3-(4-Chloro­phen­yl)-1-[(E)-1-(4-chloro­phen­yl)-2-(4-methyl­phenyl­sulfan­yl)ethen­yl]-4-(4-methyl­phenyl­sulfan­yl)-1H-pyrazole

Ramesh, P.; Manikannan, R.; Muthusubramanian, S.; Sundaresan, S.S.; Ponnuswamy, M.N.

doi:10.1107/S1600536809043293

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages o2881-o2882

https://doi.org/10.1107/S1600536809043293

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3-(4-Chlorophenyl)-1-[(E)-1-(4-chlorophenyl)-2-(4-methylphenylsulfanyl)ethenyl]-4-(4-methylphenylsulfanyl)-1H-pyrazole

P. Ramesh,^a Ramaiyan Manikannan,^b S. Muthusubramanian,^b S. S. Sundaresan ^a and M. N. Ponnuswamy ^a ^*

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India
^*Correspondence e-mail: mnpsy2004@yahoo.com

(Received 4 October 2009; accepted 20 October 2009; online 28 October 2009)

In the title compound, C₃₁H₂₄Cl₂N₂S₂, the pyrazole ring adopts planar conformation with a maximum deviation of 0.002 (2) Å. The chlorophenyl rings are twisted out of the plane of the pyrazole ring by 75.1 (1) and 39.5 (1)°. The crystal packing is controlled by weak intermolecular C—H⋯π interactions.

Related literature

For the pharmacological and medicinal properties of pyrazole derivatives, see: Baraldi et al. (1998 ); Bruno et al. (1990 ); Cottineau et al. (2002 ); Londershausen (1996 ); Chen & Li (1998 ); Mishra et al. (1998 ); Smith et al. (2001 ). For sp² hybridization, see: Beddoes et al., 1986 ). For bond-length data, see: Jin et al. (2004 ).

Experimental

Crystal data

C₃₁H₂₄Cl₂N₂S₂
M_r = 559.54
Monoclinic, P 2₁ /n
a = 9.7515 (2) Å
b = 10.2097 (3) Å
c = 27.6705 (6) Å
β = 96.402 (1)°
V = 2737.69 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.883, T_max = 0.921
38656 measured reflections
9852 independent reflections
5773 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.160
S = 1.03
9852 reflections
336 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
C—H⋯π interactions (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C33—H33C⋯Cg3ⁱ	0.96	2.90	3.851 (3)	171
C9—H9⋯Cg5ⁱⁱ	0.93	3.03	3.839 (2)	147
Symmetry codes: (i) -x+2, -y, -z; (ii) -x+2, -y+1, -z. Cg3 and Cg5 are the centroids of the C14–C19 and C26–C31 rings, respectively.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, (1997 )); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809043293/bt5084sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043293/bt5084Isup2.hkl

checkCIF report

Comment top

Pyrazole derivatives possess significant antiarrhythmic and sedative (Bruno et al., 1990), hypoglycemic (Cottineau et al., 2002), antiviral (Baraldi et al., 1998), and pesticidal (Londershausen et al., 1996) properties. Some pyrazole derivatives are successfully tested for their antifungal (Chen & Li, 1998), antihistaminic (Mishra et al., 1998) and anti-inflammatory (Smith et al., 2001) activities.

The ORTEP plot of the molecule is shown in Fig. 1. The pyrazole ring adopts a planar conformation. The sum of the bond angles at N2 of the pyrazole ring (360.0°) is in accordance with sp2 hybridization (Beddoes et al., 1986). The C—N bond lengths in the pyrazole ring are 1.352 (2) and 1.328 (2) Å, which are shorter than single bond length of 1.443 Å, but longer than a double bond length of 1.269 Å (Jin et al., 2004), indicating electron delocalization. The chlorophenyl rings are twisted from the pyrazole ring at angles of 75.1 (1)° and 39.5 (1)°, respectively. The crystal packing is stabilized by weak C—H···π type of intermolecular interactions in addition to van der Waals forces.

Related literature top

For the pharmacological and medicinal properties of pyrazole derivatives, see: Baraldi et al. (1998); Bruno et al. (1990); Cottineau et al. (2002); Londershausen (1996); Chen & Li (1998); Mishra et al. (1998); Smith et al. (2001). For sp² hybridization, see: Beddoes et al., 1986). For bond-length data, see: Jin et al. (2004). Cg3 and Cg5 are the centroids of the C14–C19 and C26–C31 rings, respectively.

Experimental top

To a mixture of 1-(4-Chlorophenyl) -2-[(4-methylphenyl)sulfanyl]-1-ethanone N-(Z)-1-(4-chlorophenyl) -2-[(4-methylphenyl)sulfanyl]ethylidenehydrazone (0.003 mole) and 3 ml of dimethyl formamide kept in ice bath at 0°C, phosphorous oxycholride (0.024 mole) was added dropwise for 5–10 minutes. The reaction mixture was then irradiated under microwaves for 30 sec. The process of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was poured into crushed ice and extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate. The different compounds present in the mixture were separated by column chromatography using petroleum ether and ethyl acetate mixture as eluent. This isolated compound was recrystallized in dichloromethane to obtain 3-(4-Chlorophenyl)-1-(E)-1-(4-chlorophenyl)-2-[(4-methylphenyl) sulfanyl]ethenyl-4-[(4-methylphenyl)sulfanyl]-1H-pyrazole.

Structure description top

For the pharmacological and medicinal properties of pyrazole derivatives, see: Baraldi et al. (1998); Bruno et al. (1990); Cottineau et al. (2002); Londershausen (1996); Chen & Li (1998); Mishra et al. (1998); Smith et al. (2001). For sp² hybridization, see: Beddoes et al., 1986). For bond-length data, see: Jin et al. (2004). Cg3 and Cg5 are the centroids of the C14–C19 and C26–C31 rings, respectively.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, (1997)); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. Perspective view of the molecule showing the displacement ellipsoids are drawn at 50% probability level. H atoms have been omitted for clarity.

3-(4-Chlorophenyl)-1-[(E)-1-(4-chlorophenyl)-2-(4- methylphenylsulfanyl)ethenyl]-4-(4-methylphenylsulfanyl)-1H-pyrazole top

Crystal data top

C₃₁H₂₄Cl₂N₂S₂	F(000) = 1160
M_r = 559.54	D_x = 1.358 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2546 reflections
a = 9.7515 (2) Å	θ = 1.5–32.5°
b = 10.2097 (3) Å	µ = 0.41 mm⁻¹
c = 27.6705 (6) Å	T = 293 K
β = 96.402 (1)°	Block, colourless
V = 2737.69 (11) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII diffractometer	9852 independent reflections
Radiation source: fine-focus sealed tube	5773 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and φ scans	θ_max = 32.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −14→14
T_min = 0.883, T_max = 0.921	k = −15→15
38656 measured reflections	l = −41→39

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0723P)² + 0.5516P] where P = (F_o² + 2F_c²)/3
9852 reflections	(Δ/σ)_max = 0.003
336 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₃₁H₂₄Cl₂N₂S₂	V = 2737.69 (11) Å³
M_r = 559.54	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.7515 (2) Å	µ = 0.41 mm⁻¹
b = 10.2097 (3) Å	T = 293 K
c = 27.6705 (6) Å	0.30 × 0.25 × 0.20 mm
β = 96.402 (1)°

Data collection top

Bruker Kappa APEXII diffractometer	9852 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	5773 reflections with I > 2σ(I)
T_min = 0.883, T_max = 0.921	R_int = 0.032
38656 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.160	H-atom parameters constrained
S = 1.03	Δρ_max = 0.54 e Å⁻³
9852 reflections	Δρ_min = −0.33 e Å⁻³
336 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.08583 (6)	−0.11974 (5)	0.63584 (2)	0.05549 (15)
S2	0.25311 (5)	0.35982 (5)	0.42760 (2)	0.05549 (15)
Cl1	−0.13889 (7)	0.45353 (6)	0.68961 (2)	0.07471 (19)
Cl2	0.48797 (8)	−0.21313 (9)	0.30187 (2)	0.0905 (2)
N1	0.23543 (16)	0.02119 (14)	0.49711 (5)	0.0415 (3)
N2	0.18350 (16)	0.10815 (14)	0.52737 (5)	0.0421 (3)
C3	0.1835 (2)	0.23137 (18)	0.50948 (7)	0.0472 (4)
H3	0.1531	0.3062	0.5242	0.057*
C4	0.23608 (19)	0.22595 (18)	0.46595 (7)	0.0446 (4)
C5	0.26756 (18)	0.09181 (17)	0.45965 (6)	0.0398 (4)
C6	0.13934 (19)	0.06576 (17)	0.57196 (6)	0.0410 (4)
C7	0.1621 (2)	−0.05738 (19)	0.58678 (7)	0.0485 (4)
H7	0.2196	−0.1107	0.5707	0.058*
C8	0.2206 (2)	−0.21076 (18)	0.66790 (6)	0.0461 (4)
C9	0.3584 (2)	−0.1814 (2)	0.66695 (8)	0.0583 (5)
H9	0.3845	−0.1116	0.6484	0.070*
C10	0.4568 (3)	−0.2562 (2)	0.69371 (8)	0.0653 (6)
H10	0.5496	−0.2370	0.6924	0.078*
C11	0.4224 (3)	−0.3585 (2)	0.72236 (7)	0.0606 (5)
C12	0.2849 (3)	−0.3848 (2)	0.72369 (8)	0.0614 (6)
H12	0.2592	−0.4524	0.7433	0.074*
C13	0.1842 (2)	−0.3134 (2)	0.69661 (7)	0.0566 (5)
H13	0.0917	−0.3340	0.6976	0.068*
C14	0.07032 (18)	0.16654 (17)	0.59941 (6)	0.0389 (3)
C15	0.1380 (2)	0.2157 (2)	0.64224 (7)	0.0495 (4)
H15	0.2271	0.1877	0.6527	0.059*
C16	0.0749 (2)	0.3054 (2)	0.66948 (7)	0.0523 (5)
H16	0.1212	0.3388	0.6980	0.063*
C17	−0.0571 (2)	0.34490 (18)	0.65410 (6)	0.0459 (4)
C18	−0.1264 (2)	0.29888 (19)	0.61145 (7)	0.0478 (4)
H18	−0.2155	0.3273	0.6012	0.057*
C19	−0.06171 (19)	0.20999 (18)	0.58410 (6)	0.0443 (4)
H19	−0.1074	0.1789	0.5551	0.053*
C20	0.4342 (2)	0.38614 (17)	0.43419 (7)	0.0441 (4)
C21	0.4884 (2)	0.4601 (2)	0.39927 (7)	0.0521 (5)
H21	0.4301	0.4967	0.3740	0.063*
C22	0.6289 (2)	0.4800 (2)	0.40176 (8)	0.0549 (5)
H22	0.6639	0.5305	0.3780	0.066*
C23	0.7187 (2)	0.42680 (19)	0.43848 (8)	0.0524 (5)
C24	0.6620 (3)	0.3574 (2)	0.47388 (9)	0.0679 (6)
H24	0.7199	0.3227	0.4997	0.081*
C25	0.5222 (2)	0.3377 (2)	0.47219 (8)	0.0649 (6)
H25	0.4869	0.2914	0.4970	0.078*
C26	0.32826 (18)	0.02448 (17)	0.42028 (6)	0.0400 (4)
C27	0.2903 (2)	0.0553 (2)	0.37175 (6)	0.0510 (5)
H27	0.2310	0.1252	0.3636	0.061*
C28	0.3405 (2)	−0.0176 (2)	0.33562 (7)	0.0576 (5)
H28	0.3147	0.0028	0.3031	0.069*
C29	0.4282 (2)	−0.1200 (2)	0.34765 (7)	0.0553 (5)
C30	0.4714 (2)	−0.1501 (2)	0.39539 (8)	0.0567 (5)
H30	0.5336	−0.2178	0.4032	0.068*
C31	0.4201 (2)	−0.07719 (19)	0.43141 (7)	0.0490 (4)
H31	0.4480	−0.0969	0.4638	0.059*
C32	0.5335 (3)	−0.4378 (3)	0.75125 (10)	0.0887 (9)
H32A	0.5850	−0.4854	0.7294	0.133*
H32B	0.4918	−0.4983	0.7718	0.133*
H32C	0.5942	−0.3802	0.7709	0.133*
C33	0.8720 (2)	0.4392 (3)	0.43899 (11)	0.0728 (7)
H33A	0.9079	0.3617	0.4253	0.109*
H33B	0.9136	0.4497	0.4719	0.109*
H33C	0.8929	0.5140	0.4201	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0571 (3)	0.0534 (3)	0.0597 (3)	0.0077 (2)	0.0230 (2)	0.0147 (2)
S2	0.0492 (3)	0.0490 (3)	0.0690 (3)	0.0058 (2)	0.0096 (2)	0.0254 (2)
Cl1	0.0911 (5)	0.0722 (4)	0.0659 (3)	0.0193 (3)	0.0308 (3)	−0.0139 (3)
Cl2	0.0853 (5)	0.1220 (6)	0.0684 (4)	−0.0011 (4)	0.0276 (3)	−0.0391 (4)
N1	0.0492 (8)	0.0357 (7)	0.0409 (7)	0.0026 (6)	0.0111 (6)	0.0010 (6)
N2	0.0519 (9)	0.0344 (7)	0.0416 (7)	0.0020 (6)	0.0125 (6)	0.0017 (6)
C3	0.0532 (11)	0.0349 (9)	0.0553 (10)	0.0047 (8)	0.0140 (8)	0.0039 (7)
C4	0.0460 (10)	0.0392 (9)	0.0498 (9)	0.0025 (8)	0.0112 (8)	0.0094 (7)
C5	0.0398 (9)	0.0391 (9)	0.0411 (8)	0.0002 (7)	0.0066 (7)	0.0051 (7)
C6	0.0451 (9)	0.0391 (9)	0.0402 (8)	0.0021 (7)	0.0107 (7)	0.0008 (7)
C7	0.0563 (11)	0.0428 (10)	0.0494 (9)	0.0078 (8)	0.0193 (8)	0.0051 (8)
C8	0.0559 (11)	0.0412 (9)	0.0433 (9)	−0.0014 (8)	0.0143 (8)	0.0009 (7)
C9	0.0607 (13)	0.0519 (12)	0.0640 (12)	−0.0077 (10)	0.0141 (10)	0.0108 (9)
C10	0.0556 (13)	0.0749 (15)	0.0660 (13)	−0.0008 (11)	0.0096 (10)	0.0038 (11)
C11	0.0736 (15)	0.0634 (14)	0.0451 (10)	0.0151 (11)	0.0085 (9)	−0.0005 (9)
C12	0.0828 (16)	0.0545 (12)	0.0484 (10)	0.0020 (11)	0.0147 (10)	0.0124 (9)
C13	0.0614 (13)	0.0586 (12)	0.0522 (11)	−0.0069 (10)	0.0174 (9)	0.0101 (9)
C14	0.0424 (9)	0.0360 (8)	0.0393 (8)	−0.0002 (7)	0.0090 (7)	0.0014 (6)
C15	0.0450 (10)	0.0531 (11)	0.0491 (10)	0.0040 (8)	−0.0004 (8)	−0.0048 (8)
C16	0.0611 (12)	0.0535 (11)	0.0415 (9)	−0.0004 (9)	0.0014 (8)	−0.0081 (8)
C17	0.0562 (11)	0.0402 (9)	0.0447 (9)	0.0030 (8)	0.0198 (8)	−0.0002 (7)
C18	0.0411 (10)	0.0457 (10)	0.0574 (10)	0.0025 (8)	0.0090 (8)	−0.0002 (8)
C19	0.0433 (10)	0.0427 (9)	0.0465 (9)	−0.0016 (8)	0.0029 (7)	−0.0048 (7)
C20	0.0502 (10)	0.0361 (9)	0.0469 (9)	0.0048 (7)	0.0091 (8)	0.0047 (7)
C21	0.0570 (12)	0.0542 (11)	0.0459 (9)	0.0034 (9)	0.0086 (8)	0.0114 (8)
C22	0.0569 (12)	0.0552 (12)	0.0549 (11)	−0.0034 (10)	0.0162 (9)	0.0050 (9)
C23	0.0513 (11)	0.0397 (10)	0.0659 (12)	−0.0011 (8)	0.0060 (9)	−0.0104 (8)
C24	0.0593 (13)	0.0685 (15)	0.0720 (14)	0.0010 (11)	−0.0097 (11)	0.0181 (12)
C25	0.0635 (14)	0.0664 (14)	0.0637 (13)	−0.0024 (11)	0.0024 (10)	0.0300 (11)
C26	0.0375 (9)	0.0437 (9)	0.0396 (8)	−0.0027 (7)	0.0075 (6)	0.0031 (7)
C27	0.0421 (10)	0.0679 (13)	0.0428 (9)	0.0010 (9)	0.0043 (7)	0.0072 (8)
C28	0.0469 (11)	0.0878 (16)	0.0382 (9)	−0.0089 (11)	0.0059 (8)	0.0003 (9)
C29	0.0462 (11)	0.0725 (14)	0.0498 (10)	−0.0123 (10)	0.0173 (8)	−0.0154 (9)
C30	0.0568 (12)	0.0572 (12)	0.0578 (11)	0.0074 (10)	0.0141 (9)	−0.0059 (9)
C31	0.0563 (11)	0.0492 (10)	0.0416 (9)	0.0053 (9)	0.0060 (8)	0.0022 (7)
C32	0.100 (2)	0.100 (2)	0.0659 (15)	0.0409 (18)	0.0087 (14)	0.0101 (14)
C33	0.0553 (13)	0.0606 (14)	0.1015 (19)	−0.0034 (11)	0.0041 (12)	−0.0168 (13)

Geometric parameters (Å, º) top

S1—C7	1.7398 (19)	C16—H16	0.9300
S1—C8	1.766 (2)	C17—C18	1.376 (3)
S2—C4	1.7496 (18)	C18—C19	1.378 (3)
S2—C20	1.776 (2)	C18—H18	0.9300
Cl1—C17	1.7340 (18)	C19—H19	0.9300
Cl2—C29	1.736 (2)	C20—C25	1.373 (3)
N1—C5	1.328 (2)	C20—C21	1.377 (3)
N1—N2	1.3565 (19)	C21—C22	1.379 (3)
N2—C3	1.352 (2)	C21—H21	0.9300
N2—C6	1.419 (2)	C22—C23	1.376 (3)
C3—C4	1.362 (3)	C22—H22	0.9300
C3—H3	0.9300	C23—C24	1.374 (3)
C4—C5	1.418 (3)	C23—C33	1.500 (3)
C5—C26	1.467 (2)	C24—C25	1.373 (3)
C6—C7	1.333 (3)	C24—H24	0.9300
C6—C14	1.484 (2)	C25—H25	0.9300
C7—H7	0.9300	C26—C31	1.383 (3)
C8—C9	1.380 (3)	C26—C27	1.389 (2)
C8—C13	1.385 (3)	C27—C28	1.379 (3)
C9—C10	1.377 (3)	C27—H27	0.9300
C9—H9	0.9300	C28—C29	1.369 (3)
C10—C11	1.376 (3)	C28—H28	0.9300
C10—H10	0.9300	C29—C30	1.375 (3)
C11—C12	1.372 (4)	C30—C31	1.381 (3)
C11—C32	1.508 (3)	C30—H30	0.9300
C12—C13	1.376 (3)	C31—H31	0.9300
C12—H12	0.9300	C32—H32A	0.9600
C13—H13	0.9300	C32—H32B	0.9600
C14—C19	1.383 (3)	C32—H32C	0.9600
C14—C15	1.385 (2)	C33—H33A	0.9600
C15—C16	1.374 (3)	C33—H33B	0.9600
C15—H15	0.9300	C33—H33C	0.9600
C16—C17	1.371 (3)

C7—S1—C8	103.04 (9)	C19—C18—H18	120.5
C4—S2—C20	102.51 (9)	C18—C19—C14	120.68 (17)
C5—N1—N2	105.26 (13)	C18—C19—H19	119.7
C3—N2—N1	111.58 (14)	C14—C19—H19	119.7
C3—N2—C6	127.92 (15)	C25—C20—C21	118.63 (19)
N1—N2—C6	120.49 (14)	C25—C20—S2	123.61 (16)
N2—C3—C4	107.54 (16)	C21—C20—S2	117.76 (14)
N2—C3—H3	126.2	C20—C21—C22	120.14 (18)
C4—C3—H3	126.2	C20—C21—H21	119.9
C3—C4—C5	104.82 (15)	C22—C21—H21	119.9
C3—C4—S2	125.11 (15)	C23—C22—C21	121.67 (19)
C5—C4—S2	130.04 (14)	C23—C22—H22	119.2
N1—C5—C4	110.80 (15)	C21—C22—H22	119.2
N1—C5—C26	118.34 (15)	C24—C23—C22	117.2 (2)
C4—C5—C26	130.85 (15)	C24—C23—C33	121.1 (2)
C7—C6—N2	119.92 (16)	C22—C23—C33	121.7 (2)
C7—C6—C14	124.46 (16)	C25—C24—C23	121.9 (2)
N2—C6—C14	115.62 (14)	C25—C24—H24	119.1
C6—C7—S1	120.93 (15)	C23—C24—H24	119.1
C6—C7—H7	119.5	C20—C25—C24	120.4 (2)
S1—C7—H7	119.5	C20—C25—H25	119.8
C9—C8—C13	119.17 (19)	C24—C25—H25	119.8
C9—C8—S1	123.22 (15)	C31—C26—C27	118.79 (17)
C13—C8—S1	117.56 (16)	C31—C26—C5	119.41 (15)
C10—C9—C8	119.4 (2)	C27—C26—C5	121.71 (17)
C10—C9—H9	120.3	C28—C27—C26	120.04 (19)
C8—C9—H9	120.3	C28—C27—H27	120.0
C11—C10—C9	122.1 (2)	C26—C27—H27	120.0
C11—C10—H10	119.0	C29—C28—C27	119.92 (18)
C9—C10—H10	119.0	C29—C28—H28	120.0
C12—C11—C10	117.8 (2)	C27—C28—H28	120.0
C12—C11—C32	121.8 (2)	C28—C29—C30	121.33 (19)
C10—C11—C32	120.4 (2)	C28—C29—Cl2	119.50 (16)
C11—C12—C13	121.5 (2)	C30—C29—Cl2	119.16 (18)
C11—C12—H12	119.3	C29—C30—C31	118.5 (2)
C13—C12—H12	119.3	C29—C30—H30	120.8
C12—C13—C8	120.0 (2)	C31—C30—H30	120.8
C12—C13—H13	120.0	C30—C31—C26	121.40 (18)
C8—C13—H13	120.0	C30—C31—H31	119.3
C19—C14—C15	118.97 (16)	C26—C31—H31	119.3
C19—C14—C6	121.71 (15)	C11—C32—H32A	109.5
C15—C14—C6	119.30 (16)	C11—C32—H32B	109.5
C16—C15—C14	120.76 (18)	H32A—C32—H32B	109.5
C16—C15—H15	119.6	C11—C32—H32C	109.5
C14—C15—H15	119.6	H32A—C32—H32C	109.5
C17—C16—C15	119.21 (17)	H32B—C32—H32C	109.5
C17—C16—H16	120.4	C23—C33—H33A	109.5
C15—C16—H16	120.4	C23—C33—H33B	109.5
C16—C17—C18	121.34 (17)	H33A—C33—H33B	109.5
C16—C17—Cl1	119.20 (15)	C23—C33—H33C	109.5
C18—C17—Cl1	119.46 (16)	H33A—C33—H33C	109.5
C17—C18—C19	119.02 (18)	H33B—C33—H33C	109.5
C17—C18—H18	120.5

C5—N1—N2—C3	−0.3 (2)	C19—C14—C15—C16	0.6 (3)
C5—N1—N2—C6	−179.36 (16)	C6—C14—C15—C16	−177.49 (18)
N1—N2—C3—C4	0.4 (2)	C14—C15—C16—C17	0.8 (3)
C6—N2—C3—C4	179.37 (18)	C15—C16—C17—C18	−1.5 (3)
N2—C3—C4—C5	−0.3 (2)	C15—C16—C17—Cl1	177.69 (16)
N2—C3—C4—S2	178.16 (14)	C16—C17—C18—C19	0.8 (3)
C20—S2—C4—C3	108.01 (18)	Cl1—C17—C18—C19	−178.36 (15)
C20—S2—C4—C5	−73.92 (19)	C17—C18—C19—C14	0.6 (3)
N2—N1—C5—C4	0.10 (19)	C15—C14—C19—C18	−1.3 (3)
N2—N1—C5—C26	179.47 (15)	C6—C14—C19—C18	176.76 (17)
C3—C4—C5—N1	0.1 (2)	C4—S2—C20—C25	−18.3 (2)
S2—C4—C5—N1	−178.23 (15)	C4—S2—C20—C21	162.26 (16)
C3—C4—C5—C26	−179.13 (18)	C25—C20—C21—C22	2.6 (3)
S2—C4—C5—C26	2.5 (3)	S2—C20—C21—C22	−177.86 (16)
C3—N2—C6—C7	−171.8 (2)	C20—C21—C22—C23	0.4 (3)
N1—N2—C6—C7	7.1 (3)	C21—C22—C23—C24	−2.7 (3)
C3—N2—C6—C14	7.6 (3)	C21—C22—C23—C33	174.9 (2)
N1—N2—C6—C14	−173.51 (15)	C22—C23—C24—C25	2.0 (4)
N2—C6—C7—S1	−169.62 (14)	C33—C23—C24—C25	−175.6 (2)
C14—C6—C7—S1	11.0 (3)	C21—C20—C25—C24	−3.2 (4)
C8—S1—C7—C6	−138.30 (17)	S2—C20—C25—C24	177.26 (19)
C7—S1—C8—C9	27.9 (2)	C23—C24—C25—C20	0.9 (4)
C7—S1—C8—C13	−154.47 (16)	N1—C5—C26—C31	−37.2 (2)
C13—C8—C9—C10	1.3 (3)	C4—C5—C26—C31	142.1 (2)
S1—C8—C9—C10	178.90 (17)	N1—C5—C26—C27	139.28 (18)
C8—C9—C10—C11	−1.3 (4)	C4—C5—C26—C27	−41.5 (3)
C9—C10—C11—C12	0.0 (3)	C31—C26—C27—C28	2.1 (3)
C9—C10—C11—C32	−179.8 (2)	C5—C26—C27—C28	−174.36 (18)
C10—C11—C12—C13	1.3 (3)	C26—C27—C28—C29	−0.3 (3)
C32—C11—C12—C13	−178.9 (2)	C27—C28—C29—C30	−2.0 (3)
C11—C12—C13—C8	−1.3 (3)	C27—C28—C29—Cl2	178.72 (16)
C9—C8—C13—C12	−0.1 (3)	C28—C29—C30—C31	2.3 (3)
S1—C8—C13—C12	−177.79 (17)	Cl2—C29—C30—C31	−178.35 (16)
C7—C6—C14—C19	−108.0 (2)	C29—C30—C31—C26	−0.5 (3)
N2—C6—C14—C19	72.6 (2)	C27—C26—C31—C30	−1.7 (3)
C7—C6—C14—C15	70.0 (3)	C5—C26—C31—C30	174.82 (18)
N2—C6—C14—C15	−109.32 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C33—H33C···Cg3ⁱ	0.96	2.90	3.851 (3)	171
C9—H9···Cg5ⁱⁱ	0.93	3.03	3.839 (2)	147

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₃₁H₂₄Cl₂N₂S₂
M_r	559.54
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.7515 (2), 10.2097 (3), 27.6705 (6)
β (°)	96.402 (1)
V (Å³)	2737.69 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.883, 0.921
No. of measured, independent and observed [I > 2σ(I)] reflections	38656, 9852, 5773
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.756

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.160, 1.03
No. of reflections	9852
No. of parameters	336
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.33

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, (1997)), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C33—H33C···Cg3ⁱ	0.96	2.90	3.851 (3)	171
C9—H9···Cg5ⁱⁱ	0.93	3.03	3.839 (2)	147

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+2, −y+1, −z.

Acknowledgements

PR thanks Dr Babu Varghese, SAIF, IIT-Madras, Chennai, India, for his help with the data collection.

References

Baraldi, P. G., Manfredini, S., Romagnoli, R., Stevanato, L., Zaid, A. N. & Manservigi, R. (1998). Nucleosides Nucleotides, 17, 2165–2171. Web of Science CrossRef CAS Google Scholar
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Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Smith, S. R., Denhardt, G. & Terminelli, C. (2001). Eur. J. Pharmacol. 432, 107–119. Web of Science CrossRef PubMed CAS Google Scholar
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Volume 65| Part 11| November 2009| Pages o2881-o2882

https://doi.org/10.1107/S1600536809043293

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3-(4-Chloro­phen­yl)-1-[(E)-1-(4-chloro­phen­yl)-2-(4-methyl­phenyl­sulfan­yl)ethen­yl]-4-(4-methyl­phenyl­sulfan­yl)-1H-pyrazole

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3-(4-Chlorophenyl)-1-[(E)-1-(4-chlorophenyl)-2-(4-methylphenylsulfanyl)ethenyl]-4-(4-methylphenylsulfanyl)-1H-pyrazole