3-Methyl-5-oxo-4-(2-phenyl­hydrazinyl­idene)-4,5-dihydro-1H-pyrazole-1-carbothio­amide

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

doi:10.1107/S1600536811009779

. 2011 Mar 19;67(Pt 4):o928. doi: 10.1107/S1600536811009779

3-Methyl-5-oxo-4-(2-phenylhydrazinylidene)-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: PMC3099837 PMID: 21754198

Abstract

In the title compound, C₁₁H₁₁N₅OS, the pyrazole ring is approximately planar, with a maximum deviation of 0.010 (2) Å. The dihedral angles between the benzene ring and the pyrazole and carbothioamide groups are 5.42 (9) and 10.61 (18)°, respectively. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are connected by intermolecular N—H⋯O and C—H⋯S hydrogen bonds, forming R ₂ ²(12) ring motifs. In addition, there is a π–π stacking interaction [centroid–centroid distance = 3.5188 (11) Å] between the pyrazole and benzene rings. These interactions link the molecules into infinite chains along [001].

Related literature

For general background to and applications of pyrazole derivatives, see: Rai & Kalluraya (2006 ▶); Rai et al. (2008 ▶); Sridhar & Perumal (2003 ▶). For graph-set theory, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₁H₁₁N₅OS
M _r = 261.31
Monoclinic,
a = 7.7388 (1) Å
b = 16.1103 (3) Å
c = 11.3575 (2) Å
β = 121.058 (1)°
V = 1213.00 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 K
0.53 × 0.39 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.874, T _max = 0.967
16258 measured reflections
4393 independent reflections
3037 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.135
S = 1.05
4393 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.39 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 datablocks global, I. DOI: 10.1107/S1600536811009779/sj5118sup1.cif

e-67-0o928-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009779/sj5118Isup2.hkl

e-67-0o928-Isup2.hkl^{(215.3KB, 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—H1B⋯O1	0.86	2.16	2.8147 (16)	132
N5—H5C⋯O1ⁱ	0.86	2.03	2.8806 (15)	172
C1—H1A⋯S1ⁱⁱ	0.93	2.80	3.6838 (16)	159

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

Acknowledgments

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

supplementary crystallographic information

Comment

Pyrazole derivatives are in general well-known nitrogen-containing heterocyclic compounds and various procedures have been developed for their synthesis (Rai & Kalluraya, 2006). The chemistry of pyrazole derivatives has been the subject of much interest due to their importance for various applications and their widespread potential and proven biological and pharmacological activities (Rai et al., 2008). Steroids containing a pyrazole moiety are of interest as psychopharmacological agents. Some alkyl- and aryl-substituted pyrazoles have a sharply pronounced sedative action on the central nervous system. Furthermore, certain alkyl pyrazoles show significant bacteriostatic, bacteriocidal, fungicidal, analgesic and anti-pyretic activities (Sridhar & Perumal, 2003).

Fig.1 shows the molecular structure of (I). The pyrazole (C7–C9/N3/N4) ring is approximately planar with a maximum deviation of 0.010 (2) Å for atom C8. The dihedral angle between benzene and pyrazole rings is 5.42 (9)°. The carbothioamide group (S1/C11/N5) is twisted at a dihedral angle 10.61 (18)° from the pyrazole ring. The bond lengths (Allen et al., 1987) in (I) show normal values. An intramolecular N1—H1B···O1 hydrogen bond (Table 1) generates an S(6) ring motif (Bernstein et al., 1995).

In the crystal packing of (I) (Fig. 2), molecules are connected by N5—H5C···O1 and C1—H1A···S1 intermolecular hydrogen bonds to form R²₂(12) ring motifs. These interactions also link the molecules into infinite one-dimensional chains along [0 0 1]. In addition, there is a π–π stacking interaction between pyrazole (C7–C9/N3/N4; centroid Cg1) and benzene (C1–C6; centroid Cg2) rings with a Cg1···Cg2 separation of 3.5188 (11) Å.

Experimental

To a solution of ethyl-3-oxo-2-(2-phenylhydrazinylidene) butanoate (0.01mol) dissolved in glacial acetic acid (20ml), a solution of thiosemicarbazide (0.02mol) in glacial acetic acid (25ml) 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.