4-[(Z)-(4-Ethoxy­phenyl­amino)(phen­yl)­methyl­ene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Ma, R.; Chen, Y.; Song, Z.-Y.; Bai, Y.-Q.; Bao, F.

doi:10.1107/S1600536807026992

4-[(Z)-(4-Ethoxyphenylamino)(phenyl)methylene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

R. Ma, Y. Chen, Z.-Y. Song, Y.-Q. Bai and F. Bao

The structure of the title compound, C₂₅H₂₃N₃O₂, features a central pyrazole ring; an amine NH unit interacts with the ring CO unit through an intramolecular N—H

O hydrogen bond [N

O = 2.700 (2) Å]

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026992/hb2438sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026992/hb2438Isup2.hkl Contains datablock I

CCDC reference: 654915

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.004 Å
R factor = 0.053
wR factor = 0.211
Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      0.695
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C10

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

This study is a continuation of our investigations of 4-(Z)- [(4-ethoxyphenylamino)(phenyl)methylene]-3-methyl- 1-phenyl-1H-pyrazol-5(4H)-ones, which are readily synthesized by condensing 4-benzoyl-3-methyl-1- phenyl-5-pyrazolone with a primary amine (Bao, Lü, Wu, Kang & Ng, 2004; Bao, Lü, Wu, & Ng, 2004; Jiang et al., 2004). A characteristic of such pyrazolones is the short intramolecular hydrogen bond between the amino NH unit and the carbonyl C=O unit.

The title compound, (I), (Fig. 1), similarly exists as a monomeric molecule that features an intramolecular N—H···O hydrogen bond (Table 1) despite the presence of possible acceptor atoms in nearby molecules.

Related literature top

For related structures, see: Bao, Lü, Wu, Kang & Ng (2004); Bao, Lü, Wu, & Ng (2004); Jiang et al. (2004).

For related literature, see: Bao et al. (2006).

Experimental top

4-Benzoyl-3-methyl-1-phenyl-5-pyrazolone (1.20 g, 4.3 mmol) and 4-ethoxybenzenamine (0.62 g, 6.5 mmol) were dissolved in ethyl alcohol (20 ml). The solution was heated under reflux for 8 h. The solvent was removed and the pure product obtained upon recrystallization from ethyl alcohol (25 ml) in about 80% yield. Crystals of (I) were grown from ethanol at room temperature. Analysis calculated for C₂₅H₂₃N₃O₂: C 75.55, H 5.83, N 10.57%; found: C 75.52, H 5.85, N 10.58%.

Structure description top

For related structures, see: Bao, Lü, Wu, Kang & Ng (2004); Bao, Lü, Wu, & Ng (2004); Jiang et al. (2004).

For related literature, see: Bao et al. (2006).

Computing details top

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

Figures top

Fig. 1. Vew of (I), with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius and the hydrogen bond is indicated by a double-dashed line.

4-[(Z)-(4-Ethoxyphenylamino)(phenyl)methylene]-3-methyl-1-phenyl- 1H-pyrazol-5(4H)-one top

Crystal data top

C₂₅H₂₃N₃O₂	Z = 2
M_r = 397.46	F(000) = 420
Triclinic, P1	D_x = 1.225 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9269 (9) Å	Cell parameters from 1701 reflections
b = 10.7876 (14) Å	θ = 2.8–23.3°
c = 15.531 (2) Å	µ = 0.08 mm⁻¹
α = 71.966 (2)°	T = 293 K
β = 78.994 (2)°	Block, yellow
γ = 81.296 (3)°	0.30 × 0.20 × 0.20 mm
V = 1077.9 (2) Å³

Data collection top

Bruker SMART CCD diffractometer	2518 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.059
Graphite monochromator	θ_max = 27.0°, θ_min = 2.0°
ω scans	h = −6→8
8649 measured reflections	k = −12→13
4588 independent reflections	l = −19→19

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.211	H-atom parameters constrained
S = 0.70	w = 1/[σ²(F_o²) + (0.1794P)²] where P = (F_o² + 2F_c²)/3
4588 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₅H₂₃N₃O₂	γ = 81.296 (3)°
M_r = 397.46	V = 1077.9 (2) Å³
Triclinic, P1	Z = 2
a = 6.9269 (9) Å	Mo Kα radiation
b = 10.7876 (14) Å	µ = 0.08 mm⁻¹
c = 15.531 (2) Å	T = 293 K
α = 71.966 (2)°	0.30 × 0.20 × 0.20 mm
β = 78.994 (2)°

Data collection top

Bruker SMART CCD diffractometer	2518 reflections with I > 2σ(I)
8649 measured reflections	R_int = 0.059
4588 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.211	H-atom parameters constrained
S = 0.70	Δρ_max = 0.16 e Å⁻³
4588 reflections	Δρ_min = −0.17 e Å⁻³
271 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
O2	0.3867 (2)	0.78662 (17)	0.05284 (11)	0.0580 (5)
N1	1.2631 (3)	1.14403 (18)	0.30935 (12)	0.0503 (5)
O1	1.1023 (2)	1.17814 (16)	0.18320 (10)	0.0597 (5)
N3	0.9036 (3)	0.9699 (2)	0.20785 (13)	0.0552 (5)
H3A	0.9570	1.0391	0.1736	0.066*
N2	1.2852 (3)	1.04592 (18)	0.39146 (12)	0.0517 (5)
C11	0.9511 (3)	0.9213 (2)	0.29198 (15)	0.0461 (5)
C21	0.5236 (3)	0.8295 (2)	0.08632 (14)	0.0483 (5)
C7	1.1391 (3)	1.1128 (2)	0.26106 (14)	0.0479 (5)
C18	0.7734 (3)	0.9196 (2)	0.16823 (15)	0.0499 (6)
C9	1.1726 (3)	0.9562 (2)	0.39721 (14)	0.0468 (5)
C8	1.0718 (3)	0.9901 (2)	0.31896 (14)	0.0450 (5)
C12	0.8815 (3)	0.7945 (2)	0.35031 (15)	0.0466 (5)
C1	1.3747 (3)	1.2522 (2)	0.28323 (15)	0.0495 (6)
C19	0.5790 (4)	0.9105 (3)	0.20650 (17)	0.0622 (7)
H19A	0.5305	0.9350	0.2596	0.075*
C23	0.8423 (4)	0.8833 (3)	0.08965 (15)	0.0612 (7)
H23A	0.9745	0.8891	0.0639	0.073*
C13	0.9534 (4)	0.6814 (2)	0.32642 (18)	0.0598 (6)
H13A	1.0421	0.6854	0.2727	0.072*
C20	0.4556 (4)	0.8647 (3)	0.16570 (17)	0.0620 (7)
H20A	0.3240	0.8575	0.1923	0.074*
C6	1.5599 (4)	1.2363 (3)	0.30841 (17)	0.0605 (7)
H6A	1.6127	1.1539	0.3400	0.073*
C2	1.2973 (4)	1.3750 (2)	0.23493 (17)	0.0613 (7)
H2B	1.1738	1.3858	0.2169	0.074*
C17	0.7493 (4)	0.7871 (2)	0.43025 (16)	0.0596 (6)
H17A	0.7010	0.8625	0.4476	0.072*
C22	0.7190 (4)	0.8383 (3)	0.04823 (15)	0.0601 (7)
H22A	0.7678	0.8142	−0.0050	0.072*
C10	1.1678 (4)	0.8376 (2)	0.47893 (16)	0.0621 (7)
H10A	1.2523	0.8450	0.5191	0.093*
H10B	1.2130	0.7607	0.4592	0.093*
H10C	1.0349	0.8311	0.5109	0.093*
C5	1.6661 (5)	1.3433 (3)	0.28646 (19)	0.0718 (8)
H5A	1.7907	1.3326	0.3034	0.086*
C4	1.5899 (5)	1.4647 (3)	0.24021 (19)	0.0771 (9)
H4A	1.6619	1.5363	0.2264	0.092*
C3	1.4055 (5)	1.4812 (3)	0.21387 (19)	0.0721 (8)
H3B	1.3542	1.5639	0.1819	0.087*
C24	0.4498 (4)	0.7369 (3)	−0.02403 (17)	0.0701 (8)
H24A	0.5562	0.6673	−0.0116	0.084*
H24B	0.4972	0.8059	−0.0776	0.084*
C14	0.8941 (5)	0.5630 (3)	0.3818 (2)	0.0745 (8)
H14A	0.9448	0.4867	0.3661	0.089*
C15	0.7607 (5)	0.5564 (3)	0.4602 (2)	0.0754 (8)
H15A	0.7192	0.4761	0.4970	0.090*
C16	0.6894 (4)	0.6674 (3)	0.48406 (19)	0.0707 (8)
H16A	0.5991	0.6627	0.5374	0.085*
C25	0.2757 (5)	0.6857 (4)	−0.0402 (2)	0.0918 (10)
H25A	0.3131	0.6512	−0.0918	0.138*
H25B	0.1716	0.7554	−0.0525	0.138*
H25C	0.2303	0.6174	0.0132	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0545 (10)	0.0692 (11)	0.0609 (9)	−0.0116 (8)	−0.0103 (8)	−0.0308 (8)
N1	0.0543 (12)	0.0474 (11)	0.0531 (10)	−0.0130 (9)	−0.0112 (9)	−0.0144 (8)
O1	0.0629 (11)	0.0623 (11)	0.0537 (9)	−0.0193 (8)	−0.0154 (8)	−0.0067 (8)
N3	0.0542 (12)	0.0586 (12)	0.0565 (11)	−0.0221 (10)	−0.0102 (9)	−0.0131 (9)
N2	0.0566 (12)	0.0513 (11)	0.0506 (10)	−0.0098 (9)	−0.0113 (9)	−0.0158 (9)
C11	0.0391 (12)	0.0491 (13)	0.0529 (12)	−0.0018 (10)	−0.0039 (9)	−0.0218 (10)
C21	0.0471 (13)	0.0517 (13)	0.0501 (12)	−0.0086 (10)	−0.0095 (10)	−0.0173 (10)
C7	0.0433 (13)	0.0527 (13)	0.0517 (12)	−0.0068 (10)	−0.0045 (10)	−0.0215 (10)
C18	0.0485 (14)	0.0504 (13)	0.0534 (12)	−0.0111 (11)	−0.0123 (10)	−0.0132 (10)
C9	0.0448 (13)	0.0470 (13)	0.0512 (12)	−0.0050 (10)	−0.0044 (10)	−0.0198 (10)
C8	0.0424 (12)	0.0441 (12)	0.0517 (12)	−0.0063 (10)	−0.0050 (9)	−0.0189 (10)
C12	0.0414 (12)	0.0460 (13)	0.0570 (12)	−0.0050 (10)	−0.0101 (10)	−0.0197 (10)
C1	0.0530 (14)	0.0473 (13)	0.0531 (12)	−0.0128 (11)	−0.0025 (10)	−0.0213 (10)
C19	0.0503 (15)	0.0804 (18)	0.0705 (15)	−0.0101 (13)	−0.0020 (12)	−0.0454 (14)
C23	0.0470 (14)	0.0873 (19)	0.0517 (13)	−0.0215 (13)	−0.0002 (11)	−0.0209 (12)
C13	0.0584 (16)	0.0558 (15)	0.0727 (15)	−0.0070 (12)	−0.0074 (12)	−0.0305 (13)
C20	0.0422 (13)	0.0809 (18)	0.0745 (16)	−0.0096 (12)	0.0002 (11)	−0.0430 (14)
C6	0.0614 (16)	0.0618 (16)	0.0677 (15)	−0.0135 (13)	−0.0154 (12)	−0.0254 (12)
C2	0.0619 (16)	0.0531 (15)	0.0706 (15)	−0.0126 (13)	−0.0072 (12)	−0.0187 (12)
C17	0.0558 (15)	0.0541 (15)	0.0683 (15)	−0.0092 (12)	0.0025 (12)	−0.0221 (12)
C22	0.0552 (15)	0.0810 (18)	0.0462 (12)	−0.0155 (13)	0.0017 (11)	−0.0230 (12)
C10	0.0669 (17)	0.0562 (15)	0.0618 (14)	−0.0110 (13)	−0.0139 (12)	−0.0104 (12)
C5	0.0719 (18)	0.078 (2)	0.0764 (17)	−0.0316 (16)	−0.0116 (14)	−0.0269 (15)
C4	0.093 (2)	0.072 (2)	0.0765 (18)	−0.0439 (17)	−0.0014 (16)	−0.0270 (16)
C3	0.085 (2)	0.0532 (16)	0.0747 (17)	−0.0200 (15)	−0.0042 (15)	−0.0128 (13)
C24	0.0717 (18)	0.093 (2)	0.0563 (14)	−0.0117 (15)	−0.0104 (13)	−0.0342 (14)
C14	0.084 (2)	0.0499 (16)	0.102 (2)	−0.0068 (14)	−0.0240 (18)	−0.0336 (15)
C15	0.075 (2)	0.0558 (17)	0.093 (2)	−0.0218 (15)	−0.0171 (17)	−0.0084 (15)
C16	0.0628 (17)	0.0667 (19)	0.0743 (17)	−0.0174 (14)	0.0019 (13)	−0.0105 (14)
C25	0.088 (2)	0.129 (3)	0.088 (2)	−0.014 (2)	−0.0289 (17)	−0.062 (2)

Geometric parameters (Å, º) top

O2—C21	1.361 (3)	C13—H13A	0.9300
O2—C24	1.425 (3)	C20—H20A	0.9300
N1—C7	1.380 (3)	C6—C5	1.381 (4)
N1—N2	1.400 (2)	C6—H6A	0.9300
N1—C1	1.409 (3)	C2—C3	1.384 (4)
O1—C7	1.249 (3)	C2—H2B	0.9300
N3—C11	1.333 (3)	C17—C16	1.378 (3)
N3—C18	1.433 (3)	C17—H17A	0.9300
N3—H3A	0.8600	C22—H22A	0.9300
N2—C9	1.305 (3)	C10—H10A	0.9600
C11—C8	1.392 (3)	C10—H10B	0.9600
C11—C12	1.480 (3)	C10—H10C	0.9600
C21—C22	1.375 (3)	C5—C4	1.364 (4)
C21—C20	1.378 (3)	C5—H5A	0.9300
C7—C8	1.438 (3)	C4—C3	1.384 (4)
C18—C19	1.369 (3)	C4—H4A	0.9300
C18—C23	1.374 (3)	C3—H3B	0.9300
C9—C8	1.439 (3)	C24—C25	1.492 (4)
C9—C10	1.496 (3)	C24—H24A	0.9700
C12—C13	1.378 (3)	C24—H24B	0.9700
C12—C17	1.383 (3)	C14—C15	1.371 (4)
C1—C6	1.382 (3)	C14—H14A	0.9300
C1—C2	1.389 (3)	C15—C16	1.357 (4)
C19—C20	1.380 (3)	C15—H15A	0.9300
C19—H19A	0.9300	C16—H16A	0.9300
C23—C22	1.381 (3)	C25—H25A	0.9600
C23—H23A	0.9300	C25—H25B	0.9600
C13—C14	1.373 (4)	C25—H25C	0.9600

C21—O2—C24	118.67 (19)	C1—C6—H6A	120.1
C7—N1—N2	111.88 (18)	C3—C2—C1	119.4 (3)
C7—N1—C1	128.75 (19)	C3—C2—H2B	120.3
N2—N1—C1	119.18 (18)	C1—C2—H2B	120.3
C11—N3—C18	127.2 (2)	C16—C17—C12	119.6 (2)
C11—N3—H3A	116.4	C16—C17—H17A	120.2
C18—N3—H3A	116.4	C12—C17—H17A	120.2
C9—N2—N1	106.65 (17)	C21—C22—C23	119.4 (2)
N3—C11—C8	118.0 (2)	C21—C22—H22A	120.3
N3—C11—C12	118.73 (19)	C23—C22—H22A	120.3
C8—C11—C12	123.23 (19)	C9—C10—H10A	109.5
O2—C21—C22	125.5 (2)	C9—C10—H10B	109.5
O2—C21—C20	115.4 (2)	H10A—C10—H10B	109.5
C22—C21—C20	119.1 (2)	C9—C10—H10C	109.5
O1—C7—N1	125.8 (2)	H10A—C10—H10C	109.5
O1—C7—C8	129.6 (2)	H10B—C10—H10C	109.5
N1—C7—C8	104.61 (18)	C4—C5—C6	120.6 (3)
C19—C18—C23	119.4 (2)	C4—C5—H5A	119.7
C19—C18—N3	120.7 (2)	C6—C5—H5A	119.7
C23—C18—N3	119.9 (2)	C5—C4—C3	120.1 (3)
N2—C9—C8	111.37 (19)	C5—C4—H4A	120.0
N2—C9—C10	118.4 (2)	C3—C4—H4A	120.0
C8—C9—C10	130.2 (2)	C4—C3—C2	120.1 (3)
C11—C8—C7	122.44 (19)	C4—C3—H3B	119.9
C11—C8—C9	131.8 (2)	C2—C3—H3B	119.9
C7—C8—C9	105.41 (19)	O2—C24—C25	107.2 (2)
C13—C12—C17	119.3 (2)	O2—C24—H24A	110.3
C13—C12—C11	119.8 (2)	C25—C24—H24A	110.3
C17—C12—C11	120.8 (2)	O2—C24—H24B	110.3
C6—C1—C2	120.1 (2)	C25—C24—H24B	110.3
C6—C1—N1	119.5 (2)	H24A—C24—H24B	108.5
C2—C1—N1	120.4 (2)	C15—C14—C13	120.4 (3)
C18—C19—C20	119.5 (2)	C15—C14—H14A	119.8
C18—C19—H19A	120.3	C13—C14—H14A	119.8
C20—C19—H19A	120.3	C16—C15—C14	119.8 (3)
C18—C23—C22	121.3 (2)	C16—C15—H15A	120.1
C18—C23—H23A	119.4	C14—C15—H15A	120.1
C22—C23—H23A	119.4	C15—C16—C17	120.8 (3)
C14—C13—C12	120.0 (2)	C15—C16—H16A	119.6
C14—C13—H13A	120.0	C17—C16—H16A	119.6
C12—C13—H13A	120.0	C24—C25—H25A	109.5
C21—C20—C19	121.3 (2)	C24—C25—H25B	109.5
C21—C20—H20A	119.4	H25A—C25—H25B	109.5
C19—C20—H20A	119.4	C24—C25—H25C	109.5
C5—C6—C1	119.7 (3)	H25A—C25—H25C	109.5
C5—C6—H6A	120.1	H25B—C25—H25C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86	1.98	2.700 (3)	140

Experimental details

Crystal data
Chemical formula	C₂₅H₂₃N₃O₂
M_r	397.46
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.9269 (9), 10.7876 (14), 15.531 (2)
α, β, γ (°)	71.966 (2), 78.994 (2), 81.296 (3)
V (Å³)	1077.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8649, 4588, 2518
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.211, 0.70
No. of reflections	4588
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17

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