3-Methyl-4-[2-(4-nitro­phen­yl)hydrazin-1-yl­idene]-5-oxo-4,5-dihydro-1H-pyrazole-1-carbothio­amide

Hoong-Kun Fun; Ching Kheng Quah; Shobhitha Shetty; Balakrishna Kalluraya; M Babu

doi:10.1107/S1600536812027134

. 2012 Jun 23;68(Pt 7):o2162. doi: 10.1107/S1600536812027134

3-Methyl-4-[2-(4-nitrophenyl)hydrazin-1-ylidene]-5-oxo-4,5-dihydro-1H-pyrazole-1-carbothioamide

Hoong-Kun Fun ^a,^*,^‡, Ching Kheng Quah ^a,^§, Shobhitha Shetty ^b, Balakrishna Kalluraya ^b, M Babu ^b

PMCID: PMC3393969 PMID: 22798834

Abstract

The asymmetric unit of the title compound, C₁₁H₁₀N₆O₃S, contains two independent molecules, each of which is stabilized by an intramolecular N—H⋯O hydrogen bond, forming an S(6) ring motif. In one molecule, the pyrazole ring forms a dihedral angle of 10.93 (14)° with the benzene ring. The corresponding dihedral angle in the other molecule is 7.03 (14)°. In the crystal, molecules are linked via pairs of (N,N)—H⋯O bifurcated acceptor bonds which, together with C—H⋯O hydrogen bonds, form sheets parallel to (001).

Related literature

For general background to and the pharmacological activity of pyrazole derivatives, see: Isloor et al. (2009 ▶); Rai et al. (2008 ▶); Bradbury & Pucci (2008 ▶); Girisha et al. (2010 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₁H₁₀N₆O₃S
M _r = 306.31
Monoclinic,
a = 11.5331 (4) Å
b = 17.2540 (6) Å
c = 13.6025 (5) Å
β = 105.840 (2)°
V = 2604.01 (16) Å³
Z = 8
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 100 K
0.23 × 0.19 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.940, T _max = 0.965
29927 measured reflections
7706 independent reflections
5153 reflections with I > 2σ(I)
R _int = 0.086

Refinement

R[F ² > 2σ(F ²)] = 0.074
wR(F ²) = 0.187
S = 1.05
7706 reflections
405 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.17 e Å⁻³
Δρ_min = −0.45 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/S1600536812027134/kj2205sup1.cif

e-68-o2162-sup1.cif^{(34.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027134/kj2205Isup2.hkl

e-68-o2162-Isup2.hkl^{(377KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812027134/kj2205Isup3.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
N5B—H2N5⋯O3B	0.97 (3)	2.08 (3)	2.810 (3)	131 (3)
N1A—H1N1⋯O3B ⁱ	0.88 (4)	2.00 (4)	2.859 (3)	165 (4)
N5A—H1N5⋯O3A	0.92 (3)	2.11 (4)	2.802 (3)	131 (3)
N1B—H3N1⋯O3A ⁱⁱ	0.87 (3)	1.99 (4)	2.848 (3)	171 (3)
C10B—H10B⋯O2A ⁱⁱⁱ	0.95	2.51	3.418 (3)	161

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). CKQ also thanks USM for an Incentive Grant.

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 the focus of active research over the years (Isloor et al., 2009). Pyrazoles have been reported to possess antibacterial activity (Rai et al., 2008), and 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 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.

The asymmetric unit contains two independent molecules (Fig. 1), A and B. Each molecule is stabilized by an intramolecular N–H···O hydrogen bond (Table 1), forming a S(6) ring motif (Bernstein et al., 1995). In molecule A, the pyrazole ring (N2A/N3A/C2A-C4A) forms a dihedral angle of 10.93 (14)° with the benzene ring (C5A-C10A). The corresponding dihedral angle in the molecule B is 7.03 (14)°. Bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal (Fig.2), molecules are linked via pairs of intermolecular N5B–H2N5···O3B, N1A–H1N1···O3B and N5A–H1N5···O3A, N1B–H3N1···O3A bifurcated acceptor bonds (Table 1) which together with C10B–H10B···O2A hydrogen bonds form two-dimensional sheets parallel to (001).

Experimental

To a solution of ethyl-2-[(4-nitrophenyl)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. This was cooled and allowed to stand overnight. The solid product which separated out was filtered and dried. It was then recrystallized from ethanol. Crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the title compound in a 1:2 mixture of DMF and ethanol.