4-(3-Methyl-5-phenyl-1H-pyrazol-1-yl)benzene­sulfonamide

Asiri, A.M.; Faidallah, H.M.; Al-Youbi, A.O.; Basaif, S.A.; Ng, S.W.

doi:10.1107/S1600536811032855

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2426

doi:10.1107/S1600536811032855

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4-(3-Methyl-5-phenyl-1H-pyrazol-1-yl)benzenesulfonamide

Abdullah M. Asiri,^a,^b Hassan M. Faidallah,^a Abdulrahman O. Al-Youbi,^a Salem A. Basaif ^a and Seik Weng Ng ^c,^a ^*

^aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, ^bCenter of Excellence for Advanced Materials Research, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 11 August 2011; accepted 13 August 2011; online 27 August 2011)

With respect to the planar five-membered ring of the title compound, C₁₆H₁₅N₃O₂S, the phenyl ring is aligned at 47.0 (1)° and the phenylene ring at 37.6 (1)°. The amino group has the N atom in a pyramidal geometry; the group is a hydrogen-bond donor to the sulfonyl O atom of one molecule and to the pyrazole N atom of another molecule, resulting in the formation of a layer parallel to the bc plane.

Related literature

For the synthesis, see: Gosselin et al. (2006 ); Organ & Mayer (2003 ).

Experimental

Crystal data

C₁₆H₁₅N₃O₂S
M_r = 313.37
Monoclinic, C 2/c
a = 28.2545 (8) Å
b = 11.9135 (4) Å
c = 9.3739 (3) Å
β = 91.016 (3)°
V = 3154.85 (17) Å³
Z = 8
Cu Kα radiation
μ = 1.91 mm⁻¹
T = 100 K
0.30 × 0.03 × 0.03 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.598, T_max = 0.945
6579 measured reflections
3137 independent reflections
2689 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.115
S = 1.03
3137 reflections
208 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.92 (2)	1.98 (2)	2.878 (2)	164 (2)
N1—H2⋯O1ⁱⁱ	0.86 (2)	2.07 (2)	2.930 (2)	177 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ .

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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811032855/bt5609sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811032855/bt5609Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811032855/bt5609Isup3.cml

checkCIF report

Comment top

We are examining the medicinal properties of phenylpyrazolones of which the 4-benzenesulfamide derivative (Scheme I) is expected to show enhanced activity. As the inhibitory activity against cyclooxygenase-1 and cyclooxygenase-2 of the title compound (Scheme I) has been claimed in a number of patents, other researchers have attempted its synthesis in order to increase yield (Gosselin et al., 2006; Organ & Mayer, 2003). With respect to the planar five-membered ring, the phenyl ring is aligned at 47.0 (1) ° and the phenylene ring at 37.6 (1)°. The amino group is hydrogen bond donor to the sulfonyl O atom of one molecule and to the pyrazolyl N atom of another molecule to result in the formation of a layer parallel to the bc plane.

Related literature top

For the synthesis, see: Gosselin et al. (2006); Organ & Mayer (2003).

Experimental top

1-Phenylbutan-1,3-dione (10 mmol) and 4-hydrazinobenzenesulfonamide hydrochloride (10 mmol) were heated in ethanol (50 ml) for 4 h; water was added to precipitate the product, which was collected and recrystallized from ethanol as light yellow crystals; m.p. 471–472 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₆H₁₅N₃O₂S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-(3-Methyl-5-phenyl-1H-pyrazol-1-yl)benzenesulfonamide top

Crystal data top

C₁₆H₁₅N₃O₂S	F(000) = 1312
M_r = 313.37	D_x = 1.320 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2yc	Cell parameters from 2773 reflections
a = 28.2545 (8) Å	θ = 3.1–74.2°
b = 11.9135 (4) Å	µ = 1.91 mm⁻¹
c = 9.3739 (3) Å	T = 100 K
β = 91.016 (3)°	Prism, light-yellow
V = 3154.85 (17) Å³	0.30 × 0.03 × 0.03 mm
Z = 8

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	3137 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2689 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.035
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.4°, θ_min = 3.1°
ω scans	h = −35→31
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −12→14
T_min = 0.598, T_max = 0.945	l = −11→9
6579 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0629P)² + 1.4812P] where P = (F_o² + 2F_c²)/3
3137 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₁₆H₁₅N₃O₂S	V = 3154.85 (17) Å³
M_r = 313.37	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 28.2545 (8) Å	µ = 1.91 mm⁻¹
b = 11.9135 (4) Å	T = 100 K
c = 9.3739 (3) Å	0.30 × 0.03 × 0.03 mm
β = 91.016 (3)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	3137 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2689 reflections with I > 2σ(I)
T_min = 0.598, T_max = 0.945	R_int = 0.035
6579 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.33 e Å⁻³
3137 reflections	Δρ_min = −0.51 e Å⁻³
208 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.690362 (14)	0.48353 (4)	0.65383 (4)	0.01752 (14)
O1	0.67646 (4)	0.41033 (11)	0.76803 (13)	0.0220 (3)
O2	0.69504 (5)	0.60135 (11)	0.68142 (14)	0.0252 (3)
N1	0.65210 (5)	0.46753 (14)	0.52785 (16)	0.0191 (3)
H1	0.6414 (8)	0.395 (2)	0.516 (2)	0.026 (6)*
H2	0.6583 (8)	0.5054 (18)	0.452 (2)	0.017 (5)*
N2	0.88441 (5)	0.35478 (13)	0.48169 (15)	0.0189 (3)
N3	0.89694 (5)	0.24415 (13)	0.47817 (17)	0.0217 (3)
C1	0.96762 (7)	0.13366 (18)	0.4272 (3)	0.0341 (5)
H1A	0.9686	0.0956	0.5199	0.051*
H1B	1.0000	0.1470	0.3954	0.051*
H1C	0.9508	0.0864	0.3573	0.051*
C2	0.94240 (6)	0.24326 (17)	0.4411 (2)	0.0234 (4)
C3	0.95933 (6)	0.35272 (17)	0.42301 (19)	0.0225 (4)
H3	0.9904	0.3741	0.3974	0.027*
C4	0.92187 (6)	0.42307 (16)	0.44972 (17)	0.0193 (4)
C5	0.91994 (6)	0.54696 (16)	0.44973 (18)	0.0192 (4)
C6	0.89996 (6)	0.60729 (16)	0.5616 (2)	0.0229 (4)
H6	0.8878	0.5683	0.6413	0.028*
C7	0.89779 (7)	0.72353 (17)	0.5573 (2)	0.0284 (4)
H7	0.8840	0.7639	0.6335	0.034*
C8	0.91585 (7)	0.78079 (17)	0.4409 (2)	0.0307 (5)
H8	0.9138	0.8603	0.4365	0.037*
C9	0.93685 (7)	0.72183 (18)	0.3313 (2)	0.0292 (4)
H9	0.9499	0.7612	0.2531	0.035*
C10	0.93889 (6)	0.60550 (17)	0.3355 (2)	0.0235 (4)
H10	0.9533	0.5656	0.2600	0.028*
C11	0.83692 (6)	0.38175 (15)	0.51674 (18)	0.0188 (4)
C12	0.81362 (6)	0.47000 (16)	0.44808 (19)	0.0214 (4)
H12	0.8285	0.5097	0.3733	0.026*
C13	0.76862 (6)	0.49917 (16)	0.48990 (19)	0.0213 (4)
H13	0.7529	0.5611	0.4465	0.026*
C14	0.74629 (6)	0.43750 (15)	0.59607 (18)	0.0183 (4)
C15	0.76849 (6)	0.34505 (15)	0.65805 (18)	0.0193 (4)
H15	0.7523	0.3004	0.7256	0.023*
C16	0.81447 (6)	0.31858 (15)	0.62039 (19)	0.0194 (4)
H16	0.8305	0.2576	0.6652	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0180 (2)	0.0196 (2)	0.0150 (2)	−0.00041 (15)	0.00220 (16)	−0.00277 (15)
O1	0.0219 (6)	0.0280 (7)	0.0161 (6)	0.0002 (5)	0.0038 (5)	−0.0002 (5)
O2	0.0254 (7)	0.0217 (7)	0.0287 (7)	−0.0010 (5)	0.0032 (5)	−0.0067 (5)
N1	0.0192 (7)	0.0221 (8)	0.0159 (7)	−0.0009 (6)	0.0013 (6)	0.0001 (6)
N2	0.0169 (7)	0.0212 (8)	0.0187 (7)	0.0003 (6)	0.0012 (6)	−0.0010 (6)
N3	0.0201 (7)	0.0195 (8)	0.0256 (8)	0.0009 (6)	0.0010 (6)	−0.0027 (6)
C1	0.0271 (10)	0.0280 (11)	0.0474 (13)	0.0041 (8)	0.0067 (9)	−0.0085 (9)
C2	0.0198 (9)	0.0270 (10)	0.0234 (9)	0.0012 (7)	0.0000 (7)	−0.0044 (7)
C3	0.0179 (8)	0.0283 (10)	0.0212 (9)	−0.0012 (7)	0.0017 (7)	−0.0037 (7)
C4	0.0180 (8)	0.0249 (9)	0.0149 (8)	−0.0034 (7)	0.0001 (6)	−0.0002 (7)
C5	0.0148 (8)	0.0236 (9)	0.0190 (9)	−0.0015 (7)	−0.0018 (6)	0.0007 (7)
C6	0.0207 (9)	0.0264 (10)	0.0218 (9)	−0.0014 (7)	0.0010 (7)	0.0004 (7)
C7	0.0248 (9)	0.0269 (10)	0.0335 (11)	0.0031 (8)	−0.0015 (8)	−0.0050 (8)
C8	0.0288 (10)	0.0219 (10)	0.0410 (12)	0.0007 (8)	−0.0067 (8)	0.0047 (9)
C9	0.0278 (10)	0.0302 (10)	0.0293 (10)	−0.0067 (8)	−0.0037 (8)	0.0098 (8)
C10	0.0206 (9)	0.0289 (10)	0.0211 (9)	−0.0038 (7)	0.0004 (7)	0.0009 (7)
C11	0.0161 (8)	0.0223 (9)	0.0179 (8)	−0.0009 (7)	−0.0001 (6)	−0.0023 (7)
C12	0.0189 (9)	0.0279 (10)	0.0175 (9)	−0.0022 (7)	0.0014 (7)	0.0054 (7)
C13	0.0186 (8)	0.0254 (9)	0.0199 (9)	−0.0003 (7)	−0.0003 (7)	0.0036 (7)
C14	0.0171 (8)	0.0210 (9)	0.0169 (8)	−0.0025 (7)	0.0005 (6)	−0.0031 (7)
C15	0.0220 (9)	0.0189 (9)	0.0171 (8)	−0.0028 (7)	0.0028 (7)	−0.0016 (7)
C16	0.0209 (9)	0.0192 (9)	0.0182 (8)	0.0003 (7)	0.0010 (6)	−0.0004 (7)

Geometric parameters (Å, º) top

S1—O2	1.4330 (13)	C6—C7	1.387 (3)
S1—O1	1.4407 (13)	C6—H6	0.9500
S1—N1	1.5983 (15)	C7—C8	1.391 (3)
S1—C14	1.7666 (18)	C7—H7	0.9500
N1—H1	0.92 (2)	C8—C9	1.387 (3)
N1—H2	0.86 (2)	C8—H8	0.9500
N2—N3	1.365 (2)	C9—C10	1.388 (3)
N2—C4	1.372 (2)	C9—H9	0.9500
N2—C11	1.424 (2)	C10—H10	0.9500
N3—C2	1.337 (2)	C11—C16	1.391 (2)
C1—C2	1.494 (3)	C11—C12	1.392 (3)
C1—H1A	0.9800	C12—C13	1.382 (3)
C1—H1B	0.9800	C12—H12	0.9500
C1—H1C	0.9800	C13—C14	1.397 (2)
C2—C3	1.400 (3)	C13—H13	0.9500
C3—C4	1.376 (3)	C14—C15	1.390 (3)
C3—H3	0.9500	C15—C16	1.389 (2)
C4—C5	1.477 (3)	C15—H15	0.9500
C5—C10	1.393 (3)	C16—H16	0.9500
C5—C6	1.398 (3)

O2—S1—O1	118.97 (8)	C7—C6—H6	119.7
O2—S1—N1	108.01 (8)	C5—C6—H6	119.7
O1—S1—N1	106.68 (8)	C6—C7—C8	119.71 (19)
O2—S1—C14	106.21 (8)	C6—C7—H7	120.1
O1—S1—C14	107.27 (8)	C8—C7—H7	120.1
N1—S1—C14	109.49 (8)	C9—C8—C7	120.03 (19)
S1—N1—H1	114.6 (14)	C9—C8—H8	120.0
S1—N1—H2	113.6 (14)	C7—C8—H8	120.0
H1—N1—H2	117.8 (19)	C8—C9—C10	120.20 (18)
N3—N2—C4	111.46 (14)	C8—C9—H9	119.9
N3—N2—C11	117.98 (14)	C10—C9—H9	119.9
C4—N2—C11	130.56 (16)	C9—C10—C5	120.36 (18)
C2—N3—N2	105.35 (15)	C9—C10—H10	119.8
C2—C1—H1A	109.5	C5—C10—H10	119.8
C2—C1—H1B	109.5	C16—C11—C12	120.91 (16)
H1A—C1—H1B	109.5	C16—C11—N2	118.85 (16)
C2—C1—H1C	109.5	C12—C11—N2	120.24 (16)
H1A—C1—H1C	109.5	C13—C12—C11	119.26 (16)
H1B—C1—H1C	109.5	C13—C12—H12	120.4
N3—C2—C3	110.85 (16)	C11—C12—H12	120.4
N3—C2—C1	119.44 (18)	C12—C13—C14	119.97 (17)
C3—C2—C1	129.70 (17)	C12—C13—H13	120.0
C4—C3—C2	106.24 (16)	C14—C13—H13	120.0
C4—C3—H3	126.9	C15—C14—C13	120.57 (16)
C2—C3—H3	126.9	C15—C14—S1	121.16 (13)
N2—C4—C3	106.09 (16)	C13—C14—S1	118.22 (14)
N2—C4—C5	124.32 (16)	C16—C15—C14	119.42 (16)
C3—C4—C5	129.57 (16)	C16—C15—H15	120.3
C10—C5—C6	119.01 (18)	C14—C15—H15	120.3
C10—C5—C4	119.05 (16)	C15—C16—C11	119.67 (16)
C6—C5—C4	121.94 (16)	C15—C16—H16	120.2
C7—C6—C5	120.64 (18)	C11—C16—H16	120.2

C4—N2—N3—C2	−1.13 (19)	C6—C5—C10—C9	−1.6 (3)
C11—N2—N3—C2	179.13 (15)	C4—C5—C10—C9	178.87 (16)
N2—N3—C2—C3	1.0 (2)	N3—N2—C11—C16	37.9 (2)
N2—N3—C2—C1	179.95 (17)	C4—N2—C11—C16	−141.76 (18)
N3—C2—C3—C4	−0.5 (2)	N3—N2—C11—C12	−142.14 (17)
C1—C2—C3—C4	−179.3 (2)	C4—N2—C11—C12	38.2 (3)
N3—N2—C4—C3	0.86 (19)	C16—C11—C12—C13	3.9 (3)
C11—N2—C4—C3	−179.44 (16)	N2—C11—C12—C13	−176.02 (16)
N3—N2—C4—C5	−177.79 (15)	C11—C12—C13—C14	−2.5 (3)
C11—N2—C4—C5	1.9 (3)	C12—C13—C14—C15	−1.5 (3)
C2—C3—C4—N2	−0.24 (19)	C12—C13—C14—S1	176.01 (14)
C2—C3—C4—C5	178.31 (17)	O2—S1—C14—C15	128.99 (15)
N2—C4—C5—C10	−133.78 (18)	O1—S1—C14—C15	0.77 (17)
C3—C4—C5—C10	47.9 (3)	N1—S1—C14—C15	−114.63 (15)
N2—C4—C5—C6	46.7 (2)	O2—S1—C14—C13	−48.55 (16)
C3—C4—C5—C6	−131.6 (2)	O1—S1—C14—C13	−176.76 (14)
C10—C5—C6—C7	1.8 (3)	N1—S1—C14—C13	67.84 (16)
C4—C5—C6—C7	−178.70 (16)	C13—C14—C15—C16	4.2 (3)
C5—C6—C7—C8	−0.3 (3)	S1—C14—C15—C16	−173.24 (13)
C6—C7—C8—C9	−1.4 (3)	C14—C15—C16—C11	−2.8 (3)
C7—C8—C9—C10	1.6 (3)	C12—C11—C16—C15	−1.2 (3)
C8—C9—C10—C5	−0.1 (3)	N2—C11—C16—C15	178.71 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.92 (2)	1.98 (2)	2.878 (2)	164 (2)
N1—H2···O1ⁱⁱ	0.86 (2)	2.07 (2)	2.930 (2)	177 (2)

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅N₃O₂S
M_r	313.37
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	28.2545 (8), 11.9135 (4), 9.3739 (3)
β (°)	91.016 (3)
V (Å³)	3154.85 (17)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	1.91
Crystal size (mm)	0.30 × 0.03 × 0.03

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.598, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	6579, 3137, 2689
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.115, 1.03
No. of reflections	3137
No. of parameters	208
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.51

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.92 (2)	1.98 (2)	2.878 (2)	164 (2)
N1—H2···O1ⁱⁱ	0.86 (2)	2.07 (2)	2.930 (2)	177 (2)

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) x, −y+1, z−1/2.

Acknowledgements

We thank King Abdulaziz University and the University of Malaya for supporting this study.

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