2-[3-(4-Chloro­phen­yl)-5-(4-fluoro­phenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thia­zole

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

doi:10.1107/S1600536813007496

. 2013 Mar 23;69(Pt 4):o576. doi: 10.1107/S1600536813007496

2-[3-(4-Chlorophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thiazole

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

PMCID: PMC3629623 PMID: 23634110

Abstract

In the title compound, C₂₄H₁₇ClFN₃S, the pyrazole ring is almost planar (r.m.s. deviation = 0.030 Å). With the exception of the methine-bound benzene ring, which forms a dihedral angle of 85.77 (13)° with the pyrazole ring, the remaining non-C atoms lie in an approximate plane (r.m.s. deviation = 0.084 Å) so that overall the molecule has a T-shape. In the crystal, centrosymmetrically related molecules are connected via π–π interactions between pyrazole rings [centroid–centroid distance = 3.5370 (15) Å] and these stack along the a axis with no specific interactions between them.

Related literature

For the biological activity of pyrazolin-1-carbothioamides, see: Abdel-Wahab et al. (2009 ▶, 2012 ▶); Lv et al. (2011 ▶); Chimenti et al. (2010 ▶). For a related structure, see: Abdel-Wahab et al. (2013 ▶).

Experimental

Crystal data

C₂₄H₁₇ClFN₃S
M _r = 433.92
Monoclinic,
a = 11.1360 (9) Å
b = 16.4129 (16) Å
c = 11.6066 (7) Å
β = 98.170 (7)°
V = 2099.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 295 K
0.25 × 0.25 × 0.25 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.956, T _max = 1.000
11642 measured reflections
4850 independent reflections
2627 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.140
S = 1.03
4850 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.17 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.^{(21.5KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007496/hb7058sup1.cif

e-69-0o576-sup1.cif^{(21.5KB, cif)}

Click here for additional data file.^{(237.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007496/hb7058Isup2.hkl

e-69-0o576-Isup2.hkl^{(237.6KB, hkl)}

Click here for additional data file.^{(7.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007496/hb7058Isup3.cml

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

Acknowledgments

We thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/03).

supplementary crystallographic information

Comment

The title compound (I) was investigated owing to the established biological activities exhibited by related pyrazolin-1-carbothioamides (Abdel-Wahab et al. 2012; Lv et al., 2011; Chimenti et al., 2010; Abdel-Wahab et al. 2009). Herein, the crystal and molecular structure of (I) is described.

In (I), Fig. 1, the pyrazolyl ring is quite planar with a r.m.s. deviation of the five atoms being 0.030 Å. This is in contrast to the situation observed in the recently described derivative with a methyl rather than a chloride (Abdel-Wahab et al. 2013) whereby an envelope conformation was found for each of the two independent molecules; the methine-C atom was the flap atom in each case. In (I), the dihedral angle between the pyrazolyl and thiazole (r.m.s. deviation = 0.002 Å) rings is 2.83 (13)°. The thiazole-bound benzene ring is co-planar; dihedral angle = 4.34 (13)° with the thiazole. About the pyrazolyl ring, the chlorobenzene ring is co-planar, dihedral angle = 6.92 (14)°, but the benzene ring bound at C11 is perpendicular, dihedral angle = 85.77 (13)°. Thus, there are two planar, mutually perpendicular domains in the molecule which adopts a T-shape, as was the case for the aforementioned literature structure but which exhibited some twists, e.g. between the five-membered rings (Abdel-Wahab et al. 2013).

The most prominent feature of the crystal packing is the formation of dimeric aggregates between centrosymmetrically related molecules viaπ—π interactions between pyrazolyl rings [inter-centroid distance = 3.5370 (15) Å for symmetry operation: 1 - x, 1 - y, 1 - z], Fig. 2. Dimeric units stack along the a axis with no specific interactions between them, Fig. 3.

Experimental

A mixture of 3-(4-chlorophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (0.333 g, 0.001 M) and phenacyl bromide (0.2 g, 0.001 M) in anhydrous ethanol (30 ml) was heated under reflux for about 4 h. The resultant solid was filtered and dried. Recrystallization was by slow evaporation of an ethanol solution of (I) to yield yellow cubes in 55% yield; M.pt: 418–419 K.