3-Methyl-1-phenyl-1H-pyrazol-5-yl 2,4-dichloro­benzoate

Li, J.-S.; Huang, P.-M.; Fan, M.-L.; Duan, X.-M.; Zeng, T.

doi:10.1107/S1600536805039310

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3-Methyl-1-phenyl-1H-pyrazol-5-yl 2,4-dichlorobenzoate

J.-S. Li, P.-M. Huang, M.-L. Fan, X.-M. Duan and T. Zeng

In the title compound, C₁₇H₁₂Cl₂N₂O₂, the dihedral angle formed between the dichlorobenzene and pyrazolyl rings is 38.3 (3)°, that between the phenyl and pyrazolyl rings is 46.8 (3)°, and that between the two benzene rings is 69.4 (3)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039310/jh6027sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039310/jh6027Isup2.hkl Contains datablock I

CCDC reference: 296721

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.005 Å
R factor = 0.058
wR factor = 0.178
Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The title compound, (I), and some of its previously reported analogs possess herbicidal and growth-regulating activities (Vasilev et al., 1981) and anti-inflammatory properties (Terebenina et al., 1980).

In the molecular structure of (I) (Fig. 1), the dihedral angle formed between the dichlorobenzene and pyrazolyl rings is 38.3 (3)°, that between the phenyl and pyrazolyl rings is 46.8 (3)°, and that between the two phenyl rings is 69.4 (3)°.

Experimental top

To a suspension of 1-phenyl-3-methyl-1H-pyrazol-5-one (Liu & Li, 2004; 0.36 g, 2 mmol), anhydrous sodium carbonate (0.11 g, 1 mmol), and a catalytic amount of tetrabutylammonium bromide in benzene (20 ml) and water (2 ml) was added dropwise 2,4-dichlorobenzoyl chloride (0.44 g, 2.1 mmol) in benzene (5 ml) over a period of half an hour at 283 K, and the reaction mixture was stirred at ambient temperature for an additional 1 h. The reaction was quenched by aqueous saturated sodium carbonate (10 ml), and the benzene layer was collected and evaporated under reduced pressure to yield 0.65 g of (I) as an colorless solid in 94% yield (m.p. 364.0–365.5 K). ¹H NMR (CDCl₃, 500 MHz, p.p.m.): δ 7.85 (d, 1H, J = 8.5 Hz), 7.56–7.53 (m, 3H), 7.43 (t, 2H, J = 7.5 Hz), 7.34–7.31 (m, 2H), 6.28 (s, 1H), 2.36 (s, 3H); ¹³C NMR (CDCl₃, 500 MHz, p.p.m.): δ 159.5, 149.1, 144.0, 140.0, 137.9, 136.3, 133.0,131.7, 129.1 (2 C), 127.5, 127.4, 125.6, 123.5 (2 C), 95.9, 14.5. Suitable crystals were grown by evaporation from a mixture of ethyl acetate and n-hexane (2:1 v/v).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. Displacement ellipsoid plot of the molecular structure of (I). H atoms are shown as small spheres of arbitrary radii.

3-Methyl-1-phenyl-1H-pyrazol-5-yl 2,4-dichlorobenzoate top

Crystal data top

C₁₇H₁₂Cl₂N₂O₂	F(000) = 712
M_r = 347.19	D_x = 1.403 Mg m⁻³
Monoclinic, P2₁/n	Melting point = 364.0–365.5 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.799 (3) Å	Cell parameters from 2156 reflections
b = 10.385 (3) Å	θ = 2.4–21.7°
c = 14.656 (4) Å	µ = 0.41 mm⁻¹
β = 91.292 (4)°	T = 294 K
V = 1643.3 (7) Å³	Prism, colorless
Z = 4	0.24 × 0.20 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3354 independent reflections
Radiation source: fine-focus sealed tube	1837 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.892, T_max = 0.930	k = −6→12
9043 measured reflections	l = −17→18

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0805P)² + 0.7399P] where P = (F_o² + 2F_c²)/3
3354 reflections	(Δ/σ)_max = 0.002
209 parameters	Δρ_max = 0.66 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₁₇H₁₂Cl₂N₂O₂	V = 1643.3 (7) Å³
M_r = 347.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.799 (3) Å	µ = 0.41 mm⁻¹
b = 10.385 (3) Å	T = 294 K
c = 14.656 (4) Å	0.24 × 0.20 × 0.18 mm
β = 91.292 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3354 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1837 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.930	R_int = 0.044
9043 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.02	Δρ_max = 0.66 e Å⁻³
3354 reflections	Δρ_min = −0.48 e Å⁻³
209 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
Cl1	0.20027 (10)	1.12808 (11)	0.35699 (7)	0.0857 (4)
Cl2	−0.13994 (12)	1.35954 (12)	0.55581 (9)	0.1083 (5)
O1	0.25881 (19)	0.8814 (2)	0.59991 (15)	0.0554 (6)
O2	0.3494 (3)	0.9738 (4)	0.4829 (2)	0.1290 (15)
N2	0.4013 (3)	0.5871 (3)	0.65368 (19)	0.0589 (7)
N1	0.3093 (2)	0.6785 (2)	0.65378 (17)	0.0491 (7)
C1	0.1989 (3)	0.6556 (3)	0.7009 (2)	0.0476 (8)
C2	0.1527 (3)	0.7477 (3)	0.7588 (2)	0.0575 (9)
H2	0.1929	0.8263	0.7662	0.069*
C3	0.0460 (4)	0.7218 (4)	0.8059 (3)	0.0762 (11)
H3	0.0136	0.7840	0.8443	0.091*
C4	−0.0123 (4)	0.6053 (5)	0.7963 (3)	0.0855 (13)
H4	−0.0835	0.5880	0.8288	0.103*
C5	0.0343 (4)	0.5143 (4)	0.7388 (3)	0.0777 (12)
H5	−0.0053	0.4352	0.7327	0.093*
C6	0.1391 (3)	0.5385 (3)	0.6898 (2)	0.0605 (9)
H6	0.1693	0.4771	0.6498	0.073*
C7	0.6100 (3)	0.5674 (4)	0.5924 (3)	0.0850 (13)
H7A	0.6724	0.5968	0.6352	0.127*
H7B	0.6374	0.5816	0.5314	0.127*
H7C	0.5957	0.4771	0.6015	0.127*
C8	0.4916 (3)	0.6405 (3)	0.6068 (2)	0.0606 (9)
C9	0.4598 (3)	0.7642 (3)	0.5752 (2)	0.0594 (9)
H9	0.5072	0.8198	0.5406	0.071*
C10	0.3444 (3)	0.7839 (3)	0.6065 (2)	0.0490 (8)
C11	0.2647 (3)	0.9701 (3)	0.5326 (2)	0.0605 (9)
C12	0.1628 (3)	1.0635 (3)	0.5363 (2)	0.0494 (8)
C13	0.1318 (3)	1.1427 (3)	0.4620 (2)	0.0562 (8)
C14	0.0395 (3)	1.2335 (3)	0.4685 (3)	0.0662 (10)
H14	0.0192	1.2859	0.4189	0.079*
C15	−0.0220 (3)	1.2459 (3)	0.5484 (3)	0.0676 (10)
C16	0.0050 (3)	1.1684 (4)	0.6232 (3)	0.0666 (10)
H16	−0.0383	1.1774	0.6770	0.080*
C17	0.0965 (3)	1.0786 (3)	0.6161 (2)	0.0541 (8)
H17	0.1151	1.0259	0.6659	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0896 (8)	0.1028 (9)	0.0649 (6)	0.0134 (6)	0.0052 (5)	0.0277 (6)
Cl2	0.1170 (10)	0.1039 (9)	0.1021 (9)	0.0644 (7)	−0.0385 (7)	−0.0316 (7)
O1	0.0539 (13)	0.0516 (13)	0.0609 (14)	0.0134 (11)	0.0085 (11)	0.0156 (11)
O2	0.114 (2)	0.161 (3)	0.115 (3)	0.072 (2)	0.061 (2)	0.079 (2)
N2	0.0577 (17)	0.0545 (17)	0.0643 (18)	0.0173 (14)	−0.0047 (14)	0.0014 (14)
N1	0.0515 (15)	0.0472 (15)	0.0485 (15)	0.0085 (12)	0.0000 (12)	0.0053 (12)
C1	0.0500 (18)	0.0494 (19)	0.0431 (18)	0.0019 (15)	−0.0056 (14)	0.0070 (14)
C2	0.065 (2)	0.054 (2)	0.053 (2)	−0.0017 (17)	0.0039 (17)	0.0002 (16)
C3	0.080 (3)	0.085 (3)	0.064 (2)	0.011 (2)	0.018 (2)	0.002 (2)
C4	0.076 (3)	0.102 (4)	0.079 (3)	−0.015 (3)	0.013 (2)	0.029 (3)
C5	0.084 (3)	0.067 (3)	0.082 (3)	−0.023 (2)	−0.011 (2)	0.022 (2)
C6	0.073 (2)	0.051 (2)	0.058 (2)	0.0012 (18)	−0.0109 (18)	0.0091 (16)
C7	0.064 (2)	0.079 (3)	0.112 (3)	0.024 (2)	0.008 (2)	−0.010 (3)
C8	0.054 (2)	0.062 (2)	0.066 (2)	0.0130 (17)	−0.0017 (18)	−0.0075 (18)
C9	0.053 (2)	0.061 (2)	0.065 (2)	0.0075 (17)	0.0068 (17)	0.0033 (17)
C10	0.0494 (18)	0.0469 (19)	0.0505 (18)	0.0063 (15)	−0.0021 (14)	0.0010 (15)
C11	0.058 (2)	0.067 (2)	0.057 (2)	0.0100 (18)	0.0079 (17)	0.0176 (18)
C12	0.0460 (17)	0.0428 (18)	0.059 (2)	−0.0013 (14)	−0.0071 (15)	0.0020 (15)
C13	0.0552 (19)	0.053 (2)	0.060 (2)	−0.0023 (16)	−0.0103 (16)	0.0082 (16)
C14	0.072 (2)	0.060 (2)	0.065 (2)	0.0095 (19)	−0.0226 (19)	0.0025 (18)
C15	0.070 (2)	0.055 (2)	0.076 (3)	0.0148 (18)	−0.027 (2)	−0.0166 (19)
C16	0.070 (2)	0.066 (2)	0.064 (2)	0.0132 (19)	−0.0097 (18)	−0.0158 (18)
C17	0.058 (2)	0.0495 (19)	0.055 (2)	0.0036 (15)	−0.0055 (16)	−0.0031 (15)

Geometric parameters (Å, º) top

Cl1—C13	1.729 (4)	C6—H6	0.9300
Cl2—C15	1.742 (4)	C7—C8	1.507 (5)
O1—C11	1.352 (4)	C7—H7A	0.9600
O1—C10	1.373 (4)	C7—H7B	0.9600
O2—C11	1.184 (4)	C7—H7C	0.9600
N2—C8	1.327 (4)	C8—C9	1.406 (5)
N2—N1	1.374 (3)	C9—C10	1.353 (4)
N1—C10	1.355 (4)	C9—H9	0.9300
N1—C1	1.411 (4)	C11—C12	1.469 (4)
C1—C2	1.380 (4)	C12—C17	1.394 (4)
C1—C6	1.385 (4)	C12—C13	1.399 (4)
C2—C3	1.383 (5)	C13—C14	1.377 (5)
C2—H2	0.9300	C14—C15	1.365 (5)
C3—C4	1.370 (6)	C14—H14	0.9300
C3—H3	0.9300	C15—C16	1.386 (5)
C4—C5	1.370 (6)	C16—C17	1.365 (5)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.377 (5)	C17—H17	0.9300
C5—H5	0.9300

C11—O1—C10	120.7 (2)	N2—C8—C7	119.9 (3)
C8—N2—N1	104.5 (3)	C9—C8—C7	128.0 (4)
C10—N1—N2	110.3 (2)	C10—C9—C8	104.2 (3)
C10—N1—C1	129.5 (3)	C10—C9—H9	127.9
N2—N1—C1	120.2 (3)	C8—C9—H9	127.9
C2—C1—C6	120.5 (3)	C9—C10—N1	108.8 (3)
C2—C1—N1	120.4 (3)	C9—C10—O1	135.4 (3)
C6—C1—N1	119.2 (3)	N1—C10—O1	115.8 (3)
C1—C2—C3	119.3 (3)	O2—C11—O1	121.4 (3)
C1—C2—H2	120.4	O2—C11—C12	126.3 (3)
C3—C2—H2	120.4	O1—C11—C12	112.1 (3)
C4—C3—C2	120.5 (4)	C17—C12—C13	118.0 (3)
C4—C3—H3	119.8	C17—C12—C11	120.3 (3)
C2—C3—H3	119.8	C13—C12—C11	121.7 (3)
C5—C4—C3	119.8 (4)	C14—C13—C12	120.6 (3)
C5—C4—H4	120.1	C14—C13—Cl1	116.5 (3)
C3—C4—H4	120.1	C12—C13—Cl1	122.8 (3)
C4—C5—C6	120.9 (4)	C15—C14—C13	119.4 (3)
C4—C5—H5	119.6	C15—C14—H14	120.3
C6—C5—H5	119.6	C13—C14—H14	120.3
C5—C6—C1	119.0 (4)	C14—C15—C16	121.8 (3)
C5—C6—H6	120.5	C14—C15—Cl2	119.2 (3)
C1—C6—H6	120.5	C16—C15—Cl2	119.0 (3)
C8—C7—H7A	109.5	C17—C16—C15	118.5 (4)
C8—C7—H7B	109.5	C17—C16—H16	120.8
H7A—C7—H7B	109.5	C15—C16—H16	120.8
C8—C7—H7C	109.5	C16—C17—C12	121.8 (3)
H7A—C7—H7C	109.5	C16—C17—H17	119.1
H7B—C7—H7C	109.5	C12—C17—H17	119.1
N2—C8—C9	112.1 (3)

C8—N2—N1—C10	0.8 (3)	C1—N1—C10—O1	−2.9 (5)
C8—N2—N1—C1	−177.8 (3)	C11—O1—C10—C9	20.3 (5)
C10—N1—C1—C2	−46.6 (5)	C11—O1—C10—N1	−158.4 (3)
N2—N1—C1—C2	131.8 (3)	C10—O1—C11—O2	−7.1 (6)
C10—N1—C1—C6	134.8 (3)	C10—O1—C11—C12	178.4 (3)
N2—N1—C1—C6	−46.8 (4)	O2—C11—C12—C17	−155.6 (4)
C6—C1—C2—C3	0.1 (5)	O1—C11—C12—C17	18.6 (4)
N1—C1—C2—C3	−178.5 (3)	O2—C11—C12—C13	22.2 (6)
C1—C2—C3—C4	1.0 (5)	O1—C11—C12—C13	−163.6 (3)
C2—C3—C4—C5	−0.9 (6)	C17—C12—C13—C14	0.8 (5)
C3—C4—C5—C6	−0.3 (6)	C11—C12—C13—C14	−177.1 (3)
C4—C5—C6—C1	1.4 (5)	C17—C12—C13—Cl1	−176.2 (2)
C2—C1—C6—C5	−1.3 (5)	C11—C12—C13—Cl1	6.0 (4)
N1—C1—C6—C5	177.3 (3)	C12—C13—C14—C15	0.0 (5)
N1—N2—C8—C9	−0.9 (4)	Cl1—C13—C14—C15	177.1 (3)
N1—N2—C8—C7	179.9 (3)	C13—C14—C15—C16	−0.7 (5)
N2—C8—C9—C10	0.6 (4)	C13—C14—C15—Cl2	−179.3 (3)
C7—C8—C9—C10	179.8 (4)	C14—C15—C16—C17	0.6 (5)
C8—C9—C10—N1	−0.1 (4)	Cl2—C15—C16—C17	179.2 (3)
C8—C9—C10—O1	−178.9 (3)	C15—C16—C17—C12	0.2 (5)
N2—N1—C10—C9	−0.5 (4)	C13—C12—C17—C16	−0.8 (5)
C1—N1—C10—C9	178.1 (3)	C11—C12—C17—C16	177.1 (3)
N2—N1—C10—O1	178.6 (2)

Experimental details

Crystal data
Chemical formula	C₁₇H₁₂Cl₂N₂O₂
M_r	347.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	10.799 (3), 10.385 (3), 14.656 (4)
β (°)	91.292 (4)
V (Å³)	1643.3 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.892, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	9043, 3354, 1837
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.178, 1.02
No. of reflections	3354
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.48

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

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