Ethyl 1-(4-methyl­phen­yl)-5-phenyl-4-phenyl­sulfon­yl-1H-pyrazole-3-carboxyl­ate

Hatem A Abdel-Aziz; Khalid A Al-Rashood; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811036580

. 2011 Sep 14;67(Pt 10):o2623–o2624. doi: 10.1107/S1600536811036580

Ethyl 1-(4-methylphenyl)-5-phenyl-4-phenylsulfonyl-1H-pyrazole-3-carboxylate

Hatem A Abdel-Aziz ^a,^‡, Khalid A Al-Rashood ^a, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3201465 PMID: 22058766

Abstract

The title compound, C₂₅H₂₂N₂O₄S, features a tetra-substituted pyrazole ring. The dihedral angles formed between the five-membered ring (r.m.s. deviation = 0.007 Å) and the N- and C-bound phenyl rings are 48.10 (7) and 72.01 (7) °, respectively, indicating that the planes through the residues are significantly twisted from the plane through the heterocycle. The ester-CO₂ group is also twisted out of this plane, with an O—C—C—N torsion angle of −29.04 (11)°. The sulfonyl-O atoms lie to one side of the pyrazole plane and the sulfonylphenyl ring to the other. The dihedral angle between the two ring planes is 70.63 (7) °. Supramolecular arrays are formed in the crystal structure sustained by C—H⋯O and C—H⋯π(pyrazole) interactions and methyl-C—H⋯π(N-bound benzene) contacts.

Related literature

For background to the chemistry and biological activity of pyrazole derivatives, see: Abdel-Wahab et al. (2009 ▶); Abdel-Aziz et al. (2009 ▶, 2010 ▶).

Experimental

Crystal data

C₂₅H₂₂N₂O₄S
M _r = 446.51
Triclinic,
a = 7.2440 (3) Å
b = 11.0798 (5) Å
c = 14.8247 (5) Å
α = 68.818 (4)°
β = 87.773 (3)°
γ = 81.241 (4)°
V = 1096.36 (8) Å³
Z = 2
Cu Kα radiation
μ = 1.60 mm⁻¹
T = 100 K
0.40 × 0.30 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.566, T _max = 0.740
7378 measured reflections
4304 independent reflections
4106 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.091
S = 0.85
4304 reflections
290 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); 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 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036580/bt5639sup1.cif

e-67-o2623-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036580/bt5639Isup2.hkl

e-67-o2623-Isup2.hkl^{(210.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036580/bt5639Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the N1,N2,C4–C6 and C19–C24 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1ⁱ	0.95	2.45	3.2392 (19)	140
C16—H16⋯O2ⁱⁱ	0.95	2.49	3.3928 (18)	158
C17—H17⋯O1ⁱⁱⁱ	0.95	2.50	3.3895 (18)	157
C18—H18⋯O2ⁱⁱⁱ	0.95	2.58	3.4031 (17)	145
C23—H23⋯O4^iv	0.95	2.59	3.3155 (18)	133
C15—H15⋯Cg1ⁱ	0.95	2.80	3.6781 (15)	154
C25—H25c⋯Cg2^v	0.98	2.64	3.5649 (16)	157

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

Acknowledgments

The authors acknowledge the research center, College of Pharmacy, and Deanship of Scientific Research, King Saud University, for financial support of this project. The University of Malaya is also thanked for support of the crystallographic facility.

supplementary crystallographic information

Comment

Our previous work evaluating the biological potential of pyrazole derivatives (Abdel-Wahab et al., 2009; Abdel-Aziz et al., 2009; Abdel-Aziz et al., 2010) lead to the characterization of the title compound, (I).

The molecular structure of (I), Fig. 1, features a tetra-substituted pyrazole ring. The ester group is twisted out of the plane through the five-membered ring (r.m.s. deviation = 0.007 Å) as seen in the value of the O3—C3—C4—N1 torsion angle of -29.04 (11) °. The ring-connected benzene rings, (C13–C18) and (19–C24), form dihedral angles of 72.01 (7) and 48.10 (7) °, respectively, with the pyrazole ring also indicating significant twists; the dihedral angle between the two ring-bound benzene rings is 71.93 (7) °. With respect to the least-squares plane through the pyrazole ring, the sulfonyl-O atoms lie to one side, and the benzene ring to the other; the dihedral angle between the pyrazole and sulfonyl-benzene rings is 70.63 (7) °, indicating an almost orthogonal relationship.

The crystal structure features supramolecular arrays in the ac plane sustained by C—H···O and C—H···π interactions [involving the pyrazole ring as the acceptor], Fig. 2 and Table 1. Layers are connected along the b direction by C—H···.π interactions involving methyl-H and the N-bound benzene ring, Fig. 3 and Table 1.

Experimental

1-Phenyl-2-(phenylsulfonyl)ethanone (0.26 g, 1 mmol) was added to a stirred ethanolic sodium ethoxide solution [prepared from sodium metal (0.023 g, 1 mmol) and 25 ml of absolute ethanol]. After stirring for 20 min, ethyl 2-chloro-2-(2-p-tolylhydrazono)acetate (0.241 g, 1 mmol) was added and the reaction mixture was left to stir at room temperature for 12 h. Cold water (50 ml) was then added. The solid product was collected by filtration, washed with water and dried. Recrystallization from ethanol afforded the title pyrazole. The yellow blocks were isolated from its ethanol solution by slow evaporation at room temperature