(Z)-4-[(2-Amino-4,5-dichloro-anilino)(phenyl)methyl-idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one.

The mol-ecule of the title compound, C(23)H(18)Cl(2)N(4)O, assumes a non-planar conformation in which the pyrazolone ring forms dihedral angles of 32.61 (19), 76.73 (14) and 52.57 (19)° with the three benzene rings. The secondary amino group is involved in an intra-molecular N-H⋯O hydrogen bond. In the crystal, mol-ecules are linked by pairs of N-H⋯O hydrogen bonds, forming inversion dimers. An offset stacking inter-action is observed between the chloro-substituted benzene rings protruding on both sides of these dimers [centroid-centroid distance = 3.862 (1) Å].

Related literature

For related structures, see: Lu et al. (2011 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the catalytic properties of asymmetric Schiff bases, see: Caboni et al. (2012 ▶). For the synthesis, see: Hennig & Mann (1988 ▶).

Experimental

Crystal data

C23H18Cl2N4O

M = 437.31

Triclinic,

a = 8.0653 (16) Å

b = 10.931 (2) Å

c = 13.851 (3) Å

α = 111.627 (3)°

β = 90.775 (3)°

γ = 110.226 (3)°

V = 1051.1 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.33 mm−1

T = 296 K

0.30 × 0.21 × 0.18 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.857, T max = 1.000

5308 measured reflections

3688 independent reflections

1992 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.189

S = 1.03

3688 reflections

280 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.45 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 and local programs.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681204086X/fy2067sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204086X/fy2067Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681204086X/fy2067Isup3.cml

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

C23H18Cl2N4O	Z = 2
Mr = 437.31	F(000) = 452
Triclinic, P1	Dx = 1.382 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0653 (16) Å	Cell parameters from 3250 reflections
b = 10.931 (2) Å	θ = 1.8–25.2°
c = 13.851 (3) Å	µ = 0.33 mm−1
α = 111.627 (3)°	T = 296 K
β = 90.775 (3)°	Block, red
γ = 110.226 (3)°	0.30 × 0.21 × 0.18 mm
V = 1051.1 (4) Å3

Bruker SMART 1K CCD area-detector diffractometer	3688 independent reflections
Radiation source: fine-focus sealed tube	1992 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
thin–slice ω scans	θmax = 25.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→7
Tmin = 0.857, Tmax = 1.000	k = −13→12
5308 measured reflections	l = −15→16

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.189	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0881P)2] where P = (Fo2 + 2Fc2)/3
3688 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.51 e Å−3
2 restraints	Δρmin = −0.45 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl2	1.11130 (17)	0.22914 (15)	0.36132 (9)	0.0878 (5)
Cl1	1.18254 (17)	0.24718 (17)	0.59173 (10)	0.0939 (5)
O1	0.5427 (3)	0.6431 (3)	0.7490 (2)	0.0541 (7)
N2	0.2712 (4)	0.4857 (3)	0.8999 (2)	0.0573 (9)
N3	0.6743 (4)	0.4320 (3)	0.6750 (2)	0.0498 (8)
H3A	0.6612	0.5073	0.6759	0.060*
N1	0.3415 (4)	0.5927 (3)	0.8613 (2)	0.0511 (8)
C19	0.9177 (5)	0.3465 (4)	0.6293 (3)	0.0503 (10)
H19A	0.9434	0.3579	0.6985	0.060*
C22	0.8476 (5)	0.3187 (4)	0.4243 (3)	0.0502 (10)
H22A	0.8266	0.3111	0.3558	0.060*
C18	0.7801 (5)	0.3803 (4)	0.6009 (3)	0.0433 (9)
C9	0.3620 (5)	0.4033 (4)	0.8684 (3)	0.0532 (10)
C6	0.2573 (5)	0.6900 (4)	0.8746 (3)	0.0482 (9)
C23	0.7409 (5)	0.3646 (4)	0.4970 (3)	0.0451 (9)
C11	0.5925 (5)	0.3812 (4)	0.7431 (3)	0.0444 (9)
C7	0.4691 (5)	0.5709 (4)	0.8000 (3)	0.0455 (9)
C20	1.0185 (5)	0.2954 (4)	0.5552 (3)	0.0526 (10)
C12	0.6100 (5)	0.2515 (4)	0.7451 (3)	0.0459 (9)
N4	0.6018 (5)	0.3963 (4)	0.4673 (3)	0.0624 (10)
C8	0.4918 (5)	0.4480 (4)	0.8058 (3)	0.0444 (9)
C21	0.9834 (5)	0.2847 (4)	0.4539 (3)	0.0538 (10)
C13	0.7013 (5)	0.2581 (4)	0.8339 (3)	0.0537 (10)
H13A	0.7464	0.3428	0.8934	0.064*
C5	0.0782 (6)	0.6554 (5)	0.8833 (3)	0.0607 (11)
H5A	0.0107	0.5666	0.8825	0.073*
C1	0.3573 (6)	0.8244 (4)	0.8808 (3)	0.0623 (11)
H1A	0.4793	0.8504	0.8782	0.075*
C17	0.5389 (5)	0.1236 (4)	0.6589 (3)	0.0625 (11)
H17A	0.4743	0.1174	0.6000	0.075*
C15	0.6556 (7)	0.0121 (5)	0.7463 (4)	0.0749 (14)
H15A	0.6714	−0.0683	0.7462	0.090*
C10	0.3125 (6)	0.2748 (4)	0.8947 (4)	0.0731 (14)
H10A	0.2210	0.2745	0.9383	0.110*
H10B	0.4161	0.2775	0.9316	0.110*
H10C	0.2687	0.1904	0.8310	0.110*
C4	−0.0012 (6)	0.7519 (6)	0.8933 (3)	0.0719 (13)
H4C	−0.1228	0.7268	0.8969	0.086*
C2	0.2773 (7)	0.9199 (5)	0.8910 (4)	0.0775 (14)
H2B	0.3445	1.0095	0.8932	0.093*
C14	0.7249 (6)	0.1390 (5)	0.8336 (4)	0.0668 (12)
H14A	0.7879	0.1441	0.8926	0.080*
C16	0.5628 (6)	0.0062 (5)	0.6596 (4)	0.0753 (13)
H16A	0.5157	−0.0789	0.6006	0.090*
C3	0.0976 (8)	0.8833 (6)	0.8979 (4)	0.0811 (15)
H3B	0.0442	0.9486	0.9057	0.097*
H4A	0.508 (4)	0.381 (4)	0.495 (3)	0.062 (13)*
H4B	0.572 (6)	0.371 (5)	0.3997 (17)	0.092 (17)*

	U11	U22	U33	U12	U13	U23
Cl2	0.0813 (9)	0.1355 (12)	0.0620 (7)	0.0711 (9)	0.0337 (6)	0.0267 (7)
Cl1	0.0773 (9)	0.1571 (13)	0.0793 (9)	0.0818 (9)	0.0190 (7)	0.0461 (9)
O1	0.0631 (17)	0.0617 (17)	0.0604 (17)	0.0372 (14)	0.0316 (13)	0.0354 (14)
N2	0.070 (2)	0.059 (2)	0.060 (2)	0.0348 (19)	0.0336 (17)	0.0300 (17)
N3	0.062 (2)	0.058 (2)	0.0479 (19)	0.0391 (17)	0.0273 (16)	0.0249 (16)
N1	0.057 (2)	0.0536 (19)	0.058 (2)	0.0311 (17)	0.0300 (16)	0.0295 (16)
C19	0.053 (2)	0.059 (2)	0.043 (2)	0.026 (2)	0.0123 (18)	0.0201 (19)
C22	0.048 (2)	0.065 (3)	0.041 (2)	0.026 (2)	0.0137 (18)	0.0214 (19)
C18	0.044 (2)	0.048 (2)	0.046 (2)	0.0230 (18)	0.0170 (17)	0.0215 (17)
C9	0.067 (3)	0.056 (2)	0.051 (2)	0.032 (2)	0.028 (2)	0.027 (2)
C6	0.056 (3)	0.056 (2)	0.045 (2)	0.035 (2)	0.0187 (18)	0.0200 (19)
C23	0.049 (2)	0.048 (2)	0.043 (2)	0.0229 (19)	0.0135 (17)	0.0178 (18)
C11	0.046 (2)	0.051 (2)	0.040 (2)	0.0218 (19)	0.0120 (17)	0.0200 (18)
C7	0.046 (2)	0.051 (2)	0.045 (2)	0.0242 (19)	0.0168 (18)	0.0194 (18)
C20	0.046 (2)	0.066 (3)	0.051 (2)	0.031 (2)	0.0133 (19)	0.020 (2)
C12	0.047 (2)	0.046 (2)	0.049 (2)	0.0238 (19)	0.0154 (18)	0.0182 (19)
N4	0.060 (3)	0.088 (3)	0.067 (3)	0.047 (2)	0.021 (2)	0.042 (2)
C8	0.057 (2)	0.047 (2)	0.042 (2)	0.0327 (19)	0.0211 (18)	0.0192 (17)
C21	0.045 (2)	0.064 (3)	0.053 (2)	0.025 (2)	0.0189 (19)	0.019 (2)
C13	0.067 (3)	0.052 (2)	0.047 (2)	0.028 (2)	0.012 (2)	0.0184 (19)
C5	0.060 (3)	0.065 (3)	0.057 (3)	0.030 (2)	0.018 (2)	0.018 (2)
C1	0.061 (3)	0.065 (3)	0.073 (3)	0.034 (2)	0.024 (2)	0.031 (2)
C17	0.069 (3)	0.058 (3)	0.055 (3)	0.025 (2)	0.018 (2)	0.016 (2)
C15	0.109 (4)	0.071 (3)	0.087 (4)	0.064 (3)	0.056 (3)	0.046 (3)
C10	0.093 (4)	0.066 (3)	0.088 (3)	0.043 (3)	0.051 (3)	0.048 (3)
C4	0.059 (3)	0.098 (4)	0.064 (3)	0.047 (3)	0.019 (2)	0.021 (3)
C2	0.098 (4)	0.076 (3)	0.083 (3)	0.054 (3)	0.037 (3)	0.037 (3)
C14	0.085 (3)	0.078 (3)	0.067 (3)	0.053 (3)	0.032 (2)	0.039 (3)
C16	0.096 (4)	0.048 (3)	0.075 (3)	0.029 (3)	0.032 (3)	0.015 (2)
C3	0.110 (4)	0.103 (4)	0.066 (3)	0.080 (4)	0.033 (3)	0.035 (3)

Cl2—C21	1.724 (4)	C12—C17	1.380 (5)
Cl1—C20	1.716 (4)	C12—C13	1.391 (5)
O1—C7	1.254 (4)	N4—H4A	0.850 (18)
N2—C9	1.309 (4)	N4—H4B	0.876 (19)
N2—N1	1.409 (4)	C13—C14	1.378 (5)
N3—C11	1.336 (4)	C13—H13A	0.9300
N3—C18	1.424 (4)	C5—C4	1.380 (5)
N3—H3A	0.8600	C5—H5A	0.9300
N1—C7	1.372 (4)	C1—C2	1.374 (5)
N1—C6	1.409 (4)	C1—H1A	0.9300
C19—C18	1.379 (5)	C17—C16	1.365 (5)
C19—C20	1.394 (5)	C17—H17A	0.9300
C19—H19A	0.9300	C15—C16	1.375 (6)
C22—C21	1.374 (5)	C15—C14	1.380 (6)
C22—C23	1.398 (5)	C15—H15A	0.9300
C22—H22A	0.9300	C10—H10A	0.9600
C18—C23	1.404 (5)	C10—H10B	0.9600
C9—C8	1.439 (5)	C10—H10C	0.9600
C9—C10	1.502 (5)	C4—C3	1.357 (7)
C6—C1	1.379 (5)	C4—H4C	0.9300
C6—C5	1.380 (5)	C2—C3	1.378 (7)
C23—N4	1.381 (5)	C2—H2B	0.9300
C11—C8	1.382 (5)	C14—H14A	0.9300
C11—C12	1.482 (5)	C16—H16A	0.9300
C7—C8	1.448 (5)	C3—H3B	0.9300
C20—C21	1.380 (5)
C9—N2—N1	105.9 (3)	C11—C8—C7	122.6 (3)
C11—N3—C18	129.7 (3)	C9—C8—C7	104.5 (3)
C11—N3—H3A	115.2	C22—C21—C20	121.3 (3)
C18—N3—H3A	115.2	C22—C21—Cl2	118.2 (3)
C7—N1—C6	128.5 (3)	C20—C21—Cl2	120.5 (3)
C7—N1—N2	112.0 (3)	C14—C13—C12	119.9 (4)
C6—N1—N2	118.6 (3)	C14—C13—H13A	120.1
C18—C19—C20	120.5 (3)	C12—C13—H13A	120.1
C18—C19—H19A	119.7	C6—C5—C4	120.3 (4)
C20—C19—H19A	119.7	C6—C5—H5A	119.8
C21—C22—C23	120.2 (3)	C4—C5—H5A	119.8
C21—C22—H22A	119.9	C2—C1—C6	120.1 (4)
C23—C22—H22A	119.9	C2—C1—H1A	119.9
C19—C18—C23	120.3 (3)	C6—C1—H1A	119.9
C19—C18—N3	121.7 (3)	C16—C17—C12	120.4 (4)
C23—C18—N3	118.0 (3)	C16—C17—H17A	119.8
N2—C9—C8	112.2 (3)	C12—C17—H17A	119.8
N2—C9—C10	118.4 (3)	C16—C15—C14	119.1 (4)
C8—C9—C10	129.3 (3)	C16—C15—H15A	120.4
C1—C6—C5	119.1 (4)	C14—C15—H15A	120.4
C1—C6—N1	119.1 (4)	C9—C10—H10A	109.5
C5—C6—N1	121.8 (4)	C9—C10—H10B	109.5
N4—C23—C22	120.6 (3)	H10A—C10—H10B	109.5
N4—C23—C18	120.7 (3)	C9—C10—H10C	109.5
C22—C23—C18	118.6 (3)	H10A—C10—H10C	109.5
N3—C11—C8	119.3 (3)	H10B—C10—H10C	109.5
N3—C11—C12	117.7 (3)	C3—C4—C5	120.2 (4)
C8—C11—C12	123.0 (3)	C3—C4—H4C	119.9
O1—C7—N1	125.3 (3)	C5—C4—H4C	119.9
O1—C7—C8	129.5 (3)	C1—C2—C3	120.2 (5)
N1—C7—C8	105.2 (3)	C1—C2—H2B	119.9
C21—C20—C19	119.0 (3)	C3—C2—H2B	119.9
C21—C20—Cl1	121.7 (3)	C13—C14—C15	120.5 (4)
C19—C20—Cl1	119.3 (3)	C13—C14—H14A	119.8
C17—C12—C13	119.1 (3)	C15—C14—H14A	119.8
C17—C12—C11	120.8 (3)	C17—C16—C15	120.9 (4)
C13—C12—C11	120.0 (3)	C17—C16—H16A	119.5
C23—N4—H4A	120 (3)	C15—C16—H16A	119.5
C23—N4—H4B	117 (3)	C4—C3—C2	120.0 (4)
H4A—N4—H4B	110 (4)	C4—C3—H3B	120.0
C11—C8—C9	131.6 (3)	C2—C3—H3B	120.0

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86	2.01	2.735 (4)	141
N4—H4B···O1i	0.88 (2)	2.18 (2)	3.022 (5)	162 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.86	2.01	2.735 (4)	141
N4—H4B⋯O1i	0.88 (2)	2.18 (2)	3.022 (5)	162 (4)

Symmetry code: (i) .