Ali et al. (2012 ▶); Qasem Ali et al. (2011a ▶,b ▶); Ferrari et al. (2002 ▶); Pervez et al. (2010 ▶); Ramzan et al. (2010 ▶). 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 the 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

C₁₅H₁₂N₄OS
M _r = 296.35
Monoclinic,
a = 6.3674 (1) Å
b = 15.4594 (3) Å
c = 14.2199 (3) Å
β = 93.383 (1)°
V = 1397.31 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.47 × 0.13 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.897, T _max = 0.971
15557 measured reflections
4159 independent reflections
2985 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.113
S = 1.02
4159 reflections
202 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.49 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/S160053681200400X/wn2464sup1.cif

e-68-0o962-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200400X/wn2464Isup2.hkl

e-68-0o962-Isup2.hkl^{(203.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681200400X/wn2464Isup3.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 and Cg3 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ⁱ	0.88 (2)	2.00 (2)	2.8737 (18)	173.9 (18)
N3—H1N3⋯O1	0.87 (2)	2.07 (2)	2.7646 (18)	136 (2)
N4—H1N4⋯N2	0.88 (2)	2.05 (2)	2.5781 (19)	117.4 (17)
C11—H11A⋯S1ⁱⁱ	0.95	2.83	3.6017 (19)	139
C15—H15A⋯S1	0.95	2.60	3.2735 (19)	128
C2—H2A⋯Cg3ⁱⁱⁱ	0.95	2.80	3.510 (2)	132
C13—H13A⋯Cg2^iv	0.95	2.82	3.5201 (19)	131

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia for a Research University 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. The 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), antidepressant 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., 2011a). In the present paper we describe the single-crystal X-ray diffraction study of the title compound (Fig. 1).

In the title compound, C₁₅H₁₂N₄OS, the dihedral angle between the nine-membered indolin-2-one ring system and the phenyl ring is 2.72 (7)°. These two ring systems are connected by a chain of four atoms N2—N3—C9—N4; this torsion angle is 4.1 (2)°. The torsion angles C7—N2—N3—C9 and C10—N4—C9—N3 are 173.69 (15)° and 174.00 (16)°, respectively. These values are very close to those in a similar structure (Qasem Ali et al., 2011a).

The essentially planar conformation of the molecule is maintained by cyclic intramolecular N3—H1N3···O1 and C15—H15A···S1 hydrogen-bonding interactions [graph set S(6) (Bernstein et al., 1995)] (Table 1), together with a weak S(5) N4—H1N4···N2 interaction.

In the crystal structure, the molecules form centrosymmetric cyclic dimers through intermolecular N1—H1N1···O1 hydrogen bonds [graph set R²₂(8)] and are extended by C11—H11A···S1 hydrogen bond interactions.

The crystal structure (Fig. 2) is stabilized by weak C—H···π interactions (Table 1) involving the C10–C15 ring (centroid Cg3) and C1–C6 ring (centroid Cg2).

Experimental

The Schiff base has been synthesized by refluxing the reaction mixture of a hot ethanolic solution (30 ml) of 4-phenyl-3-thiosemicarbazide (0.01 mol) and a hot ethanolic solution (30 ml) of isatin (0.01 mol) for 2 h. The precipitate formed during reflux was filtered, washed with cold EtOH and recrystallized from hot EtOH. Yield (m.p.): 90% (510.2–511.6 K). The yellow crystals were grown in acetone–dimethylformamide (3:1) by slow evaporation at room temperature.