5-Hy­droxy-3-methyl-5-phenyl-4,5-di­hydro-1H-pyrazole-1-carbothio­amide

Biplab Ganguly; Ana Foi; Fabio Doctorovich; Benu K Dey; Tapashi G Roy

doi:10.1107/S1600536811036658

. 2011 Sep 30;67(Pt 10):o2777. doi: 10.1107/S1600536811036658

5-Hydroxy-3-methyl-5-phenyl-4,5-dihydro-1H-pyrazole-1-carbothioamide

Biplab Ganguly ^a, Ana Foi ^b, Fabio Doctorovich ^b, Benu K Dey ^a, Tapashi G Roy ^a,^*

PMCID: PMC3201317 PMID: 22065480

Abstract

In the title compound C₁₁H₁₃N₃OS, the aromatic ring and the dihydropyrazole ring are oriented orthogonally with respect to each other, making a dihedral angle of 89.92 (9)°. An intramolecular O—H⋯S hydrogen bond occurs. In the crystal, weak N—H⋯N and N—H⋯S hydrogen bonds link the molecules into a columnar stack propagating along the b axis.

Related literature

For the biological activity of sulfur–nitrogen ligand compounds, see: Wilder Smith (1964 ▶); Grii & Khare (1976 ▶); French & Blang (1966 ▶); Davis Parke & Co (1957 ▶); Vattum & Rao (1959 ▶); Brockaman et al. (1959 ▶). For the carcinostatics thiosemicarbazone-containing nitrogen heterocycles, see: Freedlander & French (1958 ▶); French & Blang (1965 ▶).

Experimental

Crystal data

C₁₁H₁₃N₃OS
M _r = 235.31
Monoclinic,
a = 11.6955 (6) Å
b = 7.6889 (4) Å
c = 13.7588 (10) Å
β = 111.978 (7)°
V = 1147.35 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 K
0.39 × 0.41 × 0.43 mm

Data collection

Oxford Diffraction Gemini E CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.541, T _max = 1.000
19392 measured reflections
2326 independent reflections
2161 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.130
S = 1.07
2326 reflections
157 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811036658/ds2131sup1.cif

e-67-o2777-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036658/ds2131Isup2.hkl

e-67-o2777-Isup2.hkl^{(112KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036658/ds2131Isup3.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
O1—H1O⋯S1	0.93 (3)	2.35 (3)	3.1256 (15)	141 (2)
N3—H3A⋯S1ⁱ	0.89 (2)	2.81 (2)	3.5827 (17)	145.9 (19)
N3—H3B⋯N1ⁱⁱ	0.87 (2)	2.30 (2)	3.158 (2)	168 (2)

Open in a new tab

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

Acknowledgments

The authors acknowledge the UGC, Bangladesh, for the award of a fellowship to BG and thank the TWAS, Trieste, Italy, for awarding a TWAS–UNESCO Associateship to TGR. They are also grateful to ANPCyT for a grant (PME–2006–01113) and to R. Baggio for his helpful suggestions.

supplementary crystallographic information

Comment

Sulfur-Nitrogen ligand and their metal complexes have been reported as biologically important compounds possessing antiviral (Davis et al., 1957), antibacterial (Vattum & Rao, 1959), antipyretic (Wilder Smith, 1964), fungicidal (Grii & Khare, 1976) and analgesic (Wilder Smith, 1964) activities. It was reported that pyridine-2carboxaldehyde dithiosemicarbazone displays anticancer activity. However, no mechanism of action was proposed (Brockaman et al., 1959). French and co-workers (French & Blang, 1965; Freedlander & French, 1958; French & Blang, 1966) studied the carcinostatics thiosemicarbazones containing nitrogen heterocycles. The present investigation is an attempt to prepare a Schiff base ligand (HL) by the condensation of benzoyl acetone and thiosemicarbazide. During crystallization from ethanol-petroleum ether, the crystals of the title compound appropriate for single crystal X-ray diffraction were obtained.

In the crystal structure, the aromatic ring and the dihydropyrazole ring are oriented orthogonally with respect to each other [angle between these two rings is 89.92 (9) °]. Weak N–H···N (3.158 (2) Å) and N–H···S (3.5827 (17) Å) make the moloecules pack into a columnar stack propagating along b axis (see Figure 3).

Experimental

Thiosemicarbazide purchased from the local market was crystallized from ethanol and dried under vacuum desiccator over silica gel (m.p. 441- 443 K) before use. A hot solution of benzoyl acetone (1.62 g, 10 mmol) in absolute ethanol was mixed with the hot solution of thiosemicarbazide (1.22 g, 10 mmol) in the same solvent. The mixture was refluxed for 6 h on a water bath. After reducing the volume, a white product was filtered off. This product was washed with ethanol for several times and dried in a vacuum desiccator over silica gel (m.p. 449–451 K. Yield 1.95 g (82.9%). Anal. Calc. for C₁₁H₁₃N₃OS: C, 56.15; H, 5.57; N, 17.86; S, 13.62%. Found: C, 56.03; H, 5.61; N, 17.82; S, 13.57%. FT—IR (KBr, cm^-1) νmax: 3360 (m, OH), 3260 (s, NH), 1642 (m, C=N), 999 (m, N—N). Then the crystals suitable for the crystallographic study were prepared by slow evaporation from a ethanol-petroleum ether (2:1 v/v) solution of the ligand.