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

The title compound, C(23)H(18)ClN(3)O, was synthesized by the reaction of 4-chloro-aniline and 4-benzoyl-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one. The terminal benzene rings are twisted at dihedral angles of 48.3 (2), 71.4 (2) and 36.1 (2)° with respect to the central eight-atom methyl-pyrazolone/amino-methyl-ene unit. An intra-molecular N-H⋯O hydrogen bond stabilizes the planar conformation [mean deviation = 0.0398 (5) Å] of the central unit, generating an S(6) ring motif. The crystal packing is stabilized by van der Waals forces.

Related literature

For the properties of β-enamino­ketones, see: Li et al. (2000 ▶); Zhang et al. (2003 ▶, 2008 ▶); Cingolani et al. (2006 ▶); Marchetti et al. (2005 ▶). For the preparation of β-enamino­ketones, see: Yang et al. (2004 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C23H18ClN3O

M = 387.85

Triclinic,

a = 7.4305 (15) Å

b = 11.069 (2) Å

c = 13.518 (3) Å

α = 109.28 (3)°

β = 98.78 (3)°

γ = 105.08 (3)°

V = 978.0 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.21 mm−1

T = 293 K

0.34 × 0.31 × 0.09 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.921, T max = 0.985

7818 measured reflections

3506 independent reflections

2198 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.142

S = 1.05

3506 reflections

259 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.61 e Å−3

Δρmin = −0.56 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809054816/si2229sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054816/si2229Isup2.hkl

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

C23H18ClN3O	Z = 2
Mr = 387.85	F(000) = 404
Triclinic, P1	Dx = 1.317 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4305 (15) Å	Cell parameters from 5058 reflections
b = 11.069 (2) Å	θ = 3.1–27.5°
c = 13.518 (3) Å	µ = 0.21 mm−1
α = 109.28 (3)°	T = 293 K
β = 98.78 (3)°	Platelet, yellow
γ = 105.08 (3)°	0.34 × 0.31 × 0.09 mm
V = 978.0 (5) Å3

Rigaku R-AXIS RAPID diffractometer	3506 independent reflections
Radiation source: fine-focus sealed tube	2198 reflections with I > 2σ(I)
graphite	Rint = 0.033
Detector resolution: 10.00 pixels mm-1	θmax = 25.2°, θmin = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −13→13
Tmin = 0.921, Tmax = 0.985	l = −16→16
7818 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.142	w = 1/[σ2(Fo2) + (0.0617P)2 + 0.2511P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3506 reflections	Δρmax = 0.61 e Å−3
259 parameters	Δρmin = −0.56 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (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
Cl1	1.15532 (15)	0.75138 (11)	0.40321 (8)	0.0994 (4)
O1	0.4993 (3)	1.13318 (17)	0.73705 (15)	0.0511 (5)
N1	0.6371 (3)	0.9255 (2)	0.66884 (17)	0.0474 (6)
N2	0.3133 (3)	1.10057 (19)	0.85631 (17)	0.0444 (5)
N3	0.2491 (3)	1.0019 (2)	0.89847 (17)	0.0478 (6)
C1	0.9987 (4)	0.7976 (3)	0.4798 (2)	0.0569 (8)
C2	0.8521 (4)	0.8344 (3)	0.4374 (2)	0.0568 (8)
H2	0.8337	0.8327	0.3673	0.068*
C3	0.7319 (4)	0.8742 (3)	0.5007 (2)	0.0482 (7)
H3	0.6313	0.8988	0.4725	0.058*
C4	0.7596 (4)	0.8780 (2)	0.6053 (2)	0.0428 (6)
C5	0.9092 (4)	0.8414 (3)	0.6470 (2)	0.0550 (7)
H5	0.9299	0.8450	0.7177	0.066*
C6	1.0273 (4)	0.7997 (3)	0.5837 (2)	0.0610 (8)
H6	1.1262	0.7730	0.6109	0.073*
C7	0.5574 (4)	0.8763 (2)	0.73575 (19)	0.0405 (6)
C8	0.5736 (4)	0.7455 (2)	0.7374 (2)	0.0424 (6)
C9	0.4800 (4)	0.6275 (3)	0.6453 (2)	0.0553 (8)
H9	0.4062	0.6305	0.5846	0.066*
C10	0.4969 (5)	0.5063 (3)	0.6442 (3)	0.0709 (10)
H10	0.4334	0.4271	0.5828	0.085*
C11	0.6068 (6)	0.5014 (3)	0.7330 (3)	0.0746 (10)
H11	0.6195	0.4193	0.7313	0.090*
C12	0.6985 (5)	0.6180 (3)	0.8250 (3)	0.0647 (9)
H12	0.7723	0.6145	0.8855	0.078*
C13	0.6809 (4)	0.7401 (3)	0.8275 (2)	0.0517 (7)
H13	0.7413	0.8185	0.8899	0.062*
C14	0.4532 (4)	0.9448 (2)	0.79664 (19)	0.0398 (6)
C15	0.4324 (4)	1.0689 (2)	0.7907 (2)	0.0413 (6)
C16	0.3330 (4)	0.9113 (2)	0.8635 (2)	0.0433 (6)
C17	0.2877 (5)	0.7911 (3)	0.8946 (3)	0.0597 (8)
H17A	0.1911	0.7943	0.9342	0.090*
H17B	0.4027	0.7927	0.9392	0.090*
H17C	0.2404	0.7092	0.8302	0.090*
C18	0.2310 (4)	1.2054 (2)	0.8705 (2)	0.0431 (6)
C19	0.3398 (5)	1.3293 (3)	0.8740 (2)	0.0571 (8)
H19	0.4674	1.3452	0.8704	0.069*
C20	0.2567 (5)	1.4296 (3)	0.8829 (3)	0.0682 (9)
H20	0.3288	1.5130	0.8845	0.082*
C21	0.0701 (5)	1.4074 (3)	0.8896 (2)	0.0669 (9)
H21	0.0147	1.4747	0.8944	0.080*
C22	−0.0349 (5)	1.2852 (3)	0.8891 (2)	0.0640 (9)
H22	−0.1609	1.2709	0.8953	0.077*
C23	0.0437 (4)	1.1834 (3)	0.8794 (2)	0.0554 (7)
H23	−0.0286	1.1008	0.8790	0.067*
H1	0.605 (4)	1.002 (3)	0.669 (2)	0.067 (9)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0867 (7)	0.1399 (9)	0.0781 (6)	0.0596 (6)	0.0465 (5)	0.0223 (6)
O1	0.0581 (13)	0.0564 (11)	0.0614 (12)	0.0307 (9)	0.0305 (10)	0.0351 (9)
N1	0.0555 (15)	0.0529 (13)	0.0502 (13)	0.0312 (11)	0.0243 (11)	0.0253 (11)
N2	0.0529 (14)	0.0436 (12)	0.0490 (12)	0.0244 (10)	0.0232 (11)	0.0225 (10)
N3	0.0531 (15)	0.0520 (13)	0.0505 (13)	0.0245 (11)	0.0226 (11)	0.0254 (11)
C1	0.0485 (18)	0.0643 (18)	0.0495 (17)	0.0193 (14)	0.0190 (14)	0.0085 (14)
C2	0.057 (2)	0.0678 (18)	0.0444 (15)	0.0203 (15)	0.0179 (14)	0.0192 (14)
C3	0.0483 (17)	0.0539 (16)	0.0490 (16)	0.0197 (13)	0.0147 (13)	0.0251 (13)
C4	0.0400 (16)	0.0441 (14)	0.0451 (14)	0.0153 (12)	0.0151 (12)	0.0153 (12)
C5	0.0515 (18)	0.0749 (19)	0.0425 (15)	0.0307 (15)	0.0135 (13)	0.0197 (14)
C6	0.0484 (18)	0.079 (2)	0.0564 (18)	0.0333 (15)	0.0126 (14)	0.0184 (15)
C7	0.0394 (15)	0.0438 (14)	0.0387 (13)	0.0177 (11)	0.0065 (12)	0.0152 (11)
C8	0.0470 (17)	0.0422 (14)	0.0445 (15)	0.0221 (12)	0.0190 (13)	0.0163 (12)
C9	0.065 (2)	0.0500 (16)	0.0475 (16)	0.0203 (14)	0.0168 (14)	0.0126 (13)
C10	0.101 (3)	0.0409 (17)	0.065 (2)	0.0197 (17)	0.035 (2)	0.0109 (15)
C11	0.115 (3)	0.0557 (19)	0.090 (3)	0.051 (2)	0.064 (2)	0.0407 (19)
C12	0.081 (2)	0.075 (2)	0.070 (2)	0.0506 (18)	0.0323 (18)	0.0418 (18)
C13	0.0607 (19)	0.0509 (16)	0.0500 (16)	0.0285 (14)	0.0162 (14)	0.0193 (13)
C14	0.0420 (16)	0.0412 (14)	0.0412 (13)	0.0183 (11)	0.0123 (12)	0.0180 (11)
C15	0.0409 (16)	0.0458 (14)	0.0432 (14)	0.0199 (12)	0.0134 (12)	0.0192 (12)
C16	0.0442 (16)	0.0451 (14)	0.0437 (14)	0.0185 (12)	0.0134 (12)	0.0172 (12)
C17	0.068 (2)	0.0565 (17)	0.074 (2)	0.0273 (15)	0.0325 (16)	0.0370 (15)
C18	0.0486 (17)	0.0429 (14)	0.0420 (14)	0.0238 (12)	0.0143 (12)	0.0140 (11)
C19	0.063 (2)	0.0514 (17)	0.071 (2)	0.0299 (15)	0.0297 (16)	0.0271 (15)
C20	0.090 (3)	0.0549 (18)	0.084 (2)	0.0412 (18)	0.044 (2)	0.0351 (16)
C21	0.085 (3)	0.069 (2)	0.065 (2)	0.0523 (19)	0.0249 (18)	0.0240 (16)
C22	0.052 (2)	0.072 (2)	0.0669 (19)	0.0360 (17)	0.0168 (15)	0.0136 (16)
C23	0.0482 (18)	0.0525 (16)	0.0617 (18)	0.0201 (13)	0.0164 (14)	0.0139 (14)

Cl1—C1	1.737 (3)	C10—C11	1.370 (5)
O1—C15	1.244 (3)	C10—H10	0.9300
N1—C7	1.337 (3)	C11—C12	1.379 (5)
N1—C4	1.426 (3)	C11—H11	0.9300
N1—H1	0.93 (3)	C12—C13	1.381 (4)
N2—C15	1.374 (3)	C12—H12	0.9300
N2—N3	1.403 (3)	C13—H13	0.9300
N2—C18	1.419 (3)	C14—C16	1.431 (4)
N3—C16	1.311 (3)	C14—C15	1.448 (3)
C1—C2	1.369 (4)	C16—C17	1.496 (4)
C1—C6	1.379 (4)	C17—H17A	0.9600
C2—C3	1.383 (4)	C17—H17B	0.9600
C2—H2	0.9300	C17—H17C	0.9600
C3—C4	1.382 (4)	C18—C19	1.380 (4)
C3—H3	0.9300	C18—C23	1.380 (4)
C4—C5	1.382 (4)	C19—C20	1.386 (4)
C5—C6	1.377 (4)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.366 (5)
C6—H6	0.9300	C20—H20	0.9300
C7—C14	1.393 (3)	C21—C22	1.372 (4)
C7—C8	1.491 (3)	C21—H21	0.9300
C8—C13	1.378 (4)	C22—C23	1.377 (4)
C8—C9	1.389 (4)	C22—H22	0.9300
C9—C10	1.376 (4)	C23—H23	0.9300
C9—H9	0.9300
C7—N1—C4	128.4 (2)	C11—C12—C13	120.0 (3)
C7—N1—H1	110.4 (18)	C11—C12—H12	120.0
C4—N1—H1	121.2 (18)	C13—C12—H12	120.0
C15—N2—N3	112.28 (19)	C8—C13—C12	119.9 (3)
C15—N2—C18	127.5 (2)	C8—C13—H13	120.0
N3—N2—C18	119.5 (2)	C12—C13—H13	120.0
C16—N3—N2	106.1 (2)	C7—C14—C16	132.6 (2)
C2—C1—C6	121.1 (3)	C7—C14—C15	121.7 (2)
C2—C1—Cl1	119.7 (2)	C16—C14—C15	105.3 (2)
C6—C1—Cl1	119.2 (2)	O1—C15—N2	126.0 (2)
C1—C2—C3	118.9 (3)	O1—C15—C14	129.5 (2)
C1—C2—H2	120.6	N2—C15—C14	104.4 (2)
C3—C2—H2	120.6	N3—C16—C14	111.7 (2)
C4—C3—C2	120.8 (3)	N3—C16—C17	118.0 (2)
C4—C3—H3	119.6	C14—C16—C17	130.3 (2)
C2—C3—H3	119.6	C16—C17—H17A	109.5
C5—C4—C3	119.6 (2)	C16—C17—H17B	109.5
C5—C4—N1	121.8 (2)	H17A—C17—H17B	109.5
C3—C4—N1	118.6 (2)	C16—C17—H17C	109.5
C6—C5—C4	119.8 (3)	H17A—C17—H17C	109.5
C6—C5—H5	120.1	H17B—C17—H17C	109.5
C4—C5—H5	120.1	C19—C18—C23	120.3 (2)
C5—C6—C1	119.9 (3)	C19—C18—N2	119.2 (2)
C5—C6—H6	120.1	C23—C18—N2	120.5 (2)
C1—C6—H6	120.1	C18—C19—C20	119.2 (3)
N1—C7—C14	118.9 (2)	C18—C19—H19	120.4
N1—C7—C8	118.6 (2)	C20—C19—H19	120.4
C14—C7—C8	122.4 (2)	C21—C20—C19	120.7 (3)
C13—C8—C9	119.8 (2)	C21—C20—H20	119.7
C13—C8—C7	121.4 (2)	C19—C20—H20	119.7
C9—C8—C7	118.8 (2)	C20—C21—C22	119.6 (3)
C10—C9—C8	119.7 (3)	C20—C21—H21	120.2
C10—C9—H9	120.2	C22—C21—H21	120.2
C8—C9—H9	120.2	C21—C22—C23	120.9 (3)
C11—C10—C9	120.5 (3)	C21—C22—H22	119.5
C11—C10—H10	119.8	C23—C22—H22	119.5
C9—C10—H10	119.8	C22—C23—C18	119.3 (3)
C10—C11—C12	120.0 (3)	C22—C23—H23	120.4
C10—C11—H11	120.0	C18—C23—H23	120.4
C12—C11—H11	120.0

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.93 (3)	1.87 (3)	2.701 (3)	146 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.93 (3)	1.87 (3)	2.701 (3)	146 (2)