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

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

doi:10.1107/S1600536810017964

. 2010 May 22;66(Pt 6):o1405. doi: 10.1107/S1600536810017964

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

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

PMCID: PMC2979516 PMID: 21579484

Abstract

In the title compound, C₁₅H₁₁N₅O₃S, intramolecular N—H⋯N hydrogen bonding forms an S(5) ring motif, whereas N—H⋯O and C—H⋯S interactions type complete S(6) ring motifs. The 2-oxoindoline and 3-methoxyphenyl rings are almost planar, with r.m.s. deviations of 0.0178 and 0.0149 Å, respectively, and form a dihedral angle of 33.59 (3)°. In the crystal, molecules are interlinked through the nitro groups in an end-to-end fashion via N—H⋯O and C—H⋯O interactions.

Related literature

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

Experimental

Crystal data

C₁₅H₁₁N₅O₃S
M _r = 341.35
Orthorhombic,
a = 18.5545 (10) Å
b = 15.3852 (8) Å
c = 5.3367 (4) Å
V = 1523.44 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.24 × 0.16 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.957, T _max = 0.966
7285 measured reflections
2751 independent reflections
1957 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.096
S = 1.00
2751 reflections
217 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ▶), 992 Friedel pairs
Flack parameter: −0.05 (11)

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/S1600536810017964/bq2210sup1.cif

e-66-o1405-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017964/bq2210Isup2.hkl

e-66-o1405-Isup2.hkl^{(132.3KB, 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⋯O3ⁱ	0.86	2.21	3.058 (3)	170
N3—H3⋯O1	0.86	2.13	2.797 (3)	134
N4—H4A⋯N2	0.86	2.12	2.580 (3)	113
C7—H7⋯O2ⁱ	0.93	2.55	3.358 (4)	145
C11—H11⋯S1	0.93	2.56	3.204 (3)	127

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Symmetry code: (i) Inline graphic .

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

As a part of our work on the synthesis of certain biologically important isatin derivatives (Pervez et al., 2007), 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 (Pervez et al., 2010b) and (III) i.e. 4-(3-methoxyphenyl)-1-(2-oxoindolin-3-ylidene)thiosemicarbazide (Pervez et al., 2010a) have been reported. The title compound (I) differs from (II) due to the attachment of nitro group at position-3 instead of fluoro at position-2 of the phenyl ring substituted at N⁴ of the thiosemicarbazone moiety. Similarly (I) differs from (III) due to the presence of nitro instead of methoxy function at position-3 of the phenyl ring. 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 interlinked through nitro groups (Fig. 2) in end to end fashion due to N—H···O and C–H···O interactions completing R₂²(8) ring motifs. The N=O···π and C=S···π interaction play role in stabilizing the molecules.

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-nitrophenyl)thiosemicarbazide (1.06 g, 5.0 mmol) dissolved in ethanol (10 ml) under stirring. The reaction mixture was then heated under reflux for 2 h. The orange crystalline solid formed during heating was collected by suction filtration. Thorough washing with hot ethanol followed by ether provided the desired compound (I) in pure form (1.08 g, 63%), m.p. 539 K. The single crystals of (I) were grown in ethyl acetate by slow evaporation at room temperature.