5-(4-Chloro­phen­yl)-1-(2,4-dichloro­phen­yl)-4-methyl-1H-pyrazole-3-carboxylic acid

Wang, W.; Fang, Z.

doi:10.1107/S1600536808038105

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2413

doi:10.1107/S1600536808038105

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5-(4-Chlorophenyl)-1-(2,4-dichlorophenyl)-4-methyl-1H-pyrazole-3-carboxylic acid

Wei Wang ^a and Zheng Fang ^a ^*

^aCollege of Life Sciences and Pharmaceutical Engineering, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: fzcpu@163.com

(Received 13 November 2008; accepted 16 November 2008; online 22 November 2008)

The asymmetric unit of the title compound, C₁₇H₁₁Cl₃N₂O₂, contains two independent molecules; the pyrazole rings are oriented with respect to the chlorophenyl and dichlorophenyl rings at dihedral angles of 43.00 (3) and 65.06 (4)°, respectively, in one molecule, and 51.17 (3) and 69.99 (3)°, respectively, in the other. Pairs of intermolecular O—H⋯O hydrogen bonds link the molecules into dimers. In the crystal structure, there are π–π contacts between the pyrazole rings and dichlorophenyl rings [centroid–centroid distances = 3.859 (3) and 3.835 (3) Å].

Related literature

For bond-length data, see: Allen et al. (1987 ). For the chemical background, see: Tang et al. (2007 ).

Experimental

Crystal data

C₁₇H₁₁Cl₃N₂O₂
M_r = 381.63
Monoclinic, P 2/c
a = 13.192 (3) Å
b = 8.8170 (18) Å
c = 30.012 (6) Å
β = 102.42 (3)°
V = 3409.1 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.55 mm⁻¹
T = 294 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.853, T_max = 0.947
6479 measured reflections
6190 independent reflections
2893 reflections with I > 2σ(I)
R_int = 0.038
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.181
S = 0.99
6190 reflections
433 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O4	0.85	1.74	2.564 (7)	163
O3—H3B⋯O1	0.85	1.89	2.723 (6)	165
Symmetry codes: (i) -x+1, -y, -z; (ii) -x+1, -y+1, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038105/hk2574sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038105/hk2574Isup2.hkl

checkCIF report

Comment top

Some derivatives of benzoic acid are important chemical materials. We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound contains two crystallographically independent molecules (Fig. 1). The bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6), B (C7-C12), C (N1/N2/C13-C15) and D (C18-C23), E (C24-C29), F (N3/N4/C30-C32) are, of course, planar and they are oriented at dihedral angles of A/B = 58.42 (3)°, A/C = 65.06 (4), B/C = 43.00 (3)° and D/E = 57.07 (4)°, D/F = 69.99 (3)°, E/F = 51.17 (3)°. The intramolecuar O-H···O hydrogen bonds (Table 1) link the molecules (Fig. 1), in which they may be effective in the stabilization of the structure.

In the crystal structure, there are π-π contacts between the pyrazole rings and dichlorophenyl rings, Cg1—Cg2ⁱ and Cg3—Cg5ⁱⁱ [symmetry codes: (i) x + 1, y, z; (ii) 1 - x, y, 1/2 -z, where Cg1, Cg2, Cg3 and Cg5 are centroids of the rings C (N1/N2/C13-C15), F (N3/N4/C30-C32), A (C3-C8) and D (C18-C23), respectively] may stabilize the structure, with centroid-centroid distances of 3.859 (3) Å and 3.835 (3) Å, respectively. There also exist C—H···π contacts (Table 1) between the methyl groups and the chlorophenyl rings.

Related literature top

For bond-length data, see: Allen et al. (1987). For the synthesis, see Tang et al. (2007).

Experimental top

For the preparation of the title compound, 2,4-dichlorophenylhydrazine hydrochloride (13.3 g) diluted in ethanol (20 ml) is added to ethyl 4-(4-chlorophenyl)-3-methyl-2,4-dioxobutanoate (17.6 g) diluted in toluene (50 ml) and the mixture is stirred for 18 h at room temperature. Without isolating the hydrazone, paratoluenesulfonic acid (0.56 g) is added, and the ternary azeotrope (water, ethanol, toluene) is distilled. Toluene reflux is continued for 1 h and the reaction mixture is cooled to room temperature. The insoluble material is filtered off. The solvents are removed under reduced pressure to give an oil. KOH (8.1 g) in pellets are added to a solution of the oil obtained in the previous step in MeOH (100 ml). The mixture is left for 1 h at room temperature and the solvents are decanted into water (200 ml) at 333 K. Hydrochloric acid is then added to the aqueous phase until pH = 1.5. The colorless crystals formed are filtered off, washed with water and dried under vaccum to give the expected product (yield; 9.9 g). Crystals suitable for X-ray analysis were obtained by slow evaporation of an acetic acid solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme.

5-(4-Chlorophenyl)-1-(2,4-dichlorophenyl)-4-methyl-1H-pyrazole-3- carboxylic acid top

Crystal data top

C₁₇H₁₁Cl₃N₂O₂	F(000) = 1552
M_r = 381.63	D_x = 1.487 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 25 reflections
a = 13.192 (3) Å	θ = 10–13°
b = 8.8170 (18) Å	µ = 0.55 mm⁻¹
c = 30.012 (6) Å	T = 294 K
β = 102.42 (3)°	Block, colorless
V = 3409.1 (13) Å³	0.30 × 0.20 × 0.10 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	2893 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 25.3°, θ_min = 1.4°
ω/2θ scans	h = 0→15
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
T_min = 0.853, T_max = 0.947	l = −36→36
6479 measured reflections	3 standard reflections every 120 min
6190 independent reflections	intensity decay: 1%

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.06P)² + 5P] where P = (F_o² + 2F_c²)/3
6190 reflections	(Δ/σ)_max < 0.001
433 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₇H₁₁Cl₃N₂O₂	V = 3409.1 (13) Å³
M_r = 381.63	Z = 8
Monoclinic, P2/c	Mo Kα radiation
a = 13.192 (3) Å	µ = 0.55 mm⁻¹
b = 8.8170 (18) Å	T = 294 K
c = 30.012 (6) Å	0.30 × 0.20 × 0.10 mm
β = 102.42 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2893 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.038
T_min = 0.853, T_max = 0.947	3 standard reflections every 120 min
6479 measured reflections	intensity decay: 1%
6190 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 0.99	Δρ_max = 0.33 e Å⁻³
6190 reflections	Δρ_min = −0.28 e Å⁻³
433 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	0.3235 (2)	0.6137 (2)	0.22847 (7)	0.1112 (9)
Cl2	0.41462 (12)	0.2754 (2)	0.37992 (6)	0.0718 (5)
Cl3	0.42824 (16)	0.8503 (2)	0.49709 (6)	0.0871 (7)
Cl4	−0.31722 (17)	−1.1411 (2)	0.16706 (6)	0.0858 (6)
Cl5	−0.38786 (12)	−0.7789 (2)	0.29976 (6)	0.0696 (5)
Cl6	−0.45426 (14)	−1.3607 (2)	0.39707 (6)	0.0814 (6)
O1	0.0459 (3)	−0.1244 (5)	0.43492 (13)	0.0571 (11)
O2	0.0428 (3)	−0.1317 (5)	0.35970 (14)	0.0613 (12)
H2A	0.0228	−0.2219	0.3629	0.092*
O3	−0.0346 (3)	−0.4099 (5)	0.42547 (14)	0.0648 (13)
H3B	−0.0097	−0.3220	0.4233	0.097*
O4	−0.0241 (3)	−0.4055 (5)	0.35213 (14)	0.0636 (12)
N1	0.1830 (3)	0.2661 (5)	0.37220 (15)	0.0398 (11)
N2	0.1338 (3)	0.1348 (5)	0.36084 (15)	0.0442 (12)
N3	−0.1099 (3)	−0.6749 (5)	0.33613 (15)	0.0414 (11)
N4	−0.1607 (3)	−0.8069 (5)	0.33785 (14)	0.0387 (11)
C1	0.2820 (7)	0.5083 (7)	0.2692 (2)	0.065 (2)
C2	0.1789 (7)	0.4874 (8)	0.2669 (2)	0.071 (2)
H2B	0.1303	0.5256	0.2423	0.085*
C3	0.1464 (5)	0.4081 (7)	0.3017 (2)	0.0626 (18)
H3A	0.0759	0.3967	0.3009	0.075*
C4	0.2182 (4)	0.3469 (6)	0.33725 (18)	0.0435 (14)
C5	0.3238 (5)	0.3634 (7)	0.3377 (2)	0.0519 (16)
C6	0.3555 (6)	0.4459 (7)	0.3041 (2)	0.0642 (19)
H6A	0.4258	0.4592	0.3049	0.077*
C7	0.3576 (5)	0.6908 (7)	0.4752 (2)	0.0504 (16)
C8	0.2851 (5)	0.7026 (7)	0.4350 (2)	0.0496 (16)
H8A	0.2715	0.7959	0.4205	0.060*
C9	0.2321 (4)	0.5733 (6)	0.4163 (2)	0.0446 (14)
H9A	0.1836	0.5801	0.3888	0.053*
C10	0.2507 (4)	0.4355 (6)	0.43793 (19)	0.0393 (13)
C11	0.3227 (4)	0.4274 (7)	0.4789 (2)	0.0525 (16)
H11A	0.3356	0.3349	0.4940	0.063*
C12	0.3753 (5)	0.5553 (8)	0.4976 (2)	0.0563 (17)
H12A	0.4226	0.5494	0.5254	0.068*
C13	0.1975 (4)	0.2945 (6)	0.41780 (18)	0.0399 (13)
C14	0.1523 (4)	0.1770 (6)	0.43595 (19)	0.0427 (14)
C15	0.1141 (4)	0.0811 (6)	0.39951 (18)	0.0412 (14)
C16	0.1457 (5)	0.1614 (7)	0.4862 (2)	0.0612 (18)
H16A	0.1098	0.0694	0.4902	0.092*
H16B	0.1086	0.2465	0.4948	0.092*
H16C	0.2144	0.1587	0.5050	0.092*
C17	0.0649 (4)	−0.0666 (7)	0.3986 (2)	0.0462 (15)
C18	−0.2676 (5)	−1.0395 (7)	0.21641 (19)	0.0508 (16)
C19	−0.3380 (5)	−0.9630 (7)	0.2361 (2)	0.0519 (16)
H19A	−0.4084	−0.9654	0.2227	0.062*
C20	−0.3033 (4)	−0.8837 (6)	0.27553 (19)	0.0435 (14)
C21	−0.1980 (4)	−0.8850 (6)	0.29602 (18)	0.0405 (14)
C22	−0.1292 (5)	−0.9617 (7)	0.2757 (2)	0.0549 (17)
H22A	−0.0588	−0.9621	0.2892	0.066*
C23	−0.1643 (5)	−1.0374 (7)	0.2354 (2)	0.0570 (17)
H23A	−0.1177	−1.0871	0.2212	0.068*
C24	−0.3712 (5)	−1.2088 (8)	0.3953 (2)	0.0524 (16)
C25	−0.3943 (5)	−1.0715 (8)	0.4093 (2)	0.0643 (19)
H25A	−0.4533	−1.0587	0.4212	0.077*
C26	−0.3309 (5)	−0.9481 (7)	0.4061 (2)	0.0578 (17)
H26A	−0.3466	−0.8535	0.4165	0.069*
C27	−0.2438 (4)	−0.9654 (7)	0.38723 (19)	0.0430 (14)
C28	−0.2201 (4)	−1.1102 (7)	0.37496 (19)	0.0500 (16)
H28A	−0.1604	−1.1255	0.3637	0.060*
C29	−0.2827 (5)	−1.2322 (7)	0.3790 (2)	0.0554 (17)
H29A	−0.2654	−1.3290	0.3707	0.067*
C30	−0.1821 (4)	−0.8338 (6)	0.38025 (18)	0.0380 (13)
C31	−0.1414 (4)	−0.7112 (6)	0.40758 (17)	0.0373 (13)
C32	−0.0975 (4)	−0.6191 (6)	0.37874 (18)	0.0386 (13)
C33	−0.1414 (5)	−0.6905 (7)	0.45721 (18)	0.0589 (18)
H33A	−0.1783	−0.7728	0.4674	0.088*
H33B	−0.1748	−0.5964	0.4614	0.088*
H33C	−0.0712	−0.6891	0.4746	0.088*
C34	−0.0488 (4)	−0.4708 (7)	0.3863 (2)	0.0466 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.190 (3)	0.0800 (15)	0.0846 (15)	−0.0236 (16)	0.0770 (16)	0.0149 (12)
Cl2	0.0473 (10)	0.0823 (13)	0.0861 (13)	0.0030 (9)	0.0155 (9)	0.0118 (10)
Cl3	0.1092 (16)	0.0820 (14)	0.0773 (13)	−0.0542 (12)	0.0357 (11)	−0.0305 (11)
Cl4	0.1134 (16)	0.0851 (14)	0.0521 (11)	−0.0172 (12)	0.0026 (10)	−0.0250 (10)
Cl5	0.0472 (10)	0.0915 (13)	0.0668 (11)	0.0158 (10)	0.0052 (8)	−0.0112 (10)
Cl6	0.0785 (13)	0.0780 (13)	0.0838 (13)	−0.0437 (11)	0.0093 (10)	0.0142 (11)
O1	0.070 (3)	0.057 (3)	0.044 (2)	−0.018 (2)	0.013 (2)	0.008 (2)
O2	0.076 (3)	0.048 (3)	0.056 (3)	−0.028 (2)	0.007 (2)	−0.002 (2)
O3	0.074 (3)	0.064 (3)	0.059 (3)	−0.028 (2)	0.018 (2)	−0.022 (2)
O4	0.077 (3)	0.055 (3)	0.060 (3)	−0.023 (2)	0.019 (2)	−0.010 (2)
N1	0.043 (3)	0.032 (3)	0.046 (3)	−0.012 (2)	0.012 (2)	0.006 (2)
N2	0.041 (3)	0.046 (3)	0.045 (3)	−0.007 (2)	0.008 (2)	−0.009 (2)
N3	0.036 (3)	0.038 (3)	0.048 (3)	−0.015 (2)	0.004 (2)	−0.005 (2)
N4	0.035 (3)	0.041 (3)	0.039 (3)	−0.009 (2)	0.007 (2)	−0.002 (2)
C1	0.107 (6)	0.043 (4)	0.055 (4)	−0.005 (4)	0.037 (4)	0.003 (3)
C2	0.099 (6)	0.069 (5)	0.042 (4)	−0.004 (5)	0.008 (4)	0.006 (3)
C3	0.072 (5)	0.067 (5)	0.050 (4)	−0.002 (4)	0.016 (4)	0.008 (4)
C4	0.049 (4)	0.036 (3)	0.043 (3)	−0.009 (3)	0.005 (3)	0.002 (3)
C5	0.047 (4)	0.048 (4)	0.061 (4)	−0.006 (3)	0.013 (3)	0.003 (3)
C6	0.072 (5)	0.055 (4)	0.078 (5)	−0.017 (4)	0.044 (4)	−0.013 (4)
C7	0.052 (4)	0.057 (4)	0.047 (4)	−0.027 (3)	0.021 (3)	−0.014 (3)
C8	0.062 (4)	0.035 (3)	0.060 (4)	−0.002 (3)	0.031 (3)	−0.001 (3)
C9	0.037 (3)	0.044 (4)	0.052 (4)	0.001 (3)	0.009 (3)	0.006 (3)
C10	0.036 (3)	0.039 (3)	0.046 (3)	−0.007 (3)	0.015 (3)	−0.002 (3)
C11	0.046 (4)	0.048 (4)	0.061 (4)	−0.013 (3)	0.005 (3)	0.002 (3)
C12	0.045 (4)	0.073 (5)	0.049 (4)	−0.019 (4)	0.006 (3)	−0.004 (4)
C13	0.029 (3)	0.052 (4)	0.039 (3)	−0.004 (3)	0.007 (2)	0.006 (3)
C14	0.034 (3)	0.049 (4)	0.046 (3)	−0.001 (3)	0.010 (3)	0.003 (3)
C15	0.039 (3)	0.044 (3)	0.039 (3)	−0.006 (3)	0.006 (3)	−0.008 (3)
C16	0.078 (5)	0.054 (4)	0.057 (4)	−0.013 (4)	0.027 (3)	0.002 (3)
C17	0.034 (3)	0.049 (4)	0.050 (4)	−0.003 (3)	−0.004 (3)	0.004 (3)
C18	0.070 (5)	0.053 (4)	0.031 (3)	−0.007 (4)	0.013 (3)	−0.007 (3)
C19	0.044 (4)	0.060 (4)	0.045 (4)	−0.007 (3)	−0.006 (3)	−0.001 (3)
C20	0.038 (3)	0.049 (4)	0.044 (3)	0.000 (3)	0.008 (3)	0.012 (3)
C21	0.038 (3)	0.047 (3)	0.036 (3)	−0.010 (3)	0.007 (3)	−0.003 (3)
C22	0.044 (4)	0.077 (5)	0.045 (4)	−0.008 (3)	0.012 (3)	−0.016 (3)
C23	0.057 (5)	0.065 (5)	0.054 (4)	0.000 (4)	0.024 (3)	−0.009 (3)
C24	0.052 (4)	0.059 (4)	0.044 (4)	−0.020 (3)	0.004 (3)	0.020 (3)
C25	0.053 (4)	0.064 (5)	0.083 (5)	−0.016 (4)	0.030 (4)	0.000 (4)
C26	0.053 (4)	0.056 (4)	0.074 (5)	−0.010 (3)	0.033 (4)	−0.005 (3)
C27	0.033 (3)	0.048 (4)	0.044 (3)	−0.005 (3)	0.001 (3)	0.006 (3)
C28	0.038 (4)	0.056 (4)	0.056 (4)	−0.007 (3)	0.009 (3)	0.005 (3)
C29	0.063 (4)	0.046 (4)	0.058 (4)	−0.013 (3)	0.013 (3)	0.003 (3)
C30	0.032 (3)	0.042 (3)	0.040 (3)	0.000 (3)	0.006 (2)	−0.002 (3)
C31	0.037 (3)	0.043 (3)	0.032 (3)	−0.004 (3)	0.007 (2)	−0.007 (3)
C32	0.031 (3)	0.040 (3)	0.044 (3)	−0.010 (3)	0.007 (3)	−0.002 (3)
C33	0.072 (4)	0.064 (4)	0.045 (4)	−0.011 (4)	0.022 (3)	−0.008 (3)
C34	0.038 (4)	0.056 (4)	0.046 (4)	−0.003 (3)	0.010 (3)	−0.001 (3)

Geometric parameters (Å, º) top

Cl1—C1	1.717 (7)	C11—C12	1.378 (8)
Cl2—C5	1.729 (6)	C11—H11A	0.9300
Cl3—C7	1.737 (6)	C12—H12A	0.9300
Cl4—C18	1.735 (6)	C13—C14	1.366 (7)
Cl5—C20	1.725 (6)	C14—C15	1.388 (7)
Cl6—C24	1.739 (6)	C14—C16	1.536 (7)
O1—C17	1.277 (6)	C15—C17	1.453 (8)
O2—C17	1.276 (6)	C16—H16A	0.9600
O2—H2A	0.8500	C16—H16B	0.9600
O3—C34	1.269 (6)	C16—H16C	0.9600
O3—H3B	0.8500	C18—C23	1.360 (8)
O4—C34	1.279 (6)	C18—C19	1.379 (8)
N1—N2	1.336 (6)	C19—C20	1.365 (8)
N1—C13	1.364 (6)	C19—H19A	0.9300
N1—C4	1.426 (6)	C20—C21	1.393 (7)
N2—C15	1.329 (6)	C21—C22	1.376 (7)
N3—C32	1.347 (6)	C22—C23	1.370 (8)
N3—N4	1.349 (6)	C22—H22A	0.9300
N4—C30	1.382 (6)	C23—H23A	0.9300
N4—C21	1.424 (6)	C24—C25	1.337 (9)
C1—C2	1.360 (9)	C24—C29	1.376 (8)
C1—C6	1.379 (9)	C25—C26	1.388 (8)
C2—C3	1.401 (8)	C25—H25A	0.9300
C2—H2B	0.9300	C26—C27	1.394 (7)
C3—C4	1.374 (8)	C26—H26A	0.9300
C3—H3A	0.9300	C27—C28	1.383 (8)
C4—C5	1.397 (8)	C27—C30	1.458 (7)
C5—C6	1.380 (8)	C28—C29	1.377 (8)
C6—H6A	0.9300	C28—H28A	0.9300
C7—C12	1.366 (8)	C29—H29A	0.9300
C7—C8	1.372 (8)	C30—C31	1.393 (7)
C8—C9	1.391 (8)	C31—C32	1.400 (7)
C8—H8A	0.9300	C31—C33	1.501 (7)
C9—C10	1.375 (7)	C32—C34	1.452 (8)
C9—H9A	0.9300	C33—H33A	0.9600
C10—C11	1.384 (7)	C33—H33B	0.9600
C10—C13	1.490 (7)	C33—H33C	0.9600

C17—O2—H2A	109.6	H16A—C16—H16C	109.5
C34—O3—H3B	107.3	H16B—C16—H16C	109.5
N2—N1—C13	111.8 (4)	O1—C17—O2	123.6 (5)
N2—N1—C4	117.6 (4)	O1—C17—C15	120.7 (6)
C13—N1—C4	130.5 (5)	O2—C17—C15	115.7 (5)
C15—N2—N1	105.1 (4)	C23—C18—C19	121.3 (6)
C32—N3—N4	103.9 (4)	C23—C18—Cl4	121.7 (5)
N3—N4—C30	112.6 (4)	C19—C18—Cl4	117.0 (5)
N3—N4—C21	117.6 (4)	C20—C19—C18	119.4 (6)
C30—N4—C21	129.0 (5)	C20—C19—H19A	120.3
C2—C1—C6	121.2 (6)	C18—C19—H19A	120.3
C2—C1—Cl1	120.3 (6)	C19—C20—C21	119.7 (5)
C6—C1—Cl1	118.5 (6)	C19—C20—Cl5	120.8 (5)
C1—C2—C3	119.5 (7)	C21—C20—Cl5	119.5 (4)
C1—C2—H2B	120.3	C22—C21—C20	119.9 (5)
C3—C2—H2B	120.3	C22—C21—N4	119.6 (5)
C4—C3—C2	120.3 (7)	C20—C21—N4	120.5 (5)
C4—C3—H3A	119.8	C23—C22—C21	120.0 (6)
C2—C3—H3A	119.8	C23—C22—H22A	120.0
C3—C4—C5	119.1 (5)	C21—C22—H22A	120.0
C3—C4—N1	119.2 (5)	C18—C23—C22	119.7 (6)
C5—C4—N1	121.7 (5)	C18—C23—H23A	120.2
C6—C5—C4	120.4 (6)	C22—C23—H23A	120.2
C6—C5—Cl2	120.0 (5)	C25—C24—C29	121.1 (6)
C4—C5—Cl2	119.5 (5)	C25—C24—Cl6	120.0 (5)
C1—C6—C5	119.4 (6)	C29—C24—Cl6	118.9 (6)
C1—C6—H6A	120.3	C24—C25—C26	120.4 (6)
C5—C6—H6A	120.3	C24—C25—H25A	119.8
C12—C7—C8	120.8 (5)	C26—C25—H25A	119.8
C12—C7—Cl3	120.1 (5)	C25—C26—C27	120.2 (6)
C8—C7—Cl3	119.1 (5)	C25—C26—H26A	119.9
C7—C8—C9	119.1 (6)	C27—C26—H26A	119.9
C7—C8—H8A	120.4	C28—C27—C26	117.6 (6)
C9—C8—H8A	120.4	C28—C27—C30	122.1 (5)
C10—C9—C8	120.7 (5)	C26—C27—C30	120.4 (6)
C10—C9—H9A	119.7	C29—C28—C27	121.6 (6)
C8—C9—H9A	119.7	C29—C28—H28A	119.2
C9—C10—C11	118.9 (5)	C27—C28—H28A	119.2
C9—C10—C13	121.6 (5)	C28—C29—C24	119.0 (6)
C11—C10—C13	119.4 (5)	C28—C29—H29A	120.5
C12—C11—C10	120.5 (6)	C24—C29—H29A	120.5
C12—C11—H11A	119.7	N4—C30—C31	106.3 (5)
C10—C11—H11A	119.7	N4—C30—C27	120.0 (5)
C7—C12—C11	119.8 (6)	C31—C30—C27	133.6 (5)
C7—C12—H12A	120.1	C30—C31—C32	104.2 (4)
C11—C12—H12A	120.1	C30—C31—C33	126.6 (5)
N1—C13—C14	106.4 (5)	C32—C31—C33	129.2 (5)
N1—C13—C10	120.8 (5)	N3—C32—C31	113.1 (5)
C14—C13—C10	132.8 (5)	N3—C32—C34	115.9 (5)
C13—C14—C15	105.3 (5)	C31—C32—C34	130.8 (5)
C13—C14—C16	125.6 (5)	C31—C33—H33A	109.5
C15—C14—C16	129.2 (5)	C31—C33—H33B	109.5
N2—C15—C14	111.4 (5)	H33A—C33—H33B	109.5
N2—C15—C17	118.2 (5)	C31—C33—H33C	109.5
C14—C15—C17	130.3 (5)	H33A—C33—H33C	109.5
C14—C16—H16A	109.5	H33B—C33—H33C	109.5
C14—C16—H16B	109.5	O3—C34—O4	122.7 (6)
H16A—C16—H16B	109.5	O3—C34—C32	119.9 (5)
C14—C16—H16C	109.5	O4—C34—C32	117.4 (5)

C13—N1—N2—C15	1.7 (6)	C32—N3—N4—C30	1.1 (6)
C4—N1—N2—C15	177.3 (5)	C32—N3—N4—C21	171.9 (4)
C6—C1—C2—C3	3.5 (10)	C23—C18—C19—C20	−0.1 (9)
Cl1—C1—C2—C3	−176.6 (5)	Cl4—C18—C19—C20	178.7 (5)
C1—C2—C3—C4	−2.4 (10)	C18—C19—C20—C21	−2.0 (9)
C2—C3—C4—C5	−0.8 (9)	C18—C19—C20—Cl5	176.8 (4)
C2—C3—C4—N1	−179.7 (6)	C19—C20—C21—C22	2.2 (9)
N2—N1—C4—C3	67.3 (7)	Cl5—C20—C21—C22	−176.6 (5)
C13—N1—C4—C3	−118.2 (6)	C19—C20—C21—N4	−178.1 (5)
N2—N1—C4—C5	−111.7 (6)	Cl5—C20—C21—N4	3.2 (7)
C13—N1—C4—C5	62.9 (8)	N3—N4—C21—C22	74.7 (7)
C3—C4—C5—C6	2.9 (9)	C30—N4—C21—C22	−116.2 (6)
N1—C4—C5—C6	−178.2 (5)	N3—N4—C21—C20	−105.0 (6)
C3—C4—C5—Cl2	−175.3 (5)	C30—N4—C21—C20	64.1 (8)
N1—C4—C5—Cl2	3.6 (8)	C20—C21—C22—C23	−0.4 (9)
C2—C1—C6—C5	−1.4 (10)	N4—C21—C22—C23	179.9 (5)
Cl1—C1—C6—C5	178.6 (5)	C19—C18—C23—C22	1.9 (10)
C4—C5—C6—C1	−1.8 (10)	Cl4—C18—C23—C22	−176.8 (5)
Cl2—C5—C6—C1	176.3 (5)	C21—C22—C23—C18	−1.7 (10)
C12—C7—C8—C9	−2.5 (9)	C29—C24—C25—C26	2.2 (10)
Cl3—C7—C8—C9	176.9 (4)	Cl6—C24—C25—C26	−177.1 (5)
C7—C8—C9—C10	1.0 (8)	C24—C25—C26—C27	1.6 (10)
C8—C9—C10—C11	0.4 (8)	C25—C26—C27—C28	−4.2 (9)
C8—C9—C10—C13	−178.0 (5)	C25—C26—C27—C30	174.8 (6)
C9—C10—C11—C12	−0.4 (9)	C26—C27—C28—C29	3.2 (9)
C13—C10—C11—C12	178.1 (5)	C30—C27—C28—C29	−175.7 (5)
C8—C7—C12—C11	2.6 (9)	C27—C28—C29—C24	0.4 (9)
Cl3—C7—C12—C11	−176.8 (5)	C25—C24—C29—C28	−3.1 (9)
C10—C11—C12—C7	−1.1 (9)	Cl6—C24—C29—C28	176.1 (4)
N2—N1—C13—C14	−1.8 (6)	N3—N4—C30—C31	−0.5 (6)
C4—N1—C13—C14	−176.6 (5)	C21—N4—C30—C31	−170.0 (5)
N2—N1—C13—C10	−179.9 (4)	N3—N4—C30—C27	175.2 (4)
C4—N1—C13—C10	5.3 (8)	C21—N4—C30—C27	5.7 (8)
C9—C10—C13—N1	40.9 (8)	C28—C27—C30—N4	51.7 (7)
C11—C10—C13—N1	−137.5 (5)	C26—C27—C30—N4	−127.2 (6)
C9—C10—C13—C14	−136.6 (6)	C28—C27—C30—C31	−134.0 (7)
C11—C10—C13—C14	45.0 (9)	C26—C27—C30—C31	47.1 (9)
N1—C13—C14—C15	1.1 (6)	N4—C30—C31—C32	−0.3 (6)
C10—C13—C14—C15	178.8 (6)	C27—C30—C31—C32	−175.1 (6)
N1—C13—C14—C16	−177.9 (5)	N4—C30—C31—C33	−177.6 (5)
C10—C13—C14—C16	−0.1 (10)	C27—C30—C31—C33	7.6 (10)
N1—N2—C15—C14	−1.0 (6)	N4—N3—C32—C31	−1.3 (6)
N1—N2—C15—C17	−177.0 (5)	N4—N3—C32—C34	−176.9 (4)
C13—C14—C15—N2	0.0 (6)	C30—C31—C32—N3	1.0 (6)
C16—C14—C15—N2	178.9 (5)	C33—C31—C32—N3	178.2 (5)
C13—C14—C15—C17	175.3 (5)	C30—C31—C32—C34	175.7 (5)
C16—C14—C15—C17	−5.8 (10)	C33—C31—C32—C34	−7.1 (10)
N2—C15—C17—O1	178.8 (5)	N3—C32—C34—O3	179.8 (5)
C14—C15—C17—O1	3.8 (9)	C31—C32—C34—O3	5.2 (9)
N2—C15—C17—O2	−1.3 (8)	N3—C32—C34—O4	1.3 (7)
C14—C15—C17—O2	−176.3 (6)	C31—C32—C34—O4	−173.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O4	0.85	1.74	2.564 (7)	163
O3—H3B···O1	0.85	1.89	2.723 (6)	165
C16—H16C···Cg6ⁱ	0.96	3.13	3.867 (4)	135
C33—H33B···Cg4ⁱⁱ	0.96	3.29	3.857 (3)	120

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₁Cl₃N₂O₂
M_r	381.63
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	294
a, b, c (Å)	13.192 (3), 8.8170 (18), 30.012 (6)
β (°)	102.42 (3)
V (Å³)	3409.1 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.853, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	6479, 6190, 2893
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.181, 0.99
No. of reflections	6190
No. of parameters	433
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.28

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O4	0.85	1.74	2.564 (7)	163
O3—H3B···O1	0.85	1.89	2.723 (6)	165
C16—H16C···Cg6ⁱ	0.96	3.13	3.867 (4)	135
C33—H33B···Cg4ⁱⁱ	0.96	3.29	3.857 (3)	120

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

Acknowledgements

The authors thank the Center for Testing and Analysis, Nanjing University, for the support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tang, L. H., Tao, L, Chen, H. B. & Zhong, B. H. (2007). Chin. J. Pharm. 38, 252–254. CAS Google Scholar

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Volume 64| Part 12| December 2008| Page o2413

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

5-(4-Chloro­phen­yl)-1-(2,4-di­chloro­phen­yl)-4-methyl-1H-pyrazole-3-carboxylic acid

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

5-(4-Chlorophenyl)-1-(2,4-dichlorophenyl)-4-methyl-1H-pyrazole-3-carboxylic acid