1-(4-Methyl­phenyl­sulfon­yl)-5-phenyl-4,5-dihydro-1H-pyrazole

Li, J.; Zhao, W.

doi:10.1107/S1600536811025001

organic compounds

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Volume 67| Part 8| August 2011| Page o1898

doi:10.1107/S1600536811025001

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1-(4-Methylphenylsulfonyl)-5-phenyl-4,5-dihydro-1H-pyrazole

Jie Li ^a ^* and Wei Zhao ^a

^aMedical College, Zhejiang University City College, Hangzhou 310015, Zhejiang, People's Republic of China
^*Correspondence e-mail: lijie@zucc.edu.cn

(Received 9 May 2011; accepted 25 June 2011; online 2 July 2011)

The title compound, C₁₆H₁₆N₂O₂S, was synthesized by the reaction of 5-phenyl-4,5-dihydro-1H-pyrazole and 4-methylbenzene-1-sulfonyl chloride. The five-membered pyrazoline ring is nearly planar, with a miximum deviation of 0.078 (2) Å.

Related literature

For the pharmacological properties of pyrazoline derivatives, see: Goodell et al. (2006 ); Park et al. (2005 ); Shaharyar et al. (2006 ); Suresh et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₂S
M_r = 300.37
Orthorhombic, P c a 2₁
a = 19.2938 (7) Å
b = 6.0438 (2) Å
c = 12.9812 (5) Å
V = 1513.71 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.32 × 0.28 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.933, T_max = 0.947
5286 measured reflections
2168 independent reflections
1870 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.081
S = 1.05
2168 reflections
191 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ), 711 Friedel pairs
Flack parameter: 0.00 (8)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811025001/bv2186sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025001/bv2186Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025001/bv2186Isup3.cml

checkCIF report

Comment top

5-Phenyl-1-tosyl-4,5-dihydro-1H-pyrazoles are a key intermediates which can be used to synthesize pyrazoline derivatives, which are well known for their versatile pharmacological activities such as antitumor (Park et al., 2005), antibacterial (Shaharyar et al., 2006), antifungal (Goodell et al., 2006), antiviral, antiparasitic, anti-tubercular and insecticidal agents (Suresh et al., 2009). The title compound is one of these compounds and its structure is reported here.

Related literature top

For the pharmacological properties of pyrazoline derivatives, see: Goodell et al. (2006); Park et al. (2005); Shaharyar et al. (2006); Suresh et al. (2009).

Experimental top

A CH₂Cl2 solution of 5-phenyl-4,5-dihydro-1H-pyrazole (1.46 g, 0.01 mol)with 4-methylbenzene-1-sulfonyl chloride (2.15 g, 0.011 mol) was stired at room temperature for 4 h, then saturated aqueous sodium hydrogen carbonate (50 ml) was added into the solution. The mixture was extract with CH₂Cl₂. Then the solvent was removed and to give a white powder. Single crystals were obtained from the powder in methanol after 5 days.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. The molecular structure of title compound

1-(4-Methylphenylsulfonyl)-5-phenyl-4,5-dihydro-1H-pyrazole top

Crystal data top

C₁₆H₁₆N₂O₂S	F(000) = 632
M_r = 300.37	D_x = 1.318 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2341 reflections
a = 19.2938 (7) Å	θ = 3.1–29.4°
b = 6.0438 (2) Å	µ = 0.22 mm⁻¹
c = 12.9812 (5) Å	T = 293 K
V = 1513.71 (10) Å³	Block, colorless
Z = 4	0.32 × 0.28 × 0.25 mm

Data collection top

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer	2168 independent reflections
Radiation source: fine-focus sealed tube	1870 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 10.3592 pixels mm^-1	θ_max = 25.4°, θ_min = 3.1°
ω scans	h = −17→23
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −6→7
T_min = 0.933, T_max = 0.947	l = −15→10
5286 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0441P)² + 0.0462P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2168 reflections	Δρ_max = 0.15 e Å⁻³
191 parameters	Δρ_min = −0.26 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 711 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (8)

Crystal data top

C₁₆H₁₆N₂O₂S	V = 1513.71 (10) Å³
M_r = 300.37	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 19.2938 (7) Å	µ = 0.22 mm⁻¹
b = 6.0438 (2) Å	T = 293 K
c = 12.9812 (5) Å	0.32 × 0.28 × 0.25 mm

Data collection top

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer	2168 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1870 reflections with I > 2σ(I)
T_min = 0.933, T_max = 0.947	R_int = 0.028
5286 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.081	Δρ_max = 0.15 e Å⁻³
S = 1.05	Δρ_min = −0.26 e Å⁻³
2168 reflections	Absolute structure: Flack (1983), 711 Friedel pairs
191 parameters	Absolute structure parameter: 0.00 (8)
1 restraint

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	0.36119 (3)	0.55535 (9)	0.53950 (5)	0.0517 (2)
O1	0.37103 (10)	0.7881 (3)	0.5338 (2)	0.0737 (6)
O2	0.34854 (11)	0.4301 (3)	0.44842 (16)	0.0680 (6)
N1	0.29819 (12)	0.6172 (4)	0.7097 (2)	0.0680 (7)
N2	0.29200 (10)	0.5148 (3)	0.61190 (18)	0.0511 (6)
C1	0.43222 (13)	0.4394 (4)	0.6042 (2)	0.0452 (6)
C2	0.45625 (14)	0.2327 (4)	0.5752 (2)	0.0555 (7)
H2	0.4349	0.1557	0.5218	0.067*
C3	0.51202 (15)	0.1425 (4)	0.6261 (3)	0.0581 (7)
H3	0.5285	0.0046	0.6058	0.070*
C4	0.54427 (13)	0.2507 (4)	0.7066 (2)	0.0547 (7)
C5	0.60491 (17)	0.1474 (5)	0.7611 (3)	0.0828 (10)
H5C	0.6114	0.2183	0.8266	0.124*
H5B	0.6459	0.1653	0.7201	0.124*
H5A	0.5961	−0.0073	0.7715	0.124*
C6	0.51950 (14)	0.4589 (4)	0.7345 (2)	0.0530 (7)
H6	0.5409	0.5358	0.7878	0.064*
C7	0.46389 (13)	0.5524 (4)	0.6845 (2)	0.0500 (7)
H7	0.4476	0.6908	0.7044	0.060*
C8	0.26877 (16)	0.4944 (7)	0.7745 (3)	0.0833 (11)
H8	0.2666	0.5317	0.8440	0.100*
C9	0.23803 (18)	0.2892 (6)	0.7349 (3)	0.0839 (11)
H9A	0.1878	0.2940	0.7383	0.101*
H9B	0.2545	0.1614	0.7729	0.101*
C10	0.26345 (13)	0.2845 (4)	0.6227 (2)	0.0523 (7)
H10	0.3006	0.1753	0.6148	0.063*
C11	0.20658 (11)	0.2411 (3)	0.5454 (2)	0.0428 (5)
C12	0.15381 (12)	0.3928 (4)	0.5298 (3)	0.0516 (6)
H12	0.1543	0.5262	0.5654	0.062*
C13	0.10086 (14)	0.3487 (5)	0.4626 (2)	0.0619 (8)
H13	0.0661	0.4530	0.4525	0.074*
C14	0.09883 (16)	0.1535 (5)	0.4104 (3)	0.0705 (9)
H14	0.0627	0.1240	0.3651	0.085*
C15	0.15027 (17)	0.0006 (5)	0.4250 (3)	0.0694 (9)
H15	0.1490	−0.1331	0.3895	0.083*
C16	0.20389 (14)	0.0445 (4)	0.4922 (2)	0.0576 (7)
H16	0.2387	−0.0601	0.5017	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0487 (4)	0.0551 (3)	0.0513 (4)	−0.0086 (3)	−0.0036 (4)	0.0102 (4)
O1	0.0702 (12)	0.0549 (9)	0.0961 (16)	−0.0138 (8)	−0.0086 (14)	0.0230 (14)
O2	0.0698 (14)	0.0891 (13)	0.0451 (12)	−0.0115 (10)	−0.0081 (10)	0.0042 (11)
N1	0.0476 (14)	0.0842 (16)	0.072 (2)	−0.0022 (12)	0.0035 (14)	−0.0205 (16)
N2	0.0439 (12)	0.0530 (10)	0.0564 (15)	−0.0063 (9)	−0.0051 (11)	0.0041 (11)
C1	0.0434 (14)	0.0462 (12)	0.0460 (16)	−0.0091 (10)	0.0061 (12)	−0.0001 (12)
C2	0.0560 (17)	0.0538 (13)	0.0567 (18)	−0.0112 (12)	0.0010 (14)	−0.0077 (14)
C3	0.0597 (17)	0.0482 (13)	0.0663 (19)	0.0048 (12)	0.0084 (16)	−0.0035 (15)
C4	0.0438 (15)	0.0616 (15)	0.0585 (18)	0.0016 (13)	0.0070 (14)	−0.0004 (16)
C5	0.068 (2)	0.091 (2)	0.089 (3)	0.0186 (18)	−0.0106 (19)	−0.003 (2)
C6	0.0498 (16)	0.0601 (15)	0.0491 (16)	−0.0071 (12)	−0.0003 (14)	−0.0072 (15)
C7	0.0482 (15)	0.0467 (12)	0.0551 (18)	−0.0020 (11)	0.0042 (13)	−0.0080 (13)
C8	0.051 (2)	0.143 (3)	0.056 (2)	−0.020 (2)	−0.0031 (17)	−0.010 (2)
C9	0.076 (2)	0.123 (3)	0.0524 (19)	−0.037 (2)	−0.0169 (18)	0.029 (2)
C10	0.0441 (14)	0.0538 (13)	0.0589 (18)	−0.0075 (11)	−0.0118 (15)	0.0135 (14)
C11	0.0375 (12)	0.0484 (11)	0.0424 (14)	−0.0041 (9)	0.0018 (14)	0.0101 (13)
C12	0.0450 (14)	0.0557 (12)	0.0540 (17)	0.0044 (10)	−0.0020 (16)	−0.0027 (15)
C13	0.0484 (16)	0.0702 (16)	0.067 (2)	0.0055 (14)	−0.0098 (16)	0.0054 (16)
C14	0.063 (2)	0.085 (2)	0.064 (2)	−0.0111 (16)	−0.0217 (16)	0.0068 (18)
C15	0.083 (2)	0.0592 (15)	0.066 (2)	−0.0050 (15)	−0.0100 (19)	−0.0082 (17)
C16	0.0557 (17)	0.0519 (14)	0.0653 (19)	0.0081 (12)	−0.0054 (15)	0.0044 (14)

Geometric parameters (Å, º) top

S1—O1	1.4213 (16)	C7—H7	0.9300
S1—O2	1.425 (2)	C8—C9	1.468 (5)
S1—N2	1.651 (2)	C8—H8	0.9300
S1—C1	1.754 (3)	C9—C10	1.537 (5)
N1—C8	1.257 (4)	C9—H9A	0.9700
N1—N2	1.417 (3)	C9—H9B	0.9700
N2—C10	1.504 (3)	C10—C11	1.510 (4)
C1—C2	1.385 (3)	C10—H10	0.9800
C1—C7	1.387 (4)	C11—C16	1.375 (4)
C2—C3	1.376 (4)	C11—C12	1.385 (3)
C2—H2	0.9300	C12—C13	1.370 (4)
C3—C4	1.380 (4)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.361 (4)
C4—C6	1.394 (3)	C13—H13	0.9300
C4—C5	1.503 (4)	C14—C15	1.369 (4)
C5—H5C	0.9600	C14—H14	0.9300
C5—H5B	0.9600	C15—C16	1.379 (4)
C5—H5A	0.9600	C15—H15	0.9300
C6—C7	1.376 (4)	C16—H16	0.9300
C6—H6	0.9300

O1—S1—O2	120.35 (16)	N1—C8—C9	116.5 (3)
O1—S1—N2	106.53 (13)	N1—C8—H8	121.7
O2—S1—N2	104.77 (12)	C9—C8—H8	121.7
O1—S1—C1	108.43 (12)	C8—C9—C10	102.6 (3)
O2—S1—C1	108.62 (12)	C8—C9—H9A	111.2
N2—S1—C1	107.45 (11)	C10—C9—H9A	111.2
C8—N1—N2	107.7 (3)	C8—C9—H9B	111.2
N1—N2—C10	110.6 (2)	C10—C9—H9B	111.2
N1—N2—S1	112.15 (17)	H9A—C9—H9B	109.2
C10—N2—S1	119.12 (17)	N2—C10—C11	111.4 (2)
C2—C1—C7	120.1 (2)	N2—C10—C9	100.8 (2)
C2—C1—S1	119.4 (2)	C11—C10—C9	113.7 (2)
C7—C1—S1	120.48 (18)	N2—C10—H10	110.2
C3—C2—C1	119.2 (3)	C11—C10—H10	110.2
C3—C2—H2	120.4	C9—C10—H10	110.2
C1—C2—H2	120.4	C16—C11—C12	118.1 (2)
C2—C3—C4	121.9 (2)	C16—C11—C10	120.7 (2)
C2—C3—H3	119.0	C12—C11—C10	121.1 (2)
C4—C3—H3	119.0	C13—C12—C11	120.9 (2)
C3—C4—C6	118.0 (3)	C13—C12—H12	119.6
C3—C4—C5	120.7 (2)	C11—C12—H12	119.6
C6—C4—C5	121.3 (3)	C14—C13—C12	120.4 (3)
C4—C5—H5C	109.5	C14—C13—H13	119.8
C4—C5—H5B	109.5	C12—C13—H13	119.8
H5C—C5—H5B	109.5	C13—C14—C15	119.7 (3)
C4—C5—H5A	109.5	C13—C14—H14	120.1
H5C—C5—H5A	109.5	C15—C14—H14	120.1
H5B—C5—H5A	109.5	C14—C15—C16	120.1 (3)
C7—C6—C4	121.0 (3)	C14—C15—H15	120.0
C7—C6—H6	119.5	C16—C15—H15	120.0
C4—C6—H6	119.5	C11—C16—C15	120.8 (3)
C6—C7—C1	119.7 (2)	C11—C16—H16	119.6
C6—C7—H7	120.1	C15—C16—H16	119.6
C1—C7—H7	120.1

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₂S
M_r	300.37
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	19.2938 (7), 6.0438 (2), 12.9812 (5)
V (Å³)	1513.71 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.32 × 0.28 × 0.25

Data collection
Diffractometer	Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.933, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	5286, 2168, 1870
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.081, 1.05
No. of reflections	2168
No. of parameters	191
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.26
Absolute structure	Flack (1983), 711 Friedel pairs
Absolute structure parameter	0.00 (8)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

The authors thank Mr Ji-Yong Liu of Zhejiang University for the X-ray data collection. This paper was supported by the Research Fund for teachers of Zhejiang University City College.

References

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