4-[(2,4-Dichloro­benzyl­idene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydro­pyrazol-3-one

Jing, Z.-L.; Yu, M.; Chen, X.; Deng, Q.-L.

doi:10.1107/S1600536805029624

4-[(2,4-Dichlorobenzylidene)amino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

Z.-L. Jing, M. Yu, X. Chen and Q.-L. Deng

The crystal structure of the title compound, C₁₈H₁₅Cl₂N₃O, shows that the Cl atoms take part in intermolecular C—H

Cl interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029624/jh6017sup1.cif Contains datablocks I, 50808a
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029624/jh6017Isup2.hkl Contains datablock I

CCDC reference: 287615

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Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.003 Å
R factor = 0.034
wR factor = 0.094
Data-to-parameter ratio = 13.4

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Comment top

Schiff base ligands derived from 4-aminoantipyrine, such as thenoyltrifluoroacetone and 4-hydroxy-3-methoxybenzaldehyde, have been reported (Yu et al., 2002; Diao et al., 2005), which show the synthesis and crystal structure. In the present study, we report the synthesis and structure of the title compound, (I).

In (I) (Fig. 1), the central system (C7–C10/N1–N3/O1) is planar, with an r.m.s. deviation of fitted atoms of 0.0776 Å, and the dihedral angle with the phenyl ring (C13–C18) is 55.98 (6)°. The 2,4-dichlorobenzene group (C1–C7/Cl1/Cl2) is planar, with an r.m.s. deviation of fitted atoms of 0.0192 Å, and the dihedral angle to the central system is 24.25 (5)°. The Cl atoms participate in C—H···Cl interactions (Table 2).

Experimental top

An anhydrous ethanol solution of 2,4-dichlorobenzaldehyde (1.75 g, 10 mmol) was added to an anhydrous ethanol solution of 4-amino-1,5-dimethyl-2-phenylpyrazolidin-3-one (2.03 g, 10 mmol), and the mixture was stirred at 350 K for 5 h under nitrogen. A yellow precipitate appeared. The product was isolated, recrystallized from ethanol and then dried in vacuo to give pure compound (I) in 78% yield. Bright-yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution of (I).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. A view of the title compound, with 30% probability displacement ellipsoids.
	Fig. 2. Intermolecular hydrogen-bonding interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted.

(I) top

Crystal data top

C₁₈H₁₅Cl₂N₃O	F(000) = 744
M_r = 360.23	D_x = 1.426 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4236 (7) Å	Cell parameters from 3316 reflections
b = 7.3711 (5) Å	θ = 2.9–25.3°
c = 24.5011 (18) Å	µ = 0.40 mm⁻¹
β = 99.693 (1)°	T = 294 K
V = 1677.6 (2) Å³	Block, yellow
Z = 4	0.44 × 0.32 × 0.24 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2935 independent reflections
Radiation source: fine-focus sealed tube	2235 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −11→11
T_min = 0.802, T_max = 0.909	k = −8→8
8814 measured reflections	l = −26→29

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0444P)² + 0.3505P] where P = (F_o² + 2F_c²)/3
2935 reflections	(Δ/σ)_max = 0.001
219 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₈H₁₅Cl₂N₃O	V = 1677.6 (2) Å³
M_r = 360.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.4236 (7) Å	µ = 0.40 mm⁻¹
b = 7.3711 (5) Å	T = 294 K
c = 24.5011 (18) Å	0.44 × 0.32 × 0.24 mm
β = 99.693 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2935 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	2235 reflections with I > 2σ(I)
T_min = 0.802, T_max = 0.909	R_int = 0.022
8814 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.08	Δρ_max = 0.19 e Å⁻³
2935 reflections	Δρ_min = −0.29 e Å⁻³
219 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	0.44691 (6)	−0.05518 (7)	1.06469 (2)	0.06103 (19)
Cl2	0.81732 (6)	0.27063 (10)	1.22497 (2)	0.0750 (2)
C11	0.0882 (2)	0.8016 (3)	0.98549 (9)	0.0506 (5)
H11A	0.1237	0.8969	0.9648	0.076*
H11B	0.1485	0.7912	1.0211	0.076*
H11C	−0.0085	0.8290	0.9903	0.076*
N1	0.03425 (16)	0.4330 (2)	0.88548 (6)	0.0409 (4)
N2	−0.00620 (16)	0.5959 (2)	0.90848 (6)	0.0401 (4)
N3	0.28447 (15)	0.4723 (2)	1.01440 (6)	0.0382 (4)
C1	0.46740 (19)	0.3109 (2)	1.07464 (7)	0.0373 (4)
C2	0.5203 (2)	0.1435 (3)	1.09530 (8)	0.0423 (5)
C3	0.6284 (2)	0.1288 (3)	1.14104 (8)	0.0506 (5)
H3	0.6636	0.0160	1.1538	0.061*
C4	0.6822 (2)	0.2856 (3)	1.16710 (8)	0.0483 (5)
C5	0.6326 (2)	0.4533 (3)	1.14840 (8)	0.0476 (5)
H5	0.6698	0.5579	1.1667	0.057*
C6	0.5271 (2)	0.4646 (3)	1.10224 (8)	0.0432 (5)
H6	0.4950	0.5783	1.0892	0.052*
C7	0.35588 (19)	0.3251 (2)	1.02526 (7)	0.0391 (4)
H7	0.3368	0.2262	1.0016	0.047*
C8	0.18082 (18)	0.4828 (2)	0.96690 (7)	0.0354 (4)
C9	0.08972 (19)	0.6280 (2)	0.95513 (7)	0.0370 (4)
C10	0.14472 (19)	0.3513 (2)	0.92327 (7)	0.0385 (4)
O1	0.19010 (15)	0.19821 (18)	0.91639 (6)	0.0526 (4)
C12	−0.0797 (2)	0.7352 (3)	0.87217 (9)	0.0567 (6)
H12A	−0.1233	0.8212	0.8937	0.085*
H12B	−0.1528	0.6801	0.8453	0.085*
H12C	−0.0115	0.7963	0.8536	0.085*
C13	−0.0674 (2)	0.3308 (2)	0.84841 (7)	0.0401 (4)
C14	−0.0177 (2)	0.2350 (3)	0.80691 (8)	0.0522 (5)
H14	0.0783	0.2434	0.8027	0.063*
C15	−0.1117 (3)	0.1268 (3)	0.77185 (9)	0.0634 (6)
H15	−0.0788	0.0615	0.7440	0.076*
C16	−0.2532 (3)	0.1153 (3)	0.77790 (9)	0.0634 (6)
H16	−0.3160	0.0411	0.7544	0.076*
C17	−0.3025 (2)	0.2133 (3)	0.81859 (9)	0.0609 (6)
H17	−0.3992	0.2074	0.8219	0.073*
C18	−0.2097 (2)	0.3205 (3)	0.85452 (8)	0.0502 (5)
H18	−0.2429	0.3849	0.8825	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0749 (4)	0.0349 (3)	0.0688 (4)	0.0005 (2)	−0.0010 (3)	0.0033 (2)
Cl2	0.0586 (4)	0.1057 (5)	0.0524 (3)	0.0053 (3)	−0.0145 (3)	0.0102 (3)
C11	0.0579 (13)	0.0362 (11)	0.0545 (12)	0.0072 (9)	0.0000 (10)	−0.0071 (9)
N1	0.0411 (9)	0.0369 (8)	0.0417 (9)	0.0088 (7)	−0.0021 (7)	−0.0070 (7)
N2	0.0436 (9)	0.0316 (8)	0.0421 (9)	0.0093 (7)	−0.0016 (7)	−0.0014 (7)
N3	0.0379 (8)	0.0362 (9)	0.0382 (8)	0.0043 (7)	0.0002 (7)	−0.0002 (7)
C1	0.0360 (10)	0.0365 (10)	0.0390 (10)	0.0048 (8)	0.0053 (8)	0.0031 (8)
C2	0.0441 (11)	0.0368 (11)	0.0453 (11)	0.0026 (8)	0.0057 (9)	0.0035 (8)
C3	0.0493 (12)	0.0500 (12)	0.0504 (12)	0.0101 (10)	0.0020 (10)	0.0131 (10)
C4	0.0374 (11)	0.0660 (14)	0.0395 (11)	0.0035 (10)	0.0009 (9)	0.0073 (10)
C5	0.0431 (11)	0.0498 (12)	0.0481 (12)	−0.0034 (9)	0.0020 (9)	−0.0044 (10)
C6	0.0432 (11)	0.0365 (11)	0.0483 (11)	0.0039 (8)	0.0029 (9)	0.0014 (9)
C7	0.0399 (10)	0.0358 (10)	0.0396 (10)	0.0026 (8)	0.0005 (8)	−0.0016 (8)
C8	0.0366 (10)	0.0320 (9)	0.0363 (10)	0.0034 (8)	0.0029 (8)	−0.0003 (7)
C9	0.0394 (10)	0.0306 (9)	0.0396 (10)	0.0012 (8)	0.0028 (8)	0.0003 (8)
C10	0.0371 (10)	0.0357 (10)	0.0407 (10)	0.0055 (8)	0.0014 (8)	0.0004 (8)
O1	0.0561 (9)	0.0393 (8)	0.0568 (9)	0.0165 (7)	−0.0064 (7)	−0.0112 (6)
C12	0.0669 (14)	0.0482 (13)	0.0505 (13)	0.0213 (11)	−0.0036 (11)	0.0082 (10)
C13	0.0437 (11)	0.0380 (10)	0.0350 (10)	0.0044 (8)	−0.0039 (8)	−0.0001 (8)
C14	0.0519 (12)	0.0560 (13)	0.0465 (12)	0.0063 (10)	0.0020 (10)	−0.0098 (10)
C15	0.0748 (17)	0.0605 (15)	0.0508 (13)	0.0085 (12)	−0.0014 (12)	−0.0173 (11)
C16	0.0762 (17)	0.0577 (14)	0.0479 (13)	−0.0105 (12)	−0.0138 (12)	−0.0039 (11)
C17	0.0474 (12)	0.0814 (17)	0.0491 (13)	−0.0108 (12)	−0.0056 (10)	0.0055 (12)
C18	0.0468 (12)	0.0630 (14)	0.0387 (11)	0.0011 (10)	0.0015 (9)	−0.0008 (10)

Geometric parameters (Å, º) top

Cl1—C2	1.735 (2)	C5—H5	0.9300
Cl2—C4	1.742 (2)	C6—H6	0.9300
C11—C9	1.481 (3)	C7—H7	0.9300
C11—H11A	0.9600	C8—C9	1.372 (2)
C11—H11B	0.9600	C8—C10	1.440 (2)
C11—H11C	0.9600	C10—O1	1.229 (2)
N1—N2	1.406 (2)	C12—H12A	0.9600
N1—C10	1.407 (2)	C12—H12B	0.9600
N1—C13	1.420 (2)	C12—H12C	0.9600
N2—C9	1.353 (2)	C13—C18	1.377 (3)
N2—C12	1.456 (2)	C13—C14	1.383 (3)
N3—C7	1.281 (2)	C14—C15	1.379 (3)
N3—C8	1.390 (2)	C14—H14	0.9300
C1—C6	1.389 (3)	C15—C16	1.369 (3)
C1—C2	1.394 (3)	C15—H15	0.9300
C1—C7	1.467 (2)	C16—C17	1.374 (3)
C2—C3	1.386 (3)	C16—H16	0.9300
C3—C4	1.375 (3)	C17—C18	1.380 (3)
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.373 (3)	C18—H18	0.9300
C5—C6	1.377 (3)

C9—C11—H11A	109.5	C9—C8—N3	123.10 (16)
C9—C11—H11B	109.5	C9—C8—C10	107.91 (15)
H11A—C11—H11B	109.5	N3—C8—C10	128.97 (16)
C9—C11—H11C	109.5	N2—C9—C8	110.28 (15)
H11A—C11—H11C	109.5	N2—C9—C11	120.91 (16)
H11B—C11—H11C	109.5	C8—C9—C11	128.81 (17)
N2—N1—C10	108.80 (14)	O1—C10—N1	122.62 (16)
N2—N1—C13	120.67 (14)	O1—C10—C8	132.50 (17)
C10—N1—C13	122.58 (15)	N1—C10—C8	104.87 (15)
C9—N2—N1	107.46 (13)	N2—C12—H12A	109.5
C9—N2—C12	125.05 (16)	N2—C12—H12B	109.5
N1—N2—C12	119.41 (15)	H12A—C12—H12B	109.5
C7—N3—C8	119.45 (15)	N2—C12—H12C	109.5
C6—C1—C2	117.03 (17)	H12A—C12—H12C	109.5
C6—C1—C7	121.27 (16)	H12B—C12—H12C	109.5
C2—C1—C7	121.69 (17)	C18—C13—C14	120.56 (18)
C3—C2—C1	122.12 (18)	C18—C13—N1	121.62 (16)
C3—C2—Cl1	117.99 (15)	C14—C13—N1	117.77 (17)
C1—C2—Cl1	119.87 (15)	C15—C14—C13	119.5 (2)
C4—C3—C2	118.27 (19)	C15—C14—H14	120.3
C4—C3—H3	120.9	C13—C14—H14	120.3
C2—C3—H3	120.9	C16—C15—C14	120.2 (2)
C5—C4—C3	121.57 (18)	C16—C15—H15	119.9
C5—C4—Cl2	119.31 (17)	C14—C15—H15	119.9
C3—C4—Cl2	119.12 (16)	C15—C16—C17	120.0 (2)
C4—C5—C6	119.14 (19)	C15—C16—H16	120.0
C4—C5—H5	120.4	C17—C16—H16	120.0
C6—C5—H5	120.4	C16—C17—C18	120.6 (2)
C5—C6—C1	121.87 (18)	C16—C17—H17	119.7
C5—C6—H6	119.1	C18—C17—H17	119.7
C1—C6—H6	119.1	C13—C18—C17	119.10 (19)
N3—C7—C1	120.66 (17)	C13—C18—H18	120.4
N3—C7—H7	119.7	C17—C18—H18	120.4
C1—C7—H7	119.7

C10—N1—N2—C9	8.62 (19)	C12—N2—C9—C11	24.1 (3)
C13—N1—N2—C9	158.31 (16)	N3—C8—C9—N2	−175.64 (16)
C10—N1—N2—C12	158.89 (17)	C10—C8—C9—N2	2.7 (2)
C13—N1—N2—C12	−51.4 (2)	N3—C8—C9—C11	5.3 (3)
C6—C1—C2—C3	−0.4 (3)	C10—C8—C9—C11	−176.38 (19)
C7—C1—C2—C3	178.23 (17)	N2—N1—C10—O1	172.16 (17)
C6—C1—C2—Cl1	177.69 (14)	C13—N1—C10—O1	23.2 (3)
C7—C1—C2—Cl1	−3.6 (2)	N2—N1—C10—C8	−6.80 (19)
C1—C2—C3—C4	1.2 (3)	C13—N1—C10—C8	−155.80 (16)
Cl1—C2—C3—C4	−176.92 (15)	C9—C8—C10—O1	−176.2 (2)
C2—C3—C4—C5	−0.8 (3)	N3—C8—C10—O1	2.0 (3)
C2—C3—C4—Cl2	179.59 (14)	C9—C8—C10—N1	2.63 (19)
C3—C4—C5—C6	−0.4 (3)	N3—C8—C10—N1	−179.17 (17)
Cl2—C4—C5—C6	179.18 (15)	N2—N1—C13—C18	−35.2 (3)
C4—C5—C6—C1	1.3 (3)	C10—N1—C13—C18	110.3 (2)
C2—C1—C6—C5	−0.8 (3)	N2—N1—C13—C14	147.44 (18)
C7—C1—C6—C5	−179.52 (17)	C10—N1—C13—C14	−67.1 (2)
C8—N3—C7—C1	179.09 (15)	C18—C13—C14—C15	−0.7 (3)
C6—C1—C7—N3	−18.1 (3)	N1—C13—C14—C15	176.71 (19)
C2—C1—C7—N3	163.25 (17)	C13—C14—C15—C16	0.4 (4)
C7—N3—C8—C9	173.14 (17)	C14—C15—C16—C17	0.7 (4)
C7—N3—C8—C10	−4.8 (3)	C15—C16—C17—C18	−1.6 (4)
N1—N2—C9—C8	−7.0 (2)	C14—C13—C18—C17	−0.1 (3)
C12—N2—C9—C8	−155.10 (18)	N1—C13—C18—C17	−177.43 (19)
N1—N2—C9—C11	172.20 (17)	C16—C17—C18—C13	1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1	0.93	2.31	3.005 (2)	131
C6—H6···Cl1ⁱ	0.93	2.79	3.703 (2)	168

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₅Cl₂N₃O
M_r	360.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	9.4236 (7), 7.3711 (5), 24.5011 (18)
β (°)	99.693 (1)
V (Å³)	1677.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.44 × 0.32 × 0.24

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.802, 0.909
No. of measured, independent and observed [I > 2σ(I)] reflections	8814, 2935, 2235
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.08
No. of reflections	2935
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.29

Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) top

Cl1—C2	1.735 (2)	N3—C7	1.281 (2)
Cl2—C4	1.742 (2)	N3—C8	1.390 (2)
N1—N2	1.406 (2)

N2—N1—C10	108.80 (14)	C9—N2—C12	125.05 (16)
N2—N1—C13	120.67 (14)	N1—N2—C12	119.41 (15)
C10—N1—C13	122.58 (15)	C7—N3—C8	119.45 (15)
C9—N2—N1	107.46 (13)