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

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

doi:10.1107/S1600536811037883

. 2011 Sep 30;67(Pt 10):o2711. doi: 10.1107/S1600536811037883

4-[2-(2-Methoxyphenyl)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: PMC3201502 PMID: 22065021

Abstract

In the title molecule, C₁₂H₁₃N₅O₂S, a bifurcated intramolecular N—H⋯O(O) hydrogen bond forms two S(6) ring motifs. The benzene ring forms a dihedral angle of 14.36 (11)° with the pyrazole ring. In the crystal, pairs of N—H⋯S hydrogen bonds form centrosymmetric dimers, generating R ₂ ²(8) ring motifs, which stack along the b axis.

Related literature

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

Experimental

Crystal data

C₁₂H₁₃N₅O₂S
M _r = 291.33
Monoclinic,
a = 14.3207 (13) Å
b = 5.2003 (5) Å
c = 19.5919 (18) Å
β = 108.369 (2)°
V = 1384.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.61 × 0.28 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.866, T _max = 0.980
26169 measured reflections
4567 independent reflections
3273 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.187
S = 1.05
4567 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.34 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/S1600536811037883/lh5336sup1.cif

e-67-o2711-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037883/lh5336Isup3.hkl

e-67-o2711-Isup3.hkl^{(223.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037883/lh5336Isup3.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⋯O2	0.85 (3)	2.13 (3)	2.775 (2)	133 (2)
N5—H2N5⋯O2	0.89 (3)	1.98 (3)	2.715 (3)	138 (3)
N5—H1N5⋯S1ⁱ	0.86 (3)	2.52 (3)	3.366 (2)	168 (2)

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Symmetry code: (i) Inline graphic .

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

Pyrazoles are a novel class of heterocyclic compounds possessing a wide variety of application in the agrochemical and pharmaceutical industries. Derivatives of pyrazoles are found to show good antibacterial (Rai et al., 2008), anti-inflammatory, analgesic (Isloor et al., 2009), and anticancer activities. Pyrazolines are well known and important nitrogen-containing five membered heterocyclic compounds. Several pyrazoline derivatives have been found to possess considerable biological activities which stimulated research activities in this field (Girisha et al., 2010). In view of these observations and in continuation of our search for biologically active pyrazole derivatives, we herein report the crystal structure of the title compound.

In the molecular structure (Fig. 1), an intramolecular N1—H1N1···O2 and N5—H2N5···O2 hydrogen bond (Table 1) stabilize the molecular structure and forms two S(6) ring motifs (Bernstein et al., 1995). The mean planes of the benzene ring (C1–C6) and the 4,5-dihydro-1H-pyrazole ring (N3/N4/C7–C9) form a dihedral angle of 14.36 (11)°. Bond lengths (Allen et al., 1987) and angles are within normal range.

The crystal packing is shown in Fig. 2. Molecules are linked by pairs of intermolecular N5—H1N5···S1ⁱ hydrogen bonds (Table 1) to form dimers, generating R²₂(8) ring motifs (Bernstein et al., 1995) and these sets of ring motifs are stacked along the b axis.

Experimental

To a solution of ethyl 2-[(2-methoxyphenyl)hydrazono]-3-oxobutanoate (0.01 mol) in glacial acetic acid (20 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 mixtures of DMF and ethanol by slow evaporation.