3-Methyl-1-phenyl-4-[(Z)-phenyl(p-tolyl­amino)­methyl­ene]-1H-pyrazol-5(4H)-one

The NH unit on the exocyclic C=C double bond in the title compound, C₂₄H₂₁N₃O, which is on the same side of the double bond as the C=O unit of the pyrazolone ring, inter­acts with the carbonyl group through an intra­molecular N—H...O hydrogen bond [2.685 (2) Å].

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.040
• wR factor = 0.121
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT155_ALERT_4_C The Triclinic Unitcell is NOT Reduced ..........          ?

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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

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S1. Comment

5-Methyl-2-phenyl-4-[(Z)-(2-tolylamino)phenylmethylene]pyrazol-3(2H)-one exists as a monomeric compound whose NH unit is linked to the C═O unit by a short [2.695 (2) Å] hydrogen bond (Bao et al., 2004). The isomeric title compound, (I) (Fig. 1), displays a somewhat shorter hydrogen bond [2.685 (2) Å]; otherwise, there are no significant differences between the two isomers. The two hydrogen bonds are slightly shorter than that found in 4-[(phenyl)phenylmethylene]-5-methyl-2-phenyl-2H-pyrazol-3-one [2.704 (2) Å; Ma, 2005].

S2. Experimental

1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone (2.50 g, 9.0 mmol) and 4-aminotoluene (0.96 ml, 9.4 mmol) were dissolved in ethanol (35 ml) and the solution was refluxed for 6 h. The solvent was removed and the pure product was obtained upon recrystallization from a 1:1 ethanol/n-heptane mixture (35 ml) in about 75% yield. Crystals were grown from an ethanol solution. CHN elemental analysis calculated for C₂₄H₂₁N₃O: C 78.45, H 5.76, N 11.44%; found: C 78.37, H 5.42, N 11.61%.

S3. Refinement

The C-bound H atoms were positioned geometrically [C—H_aromatic = 0.93 Å and Uiso(H) = 1.2U_eq(C); C—H_methyl = 0.96 Å and U_iso(H) = 1.5U_eq(C)], and were included in the refinement in the riding model approximation; the methyl groups were rotated for a best fit with the electron density. The N-bound H atom was located in a difference Fourier map and was refined with a distance restraint of N—H = 0.86 (1) Å. The dispalcement parameter of this H atom was also refined.

Computing details

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

Figures

Fig. 1. ORTEP (Bruker, 1999) plot showing the numbering scheme of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary radii.

5-Methyl-2-phenyl-4-[(Z)-4-(tolylamino)phenylmethylene]pyrazol-3(2H)-one

Crystal data

C24H21N3O	Z = 2
Mr = 367.44	F(000) = 388
Triclinic, P1	Dx = 1.245 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4272 (10) Å	Cell parameters from 892 reflections
b = 11.0766 (14) Å	θ = 2.1–26.1°
c = 13.6124 (17) Å	µ = 0.08 mm^−1
α = 110.095 (2)°	T = 295 K
β = 99.798 (2)°	Block, yellow
γ = 104.067 (2)°	0.50 × 0.45 × 0.27 mm
V = 979.8 (2) Å^3

Data collection

Bruker SMART area-detector diffractometer	2816 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.013
Graphite monochromator	θmax = 26.1°, θmin = 2.1°
ω scans	h = −9→9
5537 measured reflections	k = −10→13
3811 independent reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0638P)^2 + 0.1375P] where P = (Fo^2 + 2Fc^2)/3
3811 reflections	(Δ/σ)max = 0.001
259 parameters	Δρmax = 0.17 e Å^−3
1 restraint	Δρmin = −0.15 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.49606 (16)	1.12709 (11)	0.23819 (9)	0.0563 (3)
N1	0.30856 (18)	1.09773 (12)	0.35506 (10)	0.0481 (3)
N2	0.24519 (19)	1.00079 (13)	0.39655 (10)	0.0512 (3)
N3	0.63223 (19)	0.91817 (13)	0.17181 (10)	0.0520 (3)
H3N	0.611 (3)	0.9941 (13)	0.1732 (14)	0.070 (5)*
C1	0.0413 (2)	1.18365 (17)	0.37729 (13)	0.0580 (4)
H1	−0.0309	1.1015	0.3761	0.070*
C2	−0.0367 (3)	1.2871 (2)	0.38764 (14)	0.0679 (5)
H2	−0.1626	1.2742	0.3929	0.081*
C3	0.0701 (3)	1.4088 (2)	0.39029 (14)	0.0683 (5)
H3	0.0166	1.4779	0.3970	0.082*
C4	0.2547 (3)	1.42792 (18)	0.38312 (15)	0.0689 (5)
H4	0.3270	1.5104	0.3850	0.083*
C5	0.3355 (3)	1.32616 (16)	0.37305 (14)	0.0587 (4)
H5	0.4623	1.3405	0.3692	0.070*
C6	0.2282 (2)	1.20374 (15)	0.36873 (11)	0.0470 (4)
C7	0.4280 (2)	1.06380 (15)	0.29099 (12)	0.0453 (3)
C8	0.4487 (2)	0.94046 (14)	0.29704 (11)	0.0443 (3)
C9	0.3285 (2)	0.90911 (15)	0.36307 (11)	0.0472 (3)
C10	0.2844 (3)	0.79083 (18)	0.39412 (15)	0.0635 (4)
H10A	0.1874	0.7952	0.4325	0.095*
H10B	0.3996	0.7932	0.4402	0.095*
H10C	0.2378	0.7079	0.3297	0.095*
C11	0.5529 (2)	0.86998 (14)	0.23734 (11)	0.0440 (3)
C12	0.5688 (2)	0.73938 (14)	0.23876 (11)	0.0459 (3)
C13	0.6766 (2)	0.73512 (16)	0.33028 (13)	0.0544 (4)
H13	0.7367	0.8142	0.3933	0.065*
C14	0.6945 (3)	0.61309 (19)	0.32770 (15)	0.0662 (5)
H14	0.7676	0.6100	0.3889	0.079*
C15	0.6043 (3)	0.49575 (18)	0.23468 (16)	0.0707 (5)
H15	0.6183	0.4139	0.2329	0.085*
C16	0.4942 (3)	0.49955 (17)	0.14488 (15)	0.0685 (5)
H16	0.4308	0.4198	0.0829	0.082*
C17	0.4773 (2)	0.62065 (16)	0.14615 (13)	0.0561 (4)
H17	0.4040	0.6230	0.0846	0.067*
C18	0.7540 (2)	0.87058 (14)	0.10822 (12)	0.0479 (4)
C19	0.8978 (2)	0.82606 (18)	0.14621 (13)	0.0594 (4)
H19	0.9173	0.8249	0.2152	0.071*
C20	1.0127 (2)	0.78317 (19)	0.08117 (14)	0.0634 (5)
H20	1.1072	0.7509	0.1066	0.076*
C21	0.9915 (2)	0.78670 (17)	−0.02061 (13)	0.0589 (4)
C22	0.8504 (3)	0.83445 (17)	−0.05586 (13)	0.0601 (4)
H22	0.8346	0.8391	−0.1236	0.072*
C23	0.7315 (2)	0.87566 (16)	0.00680 (13)	0.0530 (4)
H23	0.6360	0.9069	−0.0191	0.064*
C24	1.1209 (3)	0.7397 (3)	−0.08927 (18)	0.0919 (7)
H24A	1.0833	0.6423	−0.1184	0.138*
H24B	1.2526	0.7779	−0.0451	0.138*
H24C	1.1090	0.7691	−0.1480	0.138*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0640 (7)	0.0570 (6)	0.0666 (7)	0.0297 (5)	0.0309 (6)	0.0338 (6)
N1	0.0552 (7)	0.0450 (7)	0.0530 (7)	0.0243 (6)	0.0221 (6)	0.0212 (6)
N2	0.0585 (8)	0.0498 (7)	0.0519 (7)	0.0222 (6)	0.0214 (6)	0.0222 (6)
N3	0.0606 (8)	0.0525 (8)	0.0539 (7)	0.0294 (7)	0.0240 (6)	0.0231 (6)
C1	0.0541 (10)	0.0537 (9)	0.0603 (10)	0.0203 (8)	0.0172 (8)	0.0137 (8)
C2	0.0594 (10)	0.0784 (13)	0.0661 (11)	0.0385 (10)	0.0188 (9)	0.0175 (9)
C3	0.0912 (14)	0.0688 (12)	0.0622 (10)	0.0531 (11)	0.0278 (10)	0.0251 (9)
C4	0.0909 (14)	0.0550 (10)	0.0794 (12)	0.0389 (10)	0.0384 (11)	0.0315 (9)
C5	0.0641 (10)	0.0537 (9)	0.0682 (11)	0.0288 (8)	0.0278 (9)	0.0253 (8)
C6	0.0543 (9)	0.0455 (8)	0.0417 (7)	0.0235 (7)	0.0134 (7)	0.0130 (6)
C7	0.0465 (8)	0.0451 (8)	0.0446 (8)	0.0183 (6)	0.0127 (6)	0.0163 (6)
C8	0.0481 (8)	0.0420 (8)	0.0429 (7)	0.0193 (6)	0.0110 (6)	0.0151 (6)
C9	0.0520 (9)	0.0456 (8)	0.0434 (8)	0.0184 (7)	0.0125 (7)	0.0161 (6)
C10	0.0748 (12)	0.0592 (10)	0.0731 (11)	0.0294 (9)	0.0317 (9)	0.0358 (9)
C11	0.0450 (8)	0.0438 (8)	0.0388 (7)	0.0167 (6)	0.0070 (6)	0.0122 (6)
C12	0.0487 (8)	0.0442 (8)	0.0467 (8)	0.0206 (7)	0.0164 (7)	0.0153 (6)
C13	0.0626 (10)	0.0543 (9)	0.0489 (8)	0.0280 (8)	0.0147 (7)	0.0180 (7)
C14	0.0831 (13)	0.0764 (12)	0.0668 (11)	0.0493 (10)	0.0321 (10)	0.0399 (10)
C15	0.1013 (15)	0.0548 (10)	0.0842 (13)	0.0440 (10)	0.0533 (12)	0.0354 (10)
C16	0.0928 (14)	0.0427 (9)	0.0646 (11)	0.0198 (9)	0.0331 (10)	0.0116 (8)
C17	0.0623 (10)	0.0503 (9)	0.0483 (9)	0.0170 (8)	0.0141 (7)	0.0129 (7)
C18	0.0496 (9)	0.0430 (8)	0.0466 (8)	0.0148 (7)	0.0142 (7)	0.0127 (6)
C19	0.0546 (10)	0.0800 (12)	0.0439 (8)	0.0287 (9)	0.0127 (7)	0.0210 (8)
C20	0.0520 (10)	0.0806 (12)	0.0556 (10)	0.0303 (9)	0.0130 (8)	0.0201 (9)
C21	0.0515 (9)	0.0625 (10)	0.0502 (9)	0.0155 (8)	0.0158 (7)	0.0096 (8)
C22	0.0642 (11)	0.0679 (11)	0.0461 (9)	0.0170 (9)	0.0187 (8)	0.0220 (8)
C23	0.0544 (9)	0.0530 (9)	0.0548 (9)	0.0188 (7)	0.0155 (7)	0.0243 (7)
C24	0.0848 (15)	0.1216 (19)	0.0731 (13)	0.0455 (13)	0.0412 (12)	0.0265 (13)

Geometric parameters (Å, º)

O1—C7	1.2496 (17)	C11—C12	1.486 (2)
N1—C7	1.3741 (18)	C12—C13	1.384 (2)
N1—N2	1.3983 (17)	C12—C17	1.384 (2)
N1—C6	1.4137 (18)	C13—C14	1.379 (2)
N2—C9	1.3057 (18)	C13—H13	0.9300
N3—C11	1.3345 (19)	C14—C15	1.378 (3)
N3—C18	1.4246 (19)	C14—H14	0.9300
N3—H3N	0.886 (9)	C15—C16	1.370 (3)
C1—C6	1.382 (2)	C15—H15	0.9300
C1—C2	1.381 (2)	C16—C17	1.372 (2)
C1—H1	0.9300	C16—H16	0.9300
C2—C3	1.373 (3)	C17—H17	0.9300
C2—H2	0.9300	C18—C19	1.377 (2)
C3—C4	1.361 (3)	C18—C23	1.384 (2)
C3—H3	0.9300	C19—C20	1.379 (2)
C4—C5	1.378 (2)	C19—H19	0.9300
C4—H4	0.9300	C20—C21	1.383 (2)
C5—C6	1.372 (2)	C20—H20	0.9300
C5—H5	0.9300	C21—C22	1.371 (2)
C7—C8	1.439 (2)	C21—C24	1.511 (2)
C8—C11	1.3933 (19)	C22—C23	1.379 (2)
C8—C9	1.436 (2)	C22—H22	0.9300
C9—C10	1.490 (2)	C23—H23	0.9300
C10—H10A	0.9600	C24—H24A	0.9600
C10—H10B	0.9600	C24—H24B	0.9600
C10—H10C	0.9600	C24—H24C	0.9600
C7—N1—N2	112.07 (11)	C13—C12—C17	119.61 (14)
C7—N1—C6	127.47 (12)	C13—C12—C11	121.08 (13)
N2—N1—C6	119.82 (12)	C17—C12—C11	119.30 (13)
C9—N2—N1	106.55 (12)	C14—C13—C12	119.71 (15)
C11—N3—C18	129.25 (13)	C14—C13—H13	120.1
C11—N3—H3N	113.4 (12)	C12—C13—H13	120.1
C18—N3—H3N	117.1 (12)	C15—C14—C13	120.18 (17)
C6—C1—C2	119.15 (17)	C15—C14—H14	119.9
C6—C1—H1	120.4	C13—C14—H14	119.9
C2—C1—H1	120.4	C16—C15—C14	120.08 (16)
C3—C2—C1	120.55 (17)	C16—C15—H15	120.0
C3—C2—H2	119.7	C14—C15—H15	120.0
C1—C2—H2	119.7	C15—C16—C17	120.20 (16)
C4—C3—C2	119.74 (16)	C15—C16—H16	119.9
C4—C3—H3	120.1	C17—C16—H16	119.9
C2—C3—H3	120.1	C16—C17—C12	120.20 (16)
C3—C4—C5	120.64 (18)	C16—C17—H17	119.9
C3—C4—H4	119.7	C12—C17—H17	119.9
C5—C4—H4	119.7	C19—C18—C23	119.31 (14)
C6—C5—C4	119.76 (17)	C19—C18—N3	122.31 (14)
C6—C5—H5	120.1	C23—C18—N3	118.31 (14)
C4—C5—H5	120.1	C18—C19—C20	119.45 (15)
C5—C6—C1	120.14 (14)	C18—C19—H19	120.3
C5—C6—N1	119.90 (14)	C20—C19—H19	120.3
C1—C6—N1	119.96 (14)	C19—C20—C21	122.01 (16)
O1—C7—N1	125.94 (13)	C19—C20—H20	119.0
O1—C7—C8	129.45 (13)	C21—C20—H20	119.0
N1—C7—C8	104.59 (12)	C22—C21—C20	117.60 (15)
C11—C8—C9	132.52 (13)	C22—C21—C24	121.87 (17)
C11—C8—C7	121.77 (13)	C20—C21—C24	120.53 (17)
C9—C8—C7	105.39 (12)	C21—C22—C23	121.50 (15)
N2—C9—C8	111.33 (13)	C21—C22—H22	119.3
N2—C9—C10	118.34 (14)	C23—C22—H22	119.3
C8—C9—C10	130.31 (14)	C22—C23—C18	120.09 (15)
C9—C10—H10A	109.5	C22—C23—H23	120.0
C9—C10—H10B	109.5	C18—C23—H23	120.0
H10A—C10—H10B	109.5	C21—C24—H24A	109.5
C9—C10—H10C	109.5	C21—C24—H24B	109.5
H10A—C10—H10C	109.5	H24A—C24—H24B	109.5
H10B—C10—H10C	109.5	C21—C24—H24C	109.5
N3—C11—C8	118.41 (13)	H24A—C24—H24C	109.5
N3—C11—C12	118.92 (12)	H24B—C24—H24C	109.5
C8—C11—C12	122.56 (13)
C7—N1—N2—C9	2.34 (16)	C18—N3—C11—C12	−8.0 (2)
C6—N1—N2—C9	173.82 (13)	C9—C8—C11—N3	171.34 (15)
C6—C1—C2—C3	−0.5 (3)	C7—C8—C11—N3	−1.1 (2)
C1—C2—C3—C4	−0.3 (3)	C9—C8—C11—C12	−4.8 (2)
C2—C3—C4—C5	0.1 (3)	C7—C8—C11—C12	−177.26 (13)
C3—C4—C5—C6	0.9 (3)	N3—C11—C12—C13	113.28 (16)
C4—C5—C6—C1	−1.7 (2)	C8—C11—C12—C13	−70.6 (2)
C4—C5—C6—N1	178.06 (15)	N3—C11—C12—C17	−65.4 (2)
C2—C1—C6—C5	1.5 (2)	C8—C11—C12—C17	110.76 (17)
C2—C1—C6—N1	−178.26 (14)	C17—C12—C13—C14	1.1 (2)
C7—N1—C6—C5	−38.0 (2)	C11—C12—C13—C14	−177.57 (15)
N2—N1—C6—C5	151.93 (14)	C12—C13—C14—C15	−0.4 (3)
C7—N1—C6—C1	141.71 (16)	C13—C14—C15—C16	−1.0 (3)
N2—N1—C6—C1	−28.3 (2)	C14—C15—C16—C17	1.7 (3)
N2—N1—C7—O1	175.35 (14)	C15—C16—C17—C12	−1.0 (3)
C6—N1—C7—O1	4.7 (2)	C13—C12—C17—C16	−0.4 (2)
N2—N1—C7—C8	−2.96 (16)	C11—C12—C17—C16	178.32 (15)
C6—N1—C7—C8	−173.64 (13)	C11—N3—C18—C19	−40.0 (2)
O1—C7—C8—C11	−1.6 (2)	C11—N3—C18—C23	143.00 (16)
N1—C7—C8—C11	176.62 (13)	C23—C18—C19—C20	−2.1 (3)
O1—C7—C8—C9	−175.83 (15)	N3—C18—C19—C20	−179.02 (15)
N1—C7—C8—C9	2.39 (15)	C18—C19—C20—C21	1.7 (3)
N1—N2—C9—C8	−0.66 (16)	C19—C20—C21—C22	−0.2 (3)
N1—N2—C9—C10	−179.09 (13)	C19—C20—C21—C24	179.61 (18)
C11—C8—C9—N2	−174.45 (15)	C20—C21—C22—C23	−1.0 (3)
C7—C8—C9—N2	−1.11 (17)	C24—C21—C22—C23	179.24 (17)
C11—C8—C9—C10	3.7 (3)	C21—C22—C23—C18	0.6 (3)
C7—C8—C9—C10	177.08 (16)	C19—C18—C23—C22	1.0 (2)
C18—N3—C11—C8	175.70 (14)	N3—C18—C23—C22	178.03 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1	0.89 (1)	1.91 (1)	2.6845 (16)	144 (2)