4-(4-Chloro­benz­yl)-5-methyl-2-phenyl-1H-pyrazol-3(2H)-one

Mohamed, S.K.; El-Remaily, M.A.A.; Soliman, A.M.; Abdel-Ghany, H.; Ng, S.W.

doi:10.1107/S1600536811013791

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1153

doi:10.1107/S1600536811013791

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4-(4-Chlorobenzyl)-5-methyl-2-phenyl-1H-pyrazol-3(2H)-one

Shaaban K. Mohamed,^a Mahmoud A. A. El-Remaily,^b Ahmed M. Soliman,^b Hossam Abdel-Ghany ^b and Seik Weng Ng ^c ^*

^aDivision of Chemistry and Environmental Science, Manchester Metropolitan University, Manchester, England, ^bDepartment of Chemistry, Sohag University, Egypt, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 12 April 2011; accepted 12 April 2011; online 16 April 2011)

The five-membered ring of the title compound, C₁₇H₁₅ClN₂O, is almost planar (r.m.s. deviation = 0.008 Å), and its phenyl subsitutent is aligned at 34.9 (1)° with respect to this ring. The angle at the methylene C atom is opened to 116.4 (2)°. In the crystal, adjacent molecules are linked by an N—H⋯O hydrogen bond, generating a linear chain along the a axis.

Related literature

For the synthesis, see: Pettinari et al. (1994 ).

Experimental

Crystal data

C₁₇H₁₅ClN₂O
M_r = 298.76
Orthorhombic, F d d 2
a = 23.1540 (3) Å
b = 43.8905 (6) Å
c = 5.6239 (1) Å
V = 5715.23 (15) Å³
Z = 16
Cu Kα radiation
μ = 2.36 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.03 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.538, T_max = 0.933
10182 measured reflections
2623 independent reflections
2611 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.097
S = 1.08
2623 reflections
195 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.41 e Å⁻³
Absolute structure: Flack (1983 ), 1011 Friedel pairs
Flack parameter: 0.000 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.85 (3)	1.82 (3)	2.6516 (18)	165 (2)
Symmetry code: (i) $[x+{\script{1\over 4}}, -y-{\script{1\over 4}}, z-{\script{1\over 4}}]$ .

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/S1600536811013791/bt5516sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811013791/bt5516Isup2.hkl

checkCIF report

Comment top

3-Methyl-1-phenyl-4,5-dihydro-1H-5-pyrazolone possesses an active methylene linkage that undergoes condensation with aromatic aldehydes to yield compounds that react with metal salts (Pettinari et al., 1994). In these organic compounds, the pyrazole ring is connected to the aromatic system (of the aldehyde precursor) by a methylene linkage. The five-membered ring of C₁₇H₁₅ClN₂O (Scheme I) is planar, and its phenyl subsitutent is aligned at 34.9 (1) ° with respect to this ring. The angle at the methylene C atom is opened to 116.4 (2) ° (Fig. 1). Adjacent molecules are linked by an N–H···O hydrogen bond to generate a linear chain along the a-axis of the orthorhombic unit cell (Fig. 2).

Related literature top

For the synthesis, see: Pettinari et al. (1994).

Experimental top

3-Methyl-1-phenyl-4,5-dihydro-1H-5-pyrazolone (10 mmol) and 4-chlorobenzaldehyde (10 mmol) along with few drops of concentrated hydrochloric acid were heated at 426 K in N,N-dimethylformamide (50 ml) for 8 h. The product was collected and recrystallized from ethanol; m.p. 471 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 C₁₇H₁₅ClN₂O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Hydrogen-bonded chain structure.

4-(4-Chlorobenzyl)-5-methyl-2-phenyl-1H-pyrazol-3(2H)-one top

Crystal data top

C₁₇H₁₅ClN₂O	F(000) = 2496
M_r = 298.76	D_x = 1.389 Mg m⁻³
Orthorhombic, Fdd2	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: F 2 -2d	Cell parameters from 8414 reflections
a = 23.1540 (3) Å	θ = 3.8–74.2°
b = 43.8905 (6) Å	µ = 2.36 mm⁻¹
c = 5.6239 (1) Å	T = 100 K
V = 5715.23 (15) Å³	Plate, colorless
Z = 16	0.30 × 0.30 × 0.03 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2623 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2611 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.028
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.3°, θ_min = 4.0°
ω scans	h = −24→28
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −53→54
T_min = 0.538, T_max = 0.933	l = −6→6
10182 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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0771P)² + 3.0966P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2623 reflections	Δρ_max = 0.21 e Å⁻³
195 parameters	Δρ_min = −0.41 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1011 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.000 (12)

Crystal data top

C₁₇H₁₅ClN₂O	V = 5715.23 (15) Å³
M_r = 298.76	Z = 16
Orthorhombic, Fdd2	Cu Kα radiation
a = 23.1540 (3) Å	µ = 2.36 mm⁻¹
b = 43.8905 (6) Å	T = 100 K
c = 5.6239 (1) Å	0.30 × 0.30 × 0.03 mm

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2623 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2611 reflections with I > 2σ(I)
T_min = 0.538, T_max = 0.933	R_int = 0.028
10182 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.097	Δρ_max = 0.21 e Å⁻³
S = 1.08	Δρ_min = −0.41 e Å⁻³
2623 reflections	Absolute structure: Flack (1983), 1011 Friedel pairs
195 parameters	Absolute structure parameter: 0.000 (12)
1 restraint

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

	x	y	z	U_iso*/U_eq
Cl1	0.122967 (18)	0.029555 (10)	0.59020 (10)	0.02795 (14)
O1	0.20050 (5)	−0.13339 (3)	0.3426 (3)	0.0201 (3)
N1	0.29664 (5)	−0.13658 (3)	0.2283 (3)	0.0152 (3)
N2	0.34778 (6)	−0.12275 (3)	0.2955 (3)	0.0161 (3)
H2	0.3806 (10)	−0.1243 (5)	0.228 (5)	0.019 (5)*
C1	0.29551 (6)	−0.16087 (4)	0.0632 (3)	0.0143 (3)
C2	0.25718 (7)	−0.18504 (4)	0.1001 (3)	0.0168 (3)
H2A	0.2333	−0.1854	0.2373	0.020*
C3	0.25436 (7)	−0.20838 (4)	−0.0648 (4)	0.0200 (4)
H3	0.2279	−0.2247	−0.0416	0.024*
C4	0.28990 (7)	−0.20825 (4)	−0.2645 (4)	0.0223 (4)
H4	0.2875	−0.2243	−0.3776	0.027*
C5	0.32888 (7)	−0.18450 (4)	−0.2971 (4)	0.0205 (4)
H5	0.3537	−0.1845	−0.4316	0.025*
C6	0.33170 (7)	−0.16074 (4)	−0.1343 (3)	0.0169 (3)
H6	0.3582	−0.1445	−0.1577	0.020*
C7	0.25237 (6)	−0.12512 (4)	0.3689 (3)	0.0150 (3)
C8	0.27831 (7)	−0.10413 (4)	0.5272 (3)	0.0156 (3)
C9	0.33640 (7)	−0.10305 (4)	0.4713 (3)	0.0162 (3)
C10	0.38394 (7)	−0.08494 (4)	0.5800 (4)	0.0210 (4)
H10A	0.4167	−0.0841	0.4700	0.031*
H10B	0.3961	−0.0946	0.7290	0.031*
H10C	0.3703	−0.0642	0.6126	0.031*
C11	0.24961 (7)	−0.08915 (4)	0.7360 (3)	0.0178 (3)
H11A	0.2789	−0.0863	0.8621	0.021*
H11B	0.2200	−0.1033	0.7989	0.021*
C12	0.22098 (6)	−0.05861 (4)	0.6893 (3)	0.0154 (3)
C13	0.22392 (7)	−0.03570 (4)	0.8595 (3)	0.0172 (3)
H13	0.2465	−0.0388	0.9985	0.021*
C14	0.19446 (7)	−0.00837 (4)	0.8301 (4)	0.0193 (3)
H14	0.1968	0.0072	0.9467	0.023*
C15	0.16151 (7)	−0.00439 (4)	0.6266 (3)	0.0188 (4)
C16	0.15824 (7)	−0.02657 (4)	0.4517 (3)	0.0184 (3)
H16	0.1357	−0.0234	0.3128	0.022*
C17	0.18871 (7)	−0.05357 (4)	0.4839 (3)	0.0175 (3)
H17	0.1875	−0.0688	0.3640	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0289 (2)	0.0233 (2)	0.0317 (3)	0.01125 (15)	−0.00111 (18)	0.00169 (18)
O1	0.0092 (5)	0.0249 (6)	0.0261 (7)	−0.0009 (4)	0.0031 (5)	−0.0062 (6)
N1	0.0089 (6)	0.0176 (6)	0.0191 (7)	−0.0009 (5)	0.0009 (5)	−0.0015 (6)
N2	0.0086 (6)	0.0191 (6)	0.0206 (8)	−0.0025 (5)	0.0023 (6)	−0.0025 (6)
C1	0.0110 (6)	0.0154 (7)	0.0164 (8)	0.0031 (5)	−0.0018 (6)	0.0000 (6)
C2	0.0117 (6)	0.0168 (7)	0.0220 (9)	0.0010 (5)	0.0014 (7)	0.0001 (7)
C3	0.0148 (7)	0.0174 (8)	0.0277 (10)	0.0010 (6)	−0.0018 (7)	−0.0003 (7)
C4	0.0190 (8)	0.0216 (8)	0.0262 (10)	0.0053 (6)	−0.0021 (7)	−0.0062 (8)
C5	0.0167 (7)	0.0263 (8)	0.0185 (9)	0.0057 (6)	0.0021 (7)	−0.0009 (8)
C6	0.0128 (7)	0.0187 (7)	0.0191 (9)	0.0026 (5)	−0.0007 (6)	0.0021 (7)
C7	0.0118 (7)	0.0157 (7)	0.0176 (9)	0.0027 (5)	0.0021 (6)	0.0020 (6)
C8	0.0133 (7)	0.0159 (7)	0.0177 (9)	0.0015 (6)	0.0006 (6)	0.0020 (6)
C9	0.0147 (7)	0.0162 (7)	0.0177 (9)	0.0010 (6)	0.0024 (7)	0.0018 (7)
C10	0.0174 (7)	0.0213 (8)	0.0242 (10)	−0.0036 (6)	−0.0005 (7)	−0.0023 (8)
C11	0.0185 (7)	0.0174 (7)	0.0176 (9)	0.0018 (6)	0.0024 (7)	0.0005 (7)
C12	0.0104 (6)	0.0178 (8)	0.0178 (9)	−0.0013 (5)	0.0042 (6)	0.0001 (6)
C13	0.0145 (7)	0.0212 (7)	0.0157 (9)	−0.0005 (6)	0.0003 (6)	−0.0006 (7)
C14	0.0188 (7)	0.0190 (7)	0.0203 (9)	−0.0009 (6)	0.0023 (7)	−0.0030 (7)
C15	0.0150 (7)	0.0185 (8)	0.0229 (10)	0.0032 (6)	0.0029 (6)	0.0023 (7)
C16	0.0154 (7)	0.0250 (9)	0.0149 (8)	0.0001 (6)	−0.0009 (6)	0.0019 (7)
C17	0.0149 (7)	0.0200 (8)	0.0177 (9)	−0.0015 (6)	0.0028 (6)	−0.0030 (7)

Geometric parameters (Å, º) top

Cl1—C15	1.7488 (16)	C8—C9	1.382 (2)
O1—C7	1.263 (2)	C8—C11	1.501 (2)
N1—N2	1.3833 (18)	C9—C10	1.489 (2)
N1—C7	1.389 (2)	C10—H10A	0.9800
N1—C1	1.414 (2)	C10—H10B	0.9800
N2—C9	1.340 (2)	C10—H10C	0.9800
N2—H2	0.85 (3)	C11—C12	1.519 (2)
C1—C6	1.391 (2)	C11—H11A	0.9900
C1—C2	1.398 (2)	C11—H11B	0.9900
C2—C3	1.383 (3)	C12—C13	1.390 (2)
C2—H2A	0.9500	C12—C17	1.394 (3)
C3—C4	1.392 (3)	C13—C14	1.390 (2)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.391 (3)	C14—C15	1.386 (3)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.389 (3)	C15—C16	1.386 (3)
C5—H5	0.9500	C16—C17	1.391 (2)
C6—H6	0.9500	C16—H16	0.9500
C7—C8	1.415 (2)	C17—H17	0.9500

N2—N1—C7	108.49 (14)	C8—C9—C10	130.13 (17)
N2—N1—C1	121.74 (13)	C9—C10—H10A	109.5
C7—N1—C1	129.29 (13)	C9—C10—H10B	109.5
C9—N2—N1	108.46 (13)	H10A—C10—H10B	109.5
C9—N2—H2	123.9 (16)	C9—C10—H10C	109.5
N1—N2—H2	127.2 (16)	H10A—C10—H10C	109.5
C6—C1—C2	120.26 (16)	H10B—C10—H10C	109.5
C6—C1—N1	120.65 (14)	C8—C11—C12	116.41 (15)
C2—C1—N1	119.09 (15)	C8—C11—H11A	108.2
C3—C2—C1	119.48 (16)	C12—C11—H11A	108.2
C3—C2—H2A	120.3	C8—C11—H11B	108.2
C1—C2—H2A	120.3	C12—C11—H11B	108.2
C2—C3—C4	120.66 (16)	H11A—C11—H11B	107.3
C2—C3—H3	119.7	C13—C12—C17	118.84 (15)
C4—C3—H3	119.7	C13—C12—C11	119.89 (15)
C5—C4—C3	119.54 (17)	C17—C12—C11	121.16 (16)
C5—C4—H4	120.2	C12—C13—C14	121.22 (16)
C3—C4—H4	120.2	C12—C13—H13	119.4
C6—C5—C4	120.39 (17)	C14—C13—H13	119.4
C6—C5—H5	119.8	C15—C14—C13	118.51 (16)
C4—C5—H5	119.8	C15—C14—H14	120.7
C5—C6—C1	119.65 (15)	C13—C14—H14	120.7
C5—C6—H6	120.2	C14—C15—C16	121.82 (15)
C1—C6—H6	120.2	C14—C15—Cl1	119.01 (13)
O1—C7—N1	122.06 (16)	C16—C15—Cl1	119.16 (14)
O1—C7—C8	131.63 (15)	C15—C16—C17	118.58 (17)
N1—C7—C8	106.30 (13)	C15—C16—H16	120.7
C9—C8—C7	107.01 (15)	C17—C16—H16	120.7
C9—C8—C11	126.41 (16)	C16—C17—C12	121.00 (17)
C7—C8—C11	126.12 (15)	C16—C17—H17	119.5
N2—C9—C8	109.69 (14)	C12—C17—H17	119.5
N2—C9—C10	120.14 (14)

C7—N1—N2—C9	−0.45 (19)	N1—C7—C8—C11	−170.82 (16)
C1—N1—N2—C9	−173.26 (14)	N1—N2—C9—C8	1.6 (2)
N2—N1—C1—C6	−39.1 (2)	N1—N2—C9—C10	179.61 (16)
C7—N1—C1—C6	149.68 (17)	C7—C8—C9—N2	−2.2 (2)
N2—N1—C1—C2	141.26 (16)	C11—C8—C9—N2	170.45 (15)
C7—N1—C1—C2	−29.9 (2)	C7—C8—C9—C10	−179.87 (18)
C6—C1—C2—C3	−1.8 (2)	C11—C8—C9—C10	−7.3 (3)
N1—C1—C2—C3	177.77 (15)	C9—C8—C11—C12	97.3 (2)
C1—C2—C3—C4	1.0 (2)	C7—C8—C11—C12	−91.5 (2)
C2—C3—C4—C5	0.5 (3)	C8—C11—C12—C13	−142.06 (16)
C3—C4—C5—C6	−1.2 (3)	C8—C11—C12—C17	41.7 (2)
C4—C5—C6—C1	0.4 (2)	C17—C12—C13—C14	1.3 (2)
C2—C1—C6—C5	1.1 (2)	C11—C12—C13—C14	−174.99 (15)
N1—C1—C6—C5	−178.48 (15)	C12—C13—C14—C15	0.4 (2)
N2—N1—C7—O1	178.60 (15)	C13—C14—C15—C16	−1.3 (2)
C1—N1—C7—O1	−9.3 (3)	C13—C14—C15—Cl1	178.64 (13)
N2—N1—C7—C8	−0.87 (19)	C14—C15—C16—C17	0.5 (3)
C1—N1—C7—C8	171.23 (16)	Cl1—C15—C16—C17	−179.46 (13)
O1—C7—C8—C9	−177.57 (18)	C15—C16—C17—C12	1.3 (2)
N1—C7—C8—C9	1.82 (19)	C13—C12—C17—C16	−2.2 (2)
O1—C7—C8—C11	9.8 (3)	C11—C12—C17—C16	174.10 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.85 (3)	1.82 (3)	2.6516 (18)	165 (2)

Symmetry code: (i) x+1/4, −y−1/4, z−1/4.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅ClN₂O
M_r	298.76
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	100
a, b, c (Å)	23.1540 (3), 43.8905 (6), 5.6239 (1)
V (Å³)	5715.23 (15)
Z	16
Radiation type	Cu Kα
µ (mm⁻¹)	2.36
Crystal size (mm)	0.30 × 0.30 × 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	0.538, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	10182, 2623, 2611
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.08
No. of reflections	2623
No. of parameters	195
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.41
Absolute structure	Flack (1983), 1011 Friedel pairs
Absolute structure parameter	0.000 (12)

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
N2—H2···O1ⁱ	0.85 (3)	1.82 (3)	2.6516 (18)	165 (2)

Symmetry code: (i) x+1/4, −y−1/4, z−1/4.

Acknowledgements

We thank Machester Metropolitan University, Sohag University and the University of Malaya for supporting this study.

References

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