4-(4-Chloro­benzo­yl)-3-methyl-1-phenyl-1H-pyrazol-5-yl 4-chloro­benzoate

Abstract

In the title compound, C₂₄H₁₆Cl₂N₂O₃, the three benzene rings are twisted with respect to the central pyrazole ring, making dihedral angles of 71.56 (9) (4-chloro­benzo­yloxy), 57.55 (8) (4-chloro­benzo­yl) and 39.33 (1)° (phen­yl).

Related literature

For the anti­bacterial and biological activity of 5-acyl­oxy­pyrazoles, see Bai et al. (2002 ▶); Varma (1999 ▶).

Experimental

Crystal data

• C₂₄H₁₆Cl₂N₂O₃

• M _r = 451.29

• Monoclinic,

• a = 11.4481 (4) Å

• b = 29.4169 (13) Å

• c = 6.4120 (3) Å

• β = 99.669 (3)°

• V = 2128.68 (16) ų

• Z = 4

• Mo Kα radiation

• μ = 0.33 mm⁻¹

• T = 296 K

• 0.23 × 0.18 × 0.16 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.930, T _max = 0.948

• 16531 measured reflections

• 3765 independent reflections

• 1884 reflections with I > 2σ(I)

• R _int = 0.067

Refinement

• R[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 0.093

• S = 1.03

• 3765 reflections

• 281 parameters

• H-atom parameters constrained

• Δρ_max = 0.15 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811048136/vm2134Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

5-Acyloxypyrazoles have received considerable attention due to their high antibacterial and biological activities (Bai et al., 2002, Varma, 1999). As part of our ongoing search for biologically active molecules, the title compound was synthesized and characterized by X-ray diffraction (Fig. 1).

The three phenyl rings (C1—C6, r.m.s. deviation = 0.0047 Å; C12—C17, r.m.s. deviation = 0.0061 Å; C19—C24, r.m.s. deviation = 0.0045 Å) are twisted with respect to the central pyrazole ring (N1,2/C8—C10, r.m.s. deviation = 0.0065 Å) making dihedral angles of 71.56 (9)°, 57.55 (8)° and 39.33 (1)°, respectively. As expected, there are no classic hydrogen bonds in the structure.

Experimental

1.74 g of 1-phenyl-3-methyl-5-pyrazolone was dissolved in 10 ml dioxane by heating to 80 °C, and 1.5 g of calcium hydroxide was added, then 2 ml of 4-chlorobenzoylchloride was added dropwise within 20 min. After refluxing for 2 h, the reaction mixture was poured into 30 ml diluted hydrochloric acid (3 N). A cream colored powder was obtained by filtration, and used for recrystallization from ethanol to give colorless needle crystals.

Refinement

All H atoms were placed in calculated positions, with the carrier atom-H distances = 0.96 Å for the methyl and 0.93 Å for aryl, and refined as riding, with the U_iso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq(C) for aryl groups.

Figures

Fig. 1.

The title molecule with the displacement ellipsoids shown at the 30% probability level.

Crystal data

C24H16Cl2N2O3	F(000) = 928
Mr = 451.29	Dx = 1.408 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1569 reflections
a = 11.4481 (4) Å	θ = 2.8–19.2°
b = 29.4169 (13) Å	µ = 0.33 mm−1
c = 6.4120 (3) Å	T = 296 K
β = 99.669 (3)°	Needle, colorless
V = 2128.68 (16) Å3	0.23 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	3765 independent reflections
Radiation source: fine-focus sealed tube	1884 reflections with I > 2σ(I)
graphite	Rint = 0.067
φ and ω scans	θmax = 25.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −13→13
Tmin = 0.930, Tmax = 0.948	k = −35→34
16531 measured reflections	l = −7→7

Refinement

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.093	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0199P)2 + 0.5P] where P = (Fo2 + 2Fc2)/3
3765 reflections	(Δ/σ)max < 0.001
281 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.69348 (7)	0.00005 (3)	0.62066 (14)	0.0918 (3)
C1	0.7963 (2)	−0.02529 (11)	0.8140 (5)	0.0605 (8)
C2	0.8162 (3)	−0.00773 (10)	1.0144 (6)	0.0689 (9)
H2A	0.7739	0.0175	1.0469	0.083*
C3	0.8991 (2)	−0.02759 (10)	1.1679 (5)	0.0609 (8)
H3A	0.9118	−0.0160	1.3048	0.073*
C4	0.9635 (2)	−0.06468 (9)	1.1194 (5)	0.0499 (7)
C5	0.9413 (2)	−0.08216 (10)	0.9159 (5)	0.0605 (8)
H5A	0.9832	−0.1074	0.8820	0.073*
C6	0.8580 (3)	−0.06247 (10)	0.7642 (5)	0.0672 (9)
H6A	0.8435	−0.0743	0.6279	0.081*
C7	1.0529 (2)	−0.08436 (9)	1.2859 (5)	0.0530 (8)
C8	1.1952 (2)	−0.14311 (9)	1.3390 (4)	0.0506 (7)
C9	1.1780 (2)	−0.17194 (9)	1.4968 (4)	0.0501 (7)
C10	1.2931 (3)	−0.18817 (9)	1.5767 (4)	0.0550 (8)
C11	1.0674 (3)	−0.18198 (9)	1.5742 (5)	0.0587 (8)
C12	0.9553 (3)	−0.18520 (9)	1.4215 (5)	0.0533 (7)
C13	0.9556 (3)	−0.19948 (9)	1.2166 (5)	0.0580 (8)
H13A	1.0271	−0.2058	1.1722	0.070*
C14	0.8509 (3)	−0.20449 (10)	1.0771 (5)	0.0695 (9)
H14A	0.8512	−0.2146	0.9398	0.083*
C15	0.7463 (3)	−0.19438 (12)	1.1436 (6)	0.0824 (11)
C16	0.7438 (3)	−0.18042 (11)	1.3472 (7)	0.0853 (11)
H16A	0.6721	−0.1739	1.3908	0.102*
C17	0.8479 (3)	−0.17622 (10)	1.4846 (5)	0.0679 (9)
H17A	0.8467	−0.1671	1.6231	0.081*
C18	1.3268 (3)	−0.22254 (10)	1.7484 (5)	0.0731 (9)
H18A	1.4014	−0.2360	1.7344	0.110*
H18C	1.2671	−0.2457	1.7372	0.110*
H18B	1.3334	−0.2079	1.8837	0.110*
C19	1.3721 (3)	−0.11677 (9)	1.1883 (5)	0.0533 (7)
C20	1.4818 (3)	−0.09849 (11)	1.2704 (5)	0.0726 (9)
H20A	1.5152	−0.1028	1.4115	0.087*
C21	1.5397 (3)	−0.07371 (13)	1.1369 (7)	0.0947 (12)
H21A	1.6136	−0.0613	1.1884	0.114*
C22	1.4902 (4)	−0.06699 (12)	0.9297 (7)	0.0928 (12)
H22A	1.5301	−0.0498	0.8422	0.111*
C23	1.3817 (3)	−0.08555 (11)	0.8510 (6)	0.0753 (9)
H23A	1.3482	−0.0810	0.7101	0.090*
C24	1.3226 (3)	−0.11086 (10)	0.9802 (5)	0.0602 (8)
H24A	1.2496	−0.1239	0.9270	0.072*
O1	1.11813 (15)	−0.11725 (6)	1.2022 (3)	0.0523 (5)
O2	1.07060 (18)	−0.07494 (7)	1.4689 (3)	0.0757 (6)
O3	1.06779 (17)	−0.18818 (7)	1.7646 (3)	0.0763 (6)
N1	1.3736 (2)	−0.17134 (8)	1.4732 (4)	0.0589 (7)
N2	1.3115 (2)	−0.14249 (8)	1.3265 (4)	0.0524 (6)
Cl2	0.61559 (9)	−0.19901 (5)	0.9673 (2)	0.1547 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0762 (6)	0.0896 (6)	0.1072 (7)	0.0202 (5)	0.0090 (5)	0.0366 (6)
C1	0.0492 (18)	0.055 (2)	0.077 (2)	0.0040 (15)	0.0114 (18)	0.0182 (19)
C2	0.064 (2)	0.053 (2)	0.094 (3)	0.0148 (17)	0.026 (2)	0.007 (2)
C3	0.067 (2)	0.053 (2)	0.067 (2)	0.0022 (16)	0.0214 (18)	−0.0036 (17)
C4	0.0458 (17)	0.0458 (18)	0.060 (2)	0.0009 (14)	0.0139 (15)	−0.0008 (16)
C5	0.0576 (19)	0.057 (2)	0.066 (2)	0.0128 (15)	0.0060 (17)	−0.0045 (17)
C6	0.066 (2)	0.066 (2)	0.066 (2)	0.0115 (18)	0.0011 (18)	0.0014 (18)
C7	0.0514 (19)	0.0457 (19)	0.064 (2)	−0.0031 (15)	0.0158 (18)	−0.0042 (18)
C8	0.0475 (19)	0.0554 (19)	0.0473 (19)	0.0039 (15)	0.0028 (15)	−0.0034 (16)
C9	0.0492 (18)	0.0528 (18)	0.0465 (19)	−0.0039 (15)	0.0025 (15)	−0.0007 (15)
C10	0.064 (2)	0.0504 (19)	0.0459 (19)	0.0000 (16)	−0.0031 (16)	−0.0006 (15)
C11	0.069 (2)	0.055 (2)	0.052 (2)	−0.0016 (16)	0.0106 (18)	−0.0029 (17)
C12	0.0540 (19)	0.0517 (19)	0.054 (2)	−0.0058 (15)	0.0089 (16)	0.0002 (16)
C13	0.0527 (18)	0.062 (2)	0.058 (2)	−0.0050 (15)	0.0068 (17)	−0.0002 (17)
C14	0.068 (2)	0.071 (2)	0.066 (2)	−0.0045 (18)	0.0012 (19)	−0.0051 (17)
C15	0.055 (2)	0.085 (3)	0.098 (3)	0.0035 (19)	−0.016 (2)	−0.016 (2)
C16	0.056 (2)	0.088 (3)	0.111 (3)	0.0097 (19)	0.011 (2)	−0.014 (2)
C17	0.062 (2)	0.069 (2)	0.074 (2)	0.0028 (17)	0.015 (2)	−0.0066 (18)
C18	0.073 (2)	0.070 (2)	0.070 (2)	0.0026 (17)	−0.0050 (18)	0.0079 (18)
C19	0.0528 (19)	0.0463 (18)	0.064 (2)	−0.0010 (15)	0.0180 (17)	−0.0075 (16)
C20	0.056 (2)	0.081 (2)	0.080 (2)	−0.0097 (18)	0.0120 (19)	−0.011 (2)
C21	0.069 (2)	0.104 (3)	0.116 (4)	−0.034 (2)	0.031 (3)	−0.017 (3)
C22	0.102 (3)	0.081 (3)	0.107 (3)	−0.020 (2)	0.050 (3)	−0.001 (2)
C23	0.091 (3)	0.064 (2)	0.077 (2)	−0.001 (2)	0.031 (2)	0.0006 (19)
C24	0.0638 (19)	0.057 (2)	0.062 (2)	−0.0030 (16)	0.0170 (18)	−0.0064 (17)
O1	0.0490 (11)	0.0569 (12)	0.0507 (12)	0.0087 (10)	0.0076 (10)	0.0031 (10)
O2	0.0890 (15)	0.0802 (16)	0.0559 (14)	0.0158 (12)	0.0069 (13)	−0.0154 (12)
O3	0.0765 (14)	0.0987 (17)	0.0542 (14)	−0.0110 (12)	0.0128 (12)	0.0034 (13)
N1	0.0559 (15)	0.0540 (16)	0.0626 (17)	0.0024 (13)	−0.0020 (14)	0.0010 (13)
N2	0.0463 (15)	0.0524 (15)	0.0580 (16)	0.0006 (12)	0.0073 (13)	−0.0002 (13)
Cl2	0.0745 (7)	0.1987 (13)	0.1694 (12)	0.0168 (7)	−0.0416 (7)	−0.0614 (10)

Geometric parameters (Å, °)

Cl1—C1	1.728 (3)	C13—C14	1.377 (4)
C1—C2	1.368 (4)	C13—H13A	0.9300
C1—C6	1.369 (4)	C14—C15	1.369 (4)
C2—C3	1.377 (4)	C14—H14A	0.9300
C2—H2A	0.9300	C15—C16	1.374 (4)
C3—C4	1.381 (3)	C15—Cl2	1.723 (3)
C3—H3A	0.9300	C16—C17	1.363 (4)
C4—C5	1.386 (4)	C16—H16A	0.9300
C4—C7	1.468 (4)	C17—H17A	0.9300
C5—C6	1.370 (3)	C18—H18A	0.9600
C5—H5A	0.9300	C18—H18C	0.9600
C6—H6A	0.9300	C18—H18B	0.9600
C7—O2	1.189 (3)	C19—C24	1.370 (4)
C7—O1	1.384 (3)	C19—C20	1.386 (4)
C8—N2	1.348 (3)	C19—N2	1.430 (3)
C8—C9	1.359 (3)	C20—C21	1.376 (4)
C8—O1	1.366 (3)	C20—H20A	0.9300
C9—C10	1.414 (3)	C21—C22	1.368 (4)
C9—C11	1.466 (4)	C21—H21A	0.9300
C10—N1	1.319 (3)	C22—C23	1.373 (4)
C10—C18	1.496 (4)	C22—H22A	0.9300
C11—O3	1.233 (3)	C23—C24	1.374 (4)
C11—C12	1.481 (4)	C23—H23A	0.9300
C12—C13	1.380 (4)	C24—H24A	0.9300
C12—C17	1.383 (4)	N1—N2	1.373 (3)
C2—C1—C6	120.6 (3)	C15—C14—H14A	120.5
C2—C1—Cl1	119.8 (3)	C13—C14—H14A	120.5
C6—C1—Cl1	119.6 (3)	C14—C15—C16	121.3 (3)
C1—C2—C3	119.8 (3)	C14—C15—Cl2	119.2 (3)
C1—C2—H2A	120.1	C16—C15—Cl2	119.5 (3)
C3—C2—H2A	120.1	C17—C16—C15	119.0 (3)
C2—C3—C4	120.2 (3)	C17—C16—H16A	120.5
C2—C3—H3A	119.9	C15—C16—H16A	120.5
C4—C3—H3A	119.9	C16—C17—C12	121.2 (3)
C3—C4—C5	119.0 (3)	C16—C17—H17A	119.4
C3—C4—C7	118.7 (3)	C12—C17—H17A	119.4
C5—C4—C7	122.2 (3)	C10—C18—H18A	109.5
C6—C5—C4	120.5 (3)	C10—C18—H18C	109.5
C6—C5—H5A	119.8	H18A—C18—H18C	109.5
C4—C5—H5A	119.8	C10—C18—H18B	109.5
C5—C6—C1	119.8 (3)	H18A—C18—H18B	109.5
C5—C6—H6A	120.1	H18C—C18—H18B	109.5
C1—C6—H6A	120.1	C24—C19—C20	121.4 (3)
O2—C7—O1	122.1 (3)	C24—C19—N2	120.4 (3)
O2—C7—C4	127.4 (3)	C20—C19—N2	118.2 (3)
O1—C7—C4	110.4 (3)	C21—C20—C19	118.0 (3)
N2—C8—C9	108.7 (2)	C21—C20—H20A	121.0
N2—C8—O1	119.5 (3)	C19—C20—H20A	121.0
C9—C8—O1	131.8 (3)	C22—C21—C20	121.1 (3)
C8—C9—C10	103.7 (3)	C22—C21—H21A	119.5
C8—C9—C11	128.2 (3)	C20—C21—H21A	119.5
C10—C9—C11	127.9 (3)	C21—C22—C23	120.1 (4)
N1—C10—C9	112.2 (3)	C21—C22—H22A	120.0
N1—C10—C18	120.5 (3)	C23—C22—H22A	120.0
C9—C10—C18	127.1 (3)	C24—C23—C22	120.0 (3)
O3—C11—C9	120.3 (3)	C24—C23—H23A	120.0
O3—C11—C12	120.3 (3)	C22—C23—H23A	120.0
C9—C11—C12	119.4 (3)	C19—C24—C23	119.4 (3)
C13—C12—C17	118.8 (3)	C19—C24—H24A	120.3
C13—C12—C11	120.6 (3)	C23—C24—H24A	120.3
C17—C12—C11	120.6 (3)	C8—O1—C7	118.2 (2)
C14—C13—C12	120.6 (3)	C10—N1—N2	104.6 (2)
C14—C13—H13A	119.7	C8—N2—N1	110.7 (2)
C12—C13—H13A	119.7	C8—N2—C19	129.1 (2)
C15—C14—C13	119.1 (3)	N1—N2—C19	120.2 (2)
C6—C1—C2—C3	0.0 (4)	C12—C13—C14—C15	1.1 (4)
Cl1—C1—C2—C3	−179.2 (2)	C13—C14—C15—C16	−1.6 (5)
C1—C2—C3—C4	1.0 (4)	C13—C14—C15—Cl2	178.1 (2)
C2—C3—C4—C5	−1.5 (4)	C14—C15—C16—C17	0.6 (5)
C2—C3—C4—C7	178.7 (2)	Cl2—C15—C16—C17	−179.0 (2)
C3—C4—C5—C6	1.0 (4)	C15—C16—C17—C12	0.8 (5)
C7—C4—C5—C6	−179.2 (3)	C13—C12—C17—C16	−1.3 (4)
C4—C5—C6—C1	0.0 (4)	C11—C12—C17—C16	−177.9 (3)
C2—C1—C6—C5	−0.5 (4)	C24—C19—C20—C21	0.6 (4)
Cl1—C1—C6—C5	178.7 (2)	N2—C19—C20—C21	−179.9 (3)
C3—C4—C7—O2	7.8 (4)	C19—C20—C21—C22	0.5 (5)
C5—C4—C7—O2	−171.9 (3)	C20—C21—C22—C23	−0.8 (6)
C3—C4—C7—O1	−172.5 (2)	C21—C22—C23—C24	0.1 (5)
C5—C4—C7—O1	7.8 (3)	C20—C19—C24—C23	−1.3 (4)
N2—C8—C9—C10	0.1 (3)	N2—C19—C24—C23	179.2 (2)
O1—C8—C9—C10	179.6 (3)	C22—C23—C24—C19	1.0 (4)
N2—C8—C9—C11	177.1 (3)	N2—C8—O1—C7	−120.0 (3)
O1—C8—C9—C11	−3.5 (5)	C9—C8—O1—C7	60.6 (4)
C8—C9—C10—N1	−1.2 (3)	O2—C7—O1—C8	7.8 (4)
C11—C9—C10—N1	−178.2 (3)	C4—C7—O1—C8	−171.9 (2)
C8—C9—C10—C18	−177.5 (3)	C9—C10—N1—N2	1.7 (3)
C11—C9—C10—C18	5.5 (5)	C18—C10—N1—N2	178.3 (2)
C8—C9—C11—O3	−142.7 (3)	C9—C8—N2—N1	0.9 (3)
C10—C9—C11—O3	33.6 (4)	O1—C8—N2—N1	−178.6 (2)
C8—C9—C11—C12	38.1 (4)	C9—C8—N2—C19	−178.7 (2)
C10—C9—C11—C12	−145.7 (3)	O1—C8—N2—C19	1.8 (4)
O3—C11—C12—C13	−149.5 (3)	C10—N1—N2—C8	−1.6 (3)
C9—C11—C12—C13	29.7 (4)	C10—N1—N2—C19	178.0 (2)
O3—C11—C12—C17	27.1 (4)	C24—C19—N2—C8	−40.2 (4)
C9—C11—C12—C17	−153.6 (3)	C20—C19—N2—C8	140.2 (3)
C17—C12—C13—C14	0.3 (4)	C24—C19—N2—N1	140.2 (3)
C11—C12—C13—C14	177.0 (3)	C20—C19—N2—N1	−39.3 (3)