3-(4-Chloro­phen­yl)-5-(4-fluoro­phen­yl)-4,5-dihydro-1H-pyrazole-1-carbothio­amide

Bakr F Abdel-Wahab; Hanan A Mohamed; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536813004492

. 2013 Feb 20;69(Pt 3):o414–o415. doi: 10.1107/S1600536813004492

3-(4-Chlorophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide

Bakr F Abdel-Wahab ^a,^‡, Hanan A Mohamed ^b, Seik Weng Ng ^c,^d, Edward R T Tiekink ^c,^*

PMCID: PMC3588515 PMID: 23476591

Abstract

In the title compound, C₁₆H₁₃ClFN₃S, the pyrazole ring adopts an envelope conformation with the methine C atom being the flap atom. The chloro- and fluorobenzene rings are twisted out of the plane of the pyrazole ring [dihedral angles = 15.12 (11) and 80.55 (10)°, respectively]. The amine group is orientated towards a ring N atom, forming an intramolecular N—H⋯N hydrogen bond. This H atom also forms a hydrogen bond to the F atom, which along with N—H⋯S hydrogen bonding leads to a supramolecular chain along the c axis. Connections between chains of the type Cl⋯π lead to a layer in the bc plane.

Related literature

For the biological activity of pyrazolin-1-ylthiazoles, see: Abdel-Wahab et al. (2009 ▶, 2012 ▶); Chimenti et al. (2010 ▶). For related structures, see: Chantrapromma et al. (2012 ▶); Abdel-Wahab et al. (2013 ▶).

Experimental

Crystal data

C₁₆H₁₃ClFN₃S
M _r = 333.80
Monoclinic,
a = 14.5402 (9) Å
b = 11.2700 (8) Å
c = 9.5169 (6) Å
β = 103.850 (6)°
V = 1514.17 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 295 K
0.40 × 0.30 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.898, T _max = 1.000
10191 measured reflections
3478 independent reflections
2570 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.111
S = 1.01
3478 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(19KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813004492/hg5293sup1.cif

e-69-0o414-sup1.cif^{(19KB, cif)}

Click here for additional data file.^{(170.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813004492/hg5293Isup2.hkl

e-69-0o414-Isup2.hkl^{(170.6KB, hkl)}

Click here for additional data file.^{(5.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813004492/hg5293Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H31⋯N1	0.88	2.24	2.617 (2)	106
N3—H31⋯F1ⁱ	0.88	2.41	3.257 (2)	163
N3—H32⋯S1ⁱⁱ	0.88	2.81	3.5203 (19)	139
C4—Cl1⋯Cg1ⁱⁱⁱ	1.735 (2)	3.9240 (12)	4.183 (2)	86.17 (17)

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

Acknowledgments

We thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/12).

supplementary crystallographic information

Comment

Pyrazolin-1-ylthiazole derivatives are known to exhibit biological potential (Abdel-Wahab et al., 2012; Abdel-Wahab et al., 2009; Chimenti et al., 2010) and motivated the investigation of the title compound, (I).

The central pyrazolyl ring in (I), Fig. 1, adopts an envelope conformation with the methine-C9 atom being the flap atom. The amine group is orientated towards the ring-N2 atom, forming a hydrogen bond, Table 1, assisted by the near co-planar relationship between the thioamide group and the pyrazolyl ring with the N1—N2—C16—N3 torsion angle being -0.7 (2)°. Both the chloro- and fluoro-benzene rings are twisted out of the least-squares plane through the five-membered ring, forming dihedral angles of 15.12 (11) and 80.55 (10)°, respectively. Quite similar conformations have been observed in related structures bearing two six-membered rings (Chantrapromma et al., 2012; Abdel-Wahab et al., 2013).

In the crystal packing, the amine-H31 atom participating in the intramolecular N—H···N hydrogen bond also forms a hydrogen bond to the F1 atom, Table 1. This interaction along with an N—H···S hydrogen bond leads to a supramolecular chain along the c axis, Table 1. Chains are connected into a layer in the bc plane by Cl···π interactions, Fig. 2 and Table 1. Layers stack along the a axis without specific interactions between them, Fig. 3.

Experimental

To a suspension of (E)-1-(4-chlorophenyl)-3-(4-fluorophenyl)prop-2-en-1-one (1 mmol, 0.26 g) and sodium hydroxide (2.5 mmol, 1.0 g) in ethanol (20 ml), thiosemicarbazide (1.2 mmol, 0.11 g) was added. The mixture was refluxed for 12 h, then left to cool. The solid product was filtered off, washed with ethanol and dried. Recrystallization was by slow evaporation of its DMF solution.