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

Muhammad Ramzan; Humayun Pervez; M Nawaz Tahir; Muhammad Yaqub

doi:10.1107/S1600536810034951

. 2010 Sep 4;66(Pt 10):o2494–o2495. doi: 10.1107/S1600536810034951

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

Muhammad Ramzan ^a, Humayun Pervez ^a, M Nawaz Tahir ^b,^*, Muhammad Yaqub ^a

PMCID: PMC2983261 PMID: 21587492

Abstract

In the title compound, C₁₅H₁₁FN₄OS, there are three independent molecules, each with a disordered 3-fluorophenyl group [occupancy ratios = 0.547 (17):0.453 (17), 0.645 (5):0.355 (5) and 0.626 (15):0.374 (15)] and displaying dihedral angles of 4.2 (3), 25.2 (6) and 32.4 (5)° between the 2-oxoindoline and fluoro-substituted phenyl rings. Strong intramolecular N—H⋯N and N—H⋯O and weak intramolecular C—H⋯S hydrogen bonds complete S(5) and S(6) ring motifs, while strong intermolecular N—H⋯O hydrogen bonds interconnect the three independent molecules through R ₃ ³(12) ring motifs. The three-molecule units are in turn linked into polymeric sheets via C—H⋯F and C—H⋯S hydrogen bonds and π–π interactions [centroid–centroid distances in the range 3.520 (2)–3.820 (9) Å].

Related literature

For our work on the synthesis of biologically important isatin (systematic name 1H-indole-2,3-dione) derivatives, see: Pervez et al. (2007 ▶, 2008 ▶, 2009 ▶). For related structures, see: Pervez et al. (2010 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₅H₁₁FN₄OS
M _r = 314.34
Triclinic,
a = 8.0582 (3) Å
b = 14.3640 (5) Å
c = 19.4456 (8) Å
α = 86.338 (2)°
β = 89.299 (1)°
γ = 75.128 (2)°
V = 2170.93 (14) Å³
Z = 6
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.28 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.942, T _max = 0.950
31845 measured reflections
7851 independent reflections
4225 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.178
S = 1.02
7851 reflections
573 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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/S1600536810034951/bg2363sup1.cif

e-66-o2494-sup1.cif^{(49.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810034951/bg2363Isup2.hkl

e-66-o2494-Isup2.hkl^{(376.3KB, 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	2.03	2.837 (3)	155
N3—H3A⋯O1	0.86	2.11	2.778 (4)	134
N4—H4A⋯N2	0.86	2.13	2.596 (4)	114
N5—H5A⋯O1ⁱⁱ	0.86	2.05	2.881 (4)	164
N7—H7⋯O2	0.86	2.11	2.785 (4)	135
N8—H8⋯N6	0.86	2.14	2.599 (4)	113
N9—H9⋯O2ⁱⁱⁱ	0.86	2.06	2.871 (3)	157
N11—H11C⋯O3	0.86	2.09	2.767 (3)	135
N12—H12C⋯N10	0.86	2.13	2.590 (4)	113
C4—H4⋯F2A^iv	0.93	2.48	3.215 (7)	136
C15A—H15A⋯S1	0.93	2.57	3.223 (18)	127
C30A—H30A⋯S2	0.93	2.54	3.208 (6)	129
C42A—H42A⋯S2^v	0.93	2.87	3.763 (12)	162
C45A—H45A⋯S3	0.93	2.72	3.260 (13)	118

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

Acknowledgments

HP, MY and MR thank the Ministry of Science & Technology (MoST), Government of Pakistan, for partial financial assistance under Projects for the Strengthening of S & T Education in Universities (project No. P&D/S&T/2001/231).

supplementary crystallographic information

Comment

In continuation of our work on the synthesis of biologically important isatin derivatives (Pervez et al., 2007, 2008, 2009), we report herein the structure and preparation of the title compound (I, Fig. 1). When compared with the crystal structure of i.e. 4-(2-fluorophenyl)-1-(2-oxoindolin-3-ylidene) thiosemicarbazide (II) (Pervez et al., 2010), it can be noticed they differ in the position of the fluoro function at the phenyl ring bound to N⁴ in the thiosemicarbazone moiety.

There are three independent molecules in (I). The 3-fluorophenyl moiety is disordered in each one with different site occupancy ratios (0.547 (17):0.453 (17), 0.645 (5):0.355 (5) and 0.626 (15):0.374 (15), respectively. In all three molecules, the 2-oxoindolin A (C1–C8/N1/O1), B (C16–C23/N5/O2) and C (C31–C38/N9/O3) groups are planar with r. m. s. deviations of 0.0054, 0.0100 and 0.0036 Å, respectively. The thiosemicarbazide D (N2/N3/C9/S1/N4), E (N6/N7/C24/S2/N8) and F (N10/N11/C39/S3/N12) groups, in turn, are also planar with r. m. s. deviations of 0.0060, 0.0336 and 0.0192 Å, respectively. The dihedral angles between A/D, B/E, C/F are 9.24 (15), 7.67 (14), 6.13 (17).

Due to strong intramolecular H-bondings of N—H···N and N—H···O type, there exist one S(5) and one S(6) (Bernstein et al., 1995) ring motif, respectively (Table 1, Fig. 2). A weak intramolecular C—H···S H-bond is also present in each molecule (Table 1). The three molecules are interconnected through strong intermolecular H-bonds of N—H···O type (Table 1, Fig. 2) and complete R₃³(12) ring motifs. The molecules are stabilized in the form of polymeric sheets which are finally formed due to C—H···F and C—H···S interactions (Table 1, Fig. 2). In the stabilization of molecules, π–π interactions present play a relevant role.

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-fluorophenyl)thiosemicarbazide (0.93 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 heating was collected by suction filtration. Thorough washing with hot ethanol followed by ether afforded the target compound (I) in pure form (1.12 g, 71%), m. p. 513 K (d). The single crystals of (I) were grown in acetone-ethanol (1:4) by diffusion method at room temperature.