4-(3-Methoxy­phen­yl)-1-(2-oxoindolin-3-yl­idene)thio­semicarbazide

Humayun Pervez; Mohammad S Iqbal; Naveeda Saira; Muhammad Yaqub; M Nawaz Tahir

doi:10.1107/S1600536810018052

. 2010 May 22;66(Pt 6):o1404. doi: 10.1107/S1600536810018052

4-(3-Methoxyphenyl)-1-(2-oxoindolin-3-ylidene)thiosemicarbazide

Humayun Pervez ^a, Mohammad S Iqbal ^b, Naveeda Saira ^a, Muhammad Yaqub ^a, M Nawaz Tahir ^c,^*

PMCID: PMC2979529 PMID: 21579483

Abstract

In the title compound, C₁₆H₁₄N₄O₂S, intramolecular N—H⋯N hydrogen bonding forms an S(5) ring, whereas N—H⋯O and C—H⋯S interactions complete S(6) ring motifs. In the crystal, molecules form inversion dimers due to N—H⋯O interactions. The dimers are interlinked through N—H⋯S hydrogen bonds and π–π interactions occur with a centroid–centroid distance of 3.8422 (11) Å between the methoxy-containing benzene ring and the five-membered heterocyclic ring.

Related literature

For the preparation and structures of biologically important N ⁴-aryl-substituted isatin-3-thiosemicarbazones, see: Pervez et al. (2007 ▶, 2008 ▶, 2009 ▶, 2010a ▶). For a related structure, see: Pervez et al. (2010b ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₁₄N₄O₂S
M _r = 326.37
Monoclinic,
a = 15.1793 (5) Å
b = 7.2473 (2) Å
c = 15.4764 (5) Å
β = 111.179 (2)°
V = 1587.55 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.34 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.946, T _max = 0.960
13861 measured reflections
3925 independent reflections
2898 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.125
S = 1.04
3925 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018052/si2262sup1.cif

e-66-o1404-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018052/si2262Isup2.hkl

e-66-o1404-Isup2.hkl^{(188.5KB, 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⋯O1ⁱ	0.86	2.04	2.875 (2)	164
N3—H3A⋯O1	0.86	2.06	2.7441 (19)	136
N4—H4A⋯N2	0.86	2.19	2.620 (2)	110
N4—H4A⋯S1ⁱⁱ	0.86	2.87	3.5806 (16)	141
C11—H11⋯S1	0.93	2.74	3.212 (2)	112

Open in a new tab

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

Acknowledgments

HP, MSI and NS thank the Higher Education Commission (HEC), Pakistan, for financial assistance under the National Research Program for Universities (project No. 20–873/R&D/07/452).

supplementary crystallographic information

Comment

In continuation of our work on the synthesis of medicinally important organic molecules (Pervez et al., 2007, 2008, 2009, 2010a), we report herein the structure and synthesis of the title compound (I, Fig. 1).

The crystal structure of (II) i.e. 4-(2-fluorophenyl)-1-(2-oxoindolin-3-ylidene)thiosemicarbazide has been published (Pervez et al., 2010b). The title compound (I) differs from (II) due to the attachment of methoxy group at position-3 instead of fluoro at position-2 of the phenyl ring substituted at N^4^ of the thiosemicarbazone moiety.

In (I) the 2-oxoindolin A (C1–C8/N1/O1), thiosemicarbazide B (N2/N3/C9/S1/N4) and the 3-methoxyphenyl C (C10—C16/O2) are planar with r. m. s. deviations of 0.0178, 0.0244 and 0.0149 Å, respectively. The dihedral angle between A/B, A/C and B/C is 8.71 (5)°, 33.59 (3)° and 39.32 (3)°, respectively. Due to intramolecular H-bondings (Table 1, Fig. 1), one S(5) and two S(6) (Bernstein et al., 1995) ring motifs are formed. The molecules are dimerised (Fig. 2) due to intermolecular H-bonding of N—H···O type with R₂²(8) ring motifs. The dimers are interlinked through N—H···S type of H-bonding. There exist π···π interaction at a distance of 3.8422 (11) Å between the benzene ring (C10—C15) and the heterocyclic ring (N1/C7/C2/C1/C8).

Experimental

To a hot solution of isatin (0.74 g, 5.0 mmol) in ethanol (10 ml) containing a few drops of glacial acetic acid was added 4-(3-methoxyphenyl)thiosemicarbazide (0.99 g, 5.0 mmol) dissolved in ethanol (10 ml) under stirring. The reaction mixture was then heated under reflux for 2 h. The yellow crystalline solid formed during refluxing was collected by suction filtration. Thorough washing with hot ethanol followed by ether afforded the target compound (I) in pure form (1.25 g, 77%), m. p. 477 K (d). The single crystals of (I) were grown in acetone by slow evaporation at room temperature.