4-[(2,4-Difluoro­phen­yl)hydrazinyl­idene]-3-methyl-5-oxo-4,5-dihydro-1H-pyrazole-1-carbothio­amide

Hoong-Kun Fun; Safra Izuani Jama Asik; Ibrahim Abdul Razak; Shobhitha Shetty; Balakrishna Kalluraya

doi:10.1107/S1600536811044576

. 2011 Oct 29;67(Pt 11):o3116. doi: 10.1107/S1600536811044576

4-[(2,4-Difluorophenyl)hydrazinylidene]-3-methyl-5-oxo-4,5-dihydro-1H-pyrazole-1-carbothioamide

Hoong-Kun Fun ^a,^*,^‡, Safra Izuani Jama Asik ^a, Ibrahim Abdul Razak ^a, Shobhitha Shetty ^b, Balakrishna Kalluraya ^b

PMCID: PMC3247501 PMID: 22220119

Abstract

In the title compound, C₁₁H₉F₂N₅OS, the pyrazole ring forms a dihedral angle of 16.42 (6)° with the benzene ring. Intramolecular N—H⋯O hydrogen bonds generate two S(6) ring motifs. In the crystal, an R ₂ ²(8) ring motif is formed by a pair of intermolecular N—H⋯S hydrogen bonds. Intermolecular C—H⋯F hydrogen bonds further link the molecules into a three-dimensional network.

Related literature

For the biological activity of pyrazole derivatives, see: Isloor et al. (2009 ▶); Rai et al. (2008 ▶); Bradbury & Pucci (2008 ▶); Girisha et al. (2010 ▶). For a related structure, see: Fun et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986) ▶.

Experimental

Crystal data

C₁₁H₉F₂N₅OS
M _r = 297.29
Triclinic,
a = 7.9003 (1) Å
b = 8.2400 (1) Å
c = 10.1378 (1) Å
α = 103.409 (1)°
β = 99.864 (1)°
γ = 99.372 (1)°
V = 618.18 (1) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.41 × 0.23 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.890, T _max = 0.977
15661 measured reflections
4211 independent reflections
3546 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.091
S = 1.06
4211 reflections
194 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811044576/is2796sup1.cif

e-67-o3116-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044576/is2796Isup2.hkl

e-67-o3116-Isup2.hkl^{(206.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811044576/is2796Isup3.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⋯O1	0.863 (17)	2.080 (17)	2.7605 (13)	135.2 (15)
N5—H1N5⋯S1ⁱ	0.842 (17)	2.607 (17)	3.4279 (11)	165.5 (15)
N5—H2N5⋯O1	0.880 (17)	2.048 (17)	2.7208 (13)	132.5 (14)
C10—H10A⋯F1ⁱⁱ	0.98	2.47	3.3016 (14)	143
C10—H10C⋯F1ⁱⁱⁱ	0.98	2.53	3.2775 (14)	133
C10—H10C⋯F2^iv	0.98	2.55	3.2145 (14)	125

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

Acknowledgments

HKF, IAR and SIJA thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grants (Nos.1001/PFIZIK/811160 and 1001/PFIZIK/ 811151).

supplementary crystallographic information

Comment

The pyrazole ring is a prominent structural moiety found in numerous pharmaceutically active compounds. This is mainly due to the easy preparation and the important pharmacological activity. Therefore, the synthesis and selective functionalization of pyrazoles have been focus of active research area over the years (Isloor et al., 2009). Pyrazoles have been reported to possess antibacterial activity (Rai et al., 2008), and found to posses inhibitor activity against DNA gyrase and topoisomerase IV at their respective ATP-binding sites (Bradbury & Pucci, 2008). Moreover, pyrazole-containing compounds have received considerable attention owing to their diverse chemotherapeutic potentials including versatile anti-inflammatory and antimicrobial activities (Girisha et al., 2010). The synthetic route followed for obtaining the title compound (I) involves the diazotization of substituted anilines to give the diazonium salts followed by coupling with ethyl acetoacetate in the presence of sodium acetate to give the corresponding oxobutanoate which on further reaction with thiosemicarbazide in acetic acid gave the required thioamides.

In the title compound of (I), (Fig. 1), the pyrazole (N3/N4/C7–C9) ring is essentially planar, with a maximum deviation of 0.007 (1) Å for atom C9 and makes a dihedral angle of 16.42 (6)° with the benzene (C1–C6) ring. The intramolecular N1—H1N1···O1 and N5—H2N5···O1 hydrogen bonds generate two S(6) ring motifs (Bernstein et al., 1995). The geometric parameters are consistent to those observed in a closely related structure (Fun et al., 2011).

In the crystal structure, (Fig. 2), an R₂²(8) ring motif is formed by intermolecular N5—H1N5···S1 hydrogen bonds (Table 1). Intermolecular C10—H10A···F1, C10—H10C···F1 and C10—H10C···F2 (Table 1) hydrogen bonds further link the molecules into a three- dimensional network.

Experimental

To a solution of ethyl-2-[(2,4-difluorophenyl)hydrazono]-3-oxobutanoate (0.01 mol) dissolved in glacial acetic acid (15 ml), a solution of thiosemicarbazide (0.02 mol) in glacial acetic acid (15 ml) was added and the mixture was refluxed for 4 h. It is cooled and allowed to stand overnight. The solid product that separated out was filtered and dried. It was then recrystallized from ethanol. Crystals suitable for X-ray analysis were obtained from 1:2 mixture of DMF and ethanol by slow evaporation.