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

Hoong-Kun Fun; Suhana Arshad; Shobhitha Shetty; Balakrishna Kalluraya

doi:10.1107/S1600536811038463

. 2011 Sep 30;67(Pt 10):o2740. doi: 10.1107/S1600536811038463

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

Hoong-Kun Fun ^a,^*,^‡, Suhana Arshad ^a, Shobhitha Shetty ^b, Balakrishna Kalluraya ^b

PMCID: PMC3201496 PMID: 22058802

Abstract

In the title molecule, C₁₁H₁₀ClN₅OS, an intramolecular N—H⋯O hydrogen forms an S(6) ring motif. The dihedral angle between the pyrazole ring and the benzene ring is 3.77 (8)°. In the crystal, molecules are linked by N—H⋯S and N—H⋯O hydrogen bonds into layers parallel to the bc plane.

Related literature

For the biological activity and pharmacological properties of pyrazole derivatives, see: Rai et al. (2008 ▶); Girisha et al. (2010 ▶); Isloor et al. (2009 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₁₀ClN₅OS
M _r = 295.75
Monoclinic,
a = 25.0899 (17) Å
b = 11.6075 (9) Å
c = 9.0806 (6) Å
β = 99.516 (1)°
V = 2608.2 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 296 K
0.48 × 0.33 × 0.17 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.812, T _max = 0.927
22139 measured reflections
3827 independent reflections
3125 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.120
S = 1.04
3827 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.49 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/S1600536811038463/lh5337sup1.cif

e-67-o2740-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038463/lh5337Isup2.hkl

e-67-o2740-Isup2.hkl^{(187.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038463/lh5337Isup3.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
N4—H1N4⋯O1	0.914 (18)	2.114 (19)	2.7903 (16)	129.9 (16)
N5—H1N5⋯S1ⁱ	0.89 (2)	2.76 (2)	3.5239 (13)	144.5 (16)
N5—H2N5⋯O1ⁱⁱ	0.91 (2)	2.00 (2)	2.9124 (15)	177.0 (19)

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). SA also thanks the Malaysian Government and USM for the Academic Staff Training Scheme (ASTS) award.

supplementary crystallographic information

Comment

Pyrazole derivatives are well established in the literatures as important biologically active heterocyclic compounds (Rai et al., 2008). These derivatives are the subject of many research studies due to their widespread pharmacological properties such as anti-inflammatory (Girisha et al., 2010), antipyretic, antimicrobial (Isloor et al., 2009), and antiviral activities. The widely prescribed anti-inflammatory pyrazole derivatives, celecoxib and deracoxib, are selective COX-2 inhibitors with reduced ulcerogenic side effects. The synthetic route followed for obtaining the title compound 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 corresponding oxobutanoate which on further reaction with thiosemicarbazide in acetic acid gave the required thioamides.

The molecular structure is shown in Fig. 1. An intramolecular N4—H1N4···O1 hydrogen bond (Table 1) stabilizes the molecular structure and forms an S(6) ring motif (Bernstein et al., 1995). The dihedral angle between the 4,5-dihydro-1H-pyrazole (N1/N2/C1–C3) ring and the phenyl (C4–C9) ring is 3.77 (8)°. Bond lengths (Allen et al., 1987) and angles are within normal ranges.

The crystal packing is shown in Fig. 2. The molecules are linked by intermolecular N5—H1N5···S1ⁱ and N5—H2N5···O1ⁱⁱ hydrogen bonds (Table 1) into layers parallel to bc plane.

Experimental

To a solution of ethyl-2-[(4-chlorophenyl)hydrazono]-3-oxobutanoate (0.01 mol) dissolved in glacial acetic acid (20 ml), a solution of thiosemicarbazide (0.02 mol) in glacial acetic acid (25 ml) was added and the mixture was refluxed for 4 h. It was 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 mixtures of DMF and ethanol by slow evaporation.