(4Z)-4-[(2-Chloro-anilino)(phen-yl)methyl-idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one.

The title compound, C(23)H(18)ClN(3)O, exists in an enamine-keto form with the amino group involved in an intra-molecular N-H⋯O hydrogen bond. The five-membered ring is nearly planar, the largest deviation being 0.0004 (7) Å, and makes dihedral angles of 16.62 (6), 41.89 (5) and 71.27 (4)° with the phenyl rings. In the crystal, weak C-H⋯O hydrogen bonds link the mol-ecules into supra-molecular chains along the b axis.

Related literature

For general background to Schiff bases derived from 1-phenyl-3-methyl-4-benzoyl-1H-pyrazol-5(4H)-one and their pharmaceutical and agrochemical applications, see: Casas et al. (2007 ▶); Zhang et al. (2008 ▶). For related structures, see: Zhang et al. (2007 ▶); Li et al. (2009 ▶); Chi et al. (2010 ▶).

Experimental

Crystal data

C23H18ClN3O

M = 387.85

Monoclinic,

a = 9.0425 (3) Å

b = 18.5180 (7) Å

c = 11.1983 (4) Å

β = 90.423 (1)°

V = 1875.09 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 296 K

0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.951, T max = 0.959

17018 measured reflections

4637 independent reflections

4251 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.095

S = 1.04

4613 reflections

258 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020004/zq2164sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020004/zq2164Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812020004/zq2164Isup3.cml

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

C23H18ClN3O	F(000) = 808.0
Mr = 387.85	Dx = 1.374 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 9949 reflections
a = 9.0425 (3) Å	θ = 3.1–28.2°
b = 18.5180 (7) Å	µ = 0.22 mm−1
c = 11.1983 (4) Å	T = 296 K
β = 90.423 (1)°	Block, yellow
V = 1875.09 (12) Å3	0.22 × 0.20 × 0.18 mm
Z = 4

Bruker SMART CCD diffractometer	4637 independent reflections
Radiation source: fine-focus sealed tube	4251 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
ω scans	θmax = 28.2°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
Tmin = 0.951, Tmax = 0.959	k = −24→23
17018 measured reflections	l = −14→14

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) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0482P)2 + 0.9306P] where P = (Fo2 + 2Fc2)/3
4613 reflections	(Δ/σ)max < 0.001
258 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.34 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
C1	0.86725 (13)	−0.06692 (6)	−0.09829 (10)	0.0186 (2)
C2	0.87873 (15)	−0.07367 (7)	−0.22145 (11)	0.0238 (2)
H2	0.8476	−0.0364	−0.2713	0.029*
C3	0.93725 (15)	−0.13668 (7)	−0.26969 (12)	0.0271 (3)
H3	0.9454	−0.1413	−0.3521	0.033*
C4	0.98343 (14)	−0.19250 (7)	−0.19629 (12)	0.0253 (3)
H4	1.0181	−0.2354	−0.2291	0.030*
C5	0.97757 (15)	−0.18398 (7)	−0.07385 (12)	0.0284 (3)
H5	1.0116	−0.2208	−0.0242	0.034*
C6	0.92153 (15)	−0.12112 (7)	−0.02397 (11)	0.0260 (3)
H6	0.9203	−0.1153	0.0585	0.031*
C7	0.70636 (14)	0.10296 (6)	−0.05496 (10)	0.0196 (2)
C8	0.67068 (17)	0.17489 (7)	−0.10804 (11)	0.0269 (3)
H8A	0.7155	0.1787	−0.1852	0.040*
H8B	0.7083	0.2124	−0.0570	0.040*
H8C	0.5654	0.1798	−0.1161	0.040*
C9	0.68060 (13)	0.07593 (6)	0.06368 (10)	0.0187 (2)
C10	0.74394 (13)	0.00384 (6)	0.06478 (10)	0.0198 (2)
C11	0.62430 (12)	0.10790 (6)	0.16590 (10)	0.0164 (2)
C12	0.56486 (12)	0.18268 (6)	0.16522 (10)	0.0169 (2)
C13	0.43881 (14)	0.20000 (7)	0.09874 (11)	0.0234 (2)
H13	0.3877	0.1641	0.0577	0.028*
C14	0.38969 (16)	0.27111 (8)	0.09393 (13)	0.0326 (3)
H14	0.3046	0.2826	0.0509	0.039*
C15	0.46709 (18)	0.32468 (7)	0.15296 (14)	0.0359 (3)
H15	0.4353	0.3723	0.1478	0.043*
C16	0.59174 (17)	0.30782 (7)	0.21975 (13)	0.0318 (3)
H16	0.6434	0.3442	0.2594	0.038*
C17	0.63988 (14)	0.23657 (7)	0.22775 (11)	0.0225 (2)
H17	0.7218	0.2250	0.2747	0.027*
C18	0.57642 (12)	0.08798 (6)	0.38216 (9)	0.0161 (2)
C19	0.43971 (13)	0.12143 (6)	0.39789 (10)	0.0189 (2)
H19	0.3851	0.1365	0.3317	0.023*
C20	0.38483 (13)	0.13232 (6)	0.51203 (11)	0.0211 (2)
H20	0.2938	0.1548	0.5218	0.025*
C21	0.46478 (14)	0.10990 (6)	0.61183 (10)	0.0213 (2)
H21	0.4270	0.1172	0.6879	0.026*
C22	0.60091 (13)	0.07666 (6)	0.59773 (10)	0.0196 (2)
H22	0.6550	0.0616	0.6642	0.024*
C23	0.65570 (12)	0.06605 (6)	0.48371 (10)	0.0166 (2)
Cl1	0.82565 (3)	0.023579 (16)	0.46642 (3)	0.02280 (9)
H3A	0.678 (2)	0.0288 (10)	0.2610 (16)	0.034 (5)*
N1	0.79928 (12)	−0.00523 (5)	−0.04860 (8)	0.0200 (2)
N2	0.77460 (12)	0.05536 (5)	−0.12101 (9)	0.0210 (2)
N3	0.63332 (12)	0.07069 (6)	0.26879 (8)	0.0194 (2)
O1	0.74879 (11)	−0.04063 (5)	0.14826 (8)	0.0267 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0193 (5)	0.0172 (5)	0.0194 (5)	0.0015 (4)	0.0010 (4)	−0.0038 (4)
C2	0.0306 (6)	0.0216 (6)	0.0193 (5)	0.0019 (5)	0.0034 (5)	−0.0022 (4)
C3	0.0305 (6)	0.0278 (7)	0.0232 (6)	0.0001 (5)	0.0044 (5)	−0.0099 (5)
C4	0.0191 (5)	0.0218 (6)	0.0349 (7)	0.0013 (4)	0.0014 (5)	−0.0117 (5)
C5	0.0285 (6)	0.0243 (6)	0.0322 (7)	0.0094 (5)	−0.0021 (5)	−0.0023 (5)
C6	0.0308 (6)	0.0258 (6)	0.0214 (6)	0.0095 (5)	−0.0013 (5)	−0.0023 (5)
C7	0.0268 (6)	0.0176 (5)	0.0143 (5)	0.0023 (4)	0.0000 (4)	0.0007 (4)
C8	0.0436 (7)	0.0197 (6)	0.0177 (5)	0.0079 (5)	0.0046 (5)	0.0039 (4)
C9	0.0255 (6)	0.0154 (5)	0.0152 (5)	0.0036 (4)	0.0005 (4)	0.0012 (4)
C10	0.0256 (6)	0.0175 (5)	0.0164 (5)	0.0044 (4)	0.0019 (4)	0.0001 (4)
C11	0.0179 (5)	0.0160 (5)	0.0152 (5)	0.0010 (4)	−0.0007 (4)	0.0006 (4)
C12	0.0195 (5)	0.0155 (5)	0.0158 (5)	0.0015 (4)	0.0042 (4)	0.0011 (4)
C13	0.0227 (6)	0.0242 (6)	0.0232 (6)	0.0036 (5)	0.0015 (4)	0.0052 (4)
C14	0.0303 (7)	0.0321 (7)	0.0356 (7)	0.0139 (6)	0.0092 (5)	0.0139 (6)
C15	0.0444 (8)	0.0186 (6)	0.0452 (8)	0.0103 (6)	0.0247 (7)	0.0082 (6)
C16	0.0402 (8)	0.0192 (6)	0.0362 (7)	−0.0072 (5)	0.0213 (6)	−0.0073 (5)
C17	0.0229 (6)	0.0225 (6)	0.0222 (5)	−0.0036 (4)	0.0078 (4)	−0.0049 (4)
C18	0.0201 (5)	0.0140 (5)	0.0143 (5)	−0.0007 (4)	0.0023 (4)	0.0001 (4)
C19	0.0202 (5)	0.0171 (5)	0.0193 (5)	0.0009 (4)	0.0017 (4)	0.0016 (4)
C20	0.0222 (5)	0.0159 (5)	0.0251 (6)	0.0001 (4)	0.0074 (4)	−0.0003 (4)
C21	0.0290 (6)	0.0176 (5)	0.0175 (5)	−0.0040 (4)	0.0077 (4)	−0.0023 (4)
C22	0.0263 (6)	0.0174 (5)	0.0151 (5)	−0.0040 (4)	−0.0003 (4)	0.0007 (4)
C23	0.0167 (5)	0.0149 (5)	0.0182 (5)	−0.0015 (4)	0.0008 (4)	0.0005 (4)
Cl1	0.01928 (14)	0.02670 (16)	0.02240 (15)	0.00267 (10)	−0.00047 (10)	0.00295 (10)
N1	0.0294 (5)	0.0163 (5)	0.0142 (4)	0.0054 (4)	0.0020 (4)	0.0006 (3)
N2	0.0311 (5)	0.0170 (5)	0.0150 (4)	0.0037 (4)	0.0003 (4)	0.0018 (4)
N3	0.0254 (5)	0.0179 (5)	0.0148 (4)	0.0072 (4)	0.0028 (4)	0.0007 (3)
O1	0.0408 (5)	0.0208 (4)	0.0186 (4)	0.0113 (4)	0.0073 (4)	0.0054 (3)

C1—C2	1.3895 (16)	C12—C13	1.3941 (16)
C1—C6	1.3910 (17)	C13—C14	1.3906 (18)
C1—N1	1.4133 (14)	C13—H13	0.9300
C2—C3	1.3920 (17)	C14—C15	1.380 (2)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.383 (2)	C15—C16	1.384 (2)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.3816 (19)	C16—C17	1.3921 (19)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.3885 (18)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.3950 (16)
C6—H6	0.9300	C18—C23	1.4000 (15)
C7—N2	1.3084 (15)	C18—N3	1.4102 (14)
C7—C9	1.4403 (15)	C19—C20	1.3892 (16)
C7—C8	1.4928 (16)	C19—H19	0.9300
C8—H8A	0.9600	C20—C21	1.3900 (18)
C8—H8B	0.9600	C20—H20	0.9300
C8—H8C	0.9600	C21—C22	1.3863 (17)
C9—C11	1.3887 (15)	C21—H21	0.9300
C9—C10	1.4526 (16)	C22—C23	1.3870 (15)
C10—O1	1.2464 (14)	C22—H22	0.9300
C10—N1	1.3784 (14)	C23—Cl1	1.7384 (11)
C11—N3	1.3445 (14)	N1—N2	1.4012 (13)
C11—C12	1.4855 (15)	N3—H3A	0.877 (19)
C12—C17	1.3925 (16)
C2—C1—C6	120.02 (11)	C14—C13—H13	120.1
C2—C1—N1	119.96 (11)	C12—C13—H13	120.1
C6—C1—N1	120.02 (10)	C15—C14—C13	120.10 (13)
C1—C2—C3	119.47 (12)	C15—C14—H14	120.0
C1—C2—H2	120.3	C13—C14—H14	120.0
C3—C2—H2	120.3	C14—C15—C16	120.34 (12)
C4—C3—C2	120.65 (12)	C14—C15—H15	119.8
C4—C3—H3	119.7	C16—C15—H15	119.8
C2—C3—H3	119.7	C15—C16—C17	120.11 (13)
C5—C4—C3	119.39 (12)	C15—C16—H16	119.9
C5—C4—H4	120.3	C17—C16—H16	119.9
C3—C4—H4	120.3	C16—C17—C12	119.73 (12)
C4—C5—C6	120.78 (12)	C16—C17—H17	120.1
C4—C5—H5	119.6	C12—C17—H17	120.1
C6—C5—H5	119.6	C19—C18—C23	118.37 (10)
C5—C6—C1	119.50 (12)	C19—C18—N3	122.96 (10)
C5—C6—H6	120.2	C23—C18—N3	118.51 (10)
C1—C6—H6	120.2	C20—C19—C18	120.23 (11)
N2—C7—C9	111.56 (10)	C20—C19—H19	119.9
N2—C7—C8	118.52 (10)	C18—C19—H19	119.9
C9—C7—C8	129.90 (10)	C19—C20—C21	120.61 (11)
C7—C8—H8A	109.5	C19—C20—H20	119.7
C7—C8—H8B	109.5	C21—C20—H20	119.7
H8A—C8—H8B	109.5	C22—C21—C20	119.87 (11)
C7—C8—H8C	109.5	C22—C21—H21	120.1
H8A—C8—H8C	109.5	C20—C21—H21	120.1
H8B—C8—H8C	109.5	C21—C22—C23	119.42 (11)
C11—C9—C7	132.45 (11)	C21—C22—H22	120.3
C11—C9—C10	122.12 (10)	C23—C22—H22	120.3
C7—C9—C10	105.11 (10)	C22—C23—C18	121.49 (10)
O1—C10—N1	126.82 (11)	C22—C23—Cl1	119.26 (9)
O1—C10—C9	128.70 (11)	C18—C23—Cl1	119.25 (9)
N1—C10—C9	104.48 (9)	C10—N1—N2	112.22 (9)
N3—C11—C9	117.88 (10)	C10—N1—C1	128.54 (10)
N3—C11—C12	120.12 (10)	N2—N1—C1	119.16 (9)
C9—C11—C12	121.87 (10)	C7—N2—N1	106.62 (9)
C17—C12—C13	119.80 (11)	C11—N3—C18	129.41 (10)
C17—C12—C11	119.38 (10)	C11—N3—H3A	113.1 (12)
C13—C12—C11	120.77 (10)	C18—N3—H3A	117.4 (12)
C14—C13—C12	119.87 (13)
C6—C1—C2—C3	3.56 (19)	C13—C12—C17—C16	−2.44 (17)
N1—C1—C2—C3	−175.90 (12)	C11—C12—C17—C16	174.82 (11)
C1—C2—C3—C4	0.2 (2)	C23—C18—C19—C20	−0.05 (17)
C2—C3—C4—C5	−3.0 (2)	N3—C18—C19—C20	175.29 (11)
C3—C4—C5—C6	2.1 (2)	C18—C19—C20—C21	−0.23 (18)
C4—C5—C6—C1	1.6 (2)	C19—C20—C21—C22	0.31 (18)
C2—C1—C6—C5	−4.49 (19)	C20—C21—C22—C23	−0.10 (17)
N1—C1—C6—C5	174.98 (12)	C21—C22—C23—C18	−0.18 (17)
N2—C7—C9—C11	174.02 (13)	C21—C22—C23—Cl1	−179.40 (9)
C8—C7—C9—C11	−4.3 (2)	C19—C18—C23—C22	0.26 (17)
N2—C7—C9—C10	0.57 (14)	N3—C18—C23—C22	−175.30 (10)
C8—C7—C9—C10	−177.72 (13)	C19—C18—C23—Cl1	179.47 (8)
C11—C9—C10—O1	5.5 (2)	N3—C18—C23—Cl1	3.92 (14)
C7—C9—C10—O1	179.79 (13)	O1—C10—N1—N2	179.70 (12)
C11—C9—C10—N1	−174.35 (11)	C9—C10—N1—N2	−0.45 (13)
C7—C9—C10—N1	−0.05 (13)	O1—C10—N1—C1	3.2 (2)
C7—C9—C11—N3	−170.78 (12)	C9—C10—N1—C1	−176.98 (11)
C10—C9—C11—N3	1.74 (17)	C2—C1—N1—C10	161.96 (12)
C7—C9—C11—C12	5.1 (2)	C6—C1—N1—C10	−17.50 (19)
C10—C9—C11—C12	177.64 (11)	C2—C1—N1—N2	−14.36 (17)
N3—C11—C12—C17	63.52 (15)	C6—C1—N1—N2	166.17 (11)
C9—C11—C12—C17	−112.29 (13)	C9—C7—N2—N1	−0.83 (14)
N3—C11—C12—C13	−119.24 (13)	C8—C7—N2—N1	177.68 (11)
C9—C11—C12—C13	64.95 (15)	C10—N1—N2—C7	0.81 (14)
C17—C12—C13—C14	0.82 (18)	C1—N1—N2—C7	177.71 (11)
C11—C12—C13—C14	−176.41 (11)	C9—C11—N3—C18	−175.06 (11)
C12—C13—C14—C15	1.23 (19)	C12—C11—N3—C18	8.97 (18)
C13—C14—C15—C16	−1.7 (2)	C19—C18—N3—C11	37.69 (18)
C14—C15—C16—C17	0.0 (2)	C23—C18—N3—C11	−146.98 (12)
C15—C16—C17—C12	2.03 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.879 (18)	1.915 (18)	2.6800 (14)	144.5 (16)
C6—H6···O1	0.93	2.31	2.9027 (16)	121
C16—H16···O1i	0.93	2.56	3.4797 (17)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.879 (18)	1.915 (18)	2.6800 (14)	144.5 (16)
C6—H6⋯O1	0.93	2.31	2.9027 (16)	121
C16—H16⋯O1i	0.93	2.56	3.4797 (17)	170

Symmetry code: (i) .