4-(2-Hydr­oxy-3-methyl­benzyl­idene­amino)-2,3-dimethyl-1-phenyl-1H-pyrazol-5(2H)-one

Zheng, Y.-F.; Yang, M.-H.

doi:10.1107/S1600536807032060

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4-(2-Hydroxy-3-methylbenzylideneamino)-2,3-dimethyl-1-phenyl-1H-pyrazol-5(2H)-one

Y.-F. Zheng and M.-H. Yang

In the title Schiff base, C₁₉H₁₉N₃O₂, the dihydropyrazole ring is essentially planar, with an r.m.s. deviation of 0.0289 Å for the fitted atoms. This ring makes dihedral angles of 41.8 (2) and 51.1 (3)° with the phenyl and benzene rings, respectively. In the crystal structure, there is one intramolecular O—H

N hydrogen bond.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032060/wn2162sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032060/wn2162Isup2.hkl Contains datablock I

CCDC reference: 657704

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
R factor = 0.033
wR factor = 0.063
Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C12    -   C13     ..       5.52 su
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C11

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

   1 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

Schiff base ligands have significant importance in chemistry, especially in the development of Schiff base complexes, (Johnson et al., 1996; Alizadeh et al., 1999; Wang & Zheng, 2007). Schiff bases that have solvent-dependent UV/vis spectra (solvatochromicity) can be suitable NLO (nonlinear optically active) materials (Alemi & Shaabani, 2000). They are also useful in the asymmetric oxidation of methyl phenyl sulfide and are enantioselective (Kim & Shin, 1999). In this paper, we report the synthesis and crystal structure of the title compound.

The molecular structure of the title compound, C₁₉H₁₉N₃O₂, (Fig. 1), is very similar to the compound, C₁₉H₁₉N₃OS, that was reported recently by Yan and his co-workers (Yan et al., 2007). In the latter, there are intermolecular C—H···O hydrogen bonds, leading to a chain parallel to the a axis. In contrast, the crystal structure of the title compound has only an intramolecular O—H···N hydrogen bond (Table 1).

The C12—N1 bond length is 1.29 (9) Å, indicative of a C═N double bond. The other C—N, C—O and C—C distances show no remarkable features (Cambridge Structural Database, August 2006 version; Allen, 2002; Mogul, version 1.1; Bruno et al., 2004) The dihydropyrazole ring (C7–C9/N2,N3) is essentially planar with an r.m.s. deviation of 0.0289 Å for the fitted atoms; this ring makes a dihedral angle of 41.8 (2)° and 51.1 (3)° with the phenyl and benzene rings, respectively. Bond conjugation is observed in the (N1/C12/C13) sequence of atoms (Jin et al., 2004).

Related literature top

For related literature, see: Alemi & Shaabani (2000); Alizadeh et al. (1999); Allen (2002); Bruno et al. (2004); Jin et al. (2004); Johnson et al. (1996); Kim & Shin (1999); Wang & Zheng (2007); Yan et al. (2007).

Experimental top

Under nitrogen, a mixture of 4-amino-2,3-dimethyl-1-phenyl-1,2-dihydropyrazol-5-one (1.45 g,10 mmol), Na₂SO₄ (3.0 g) and 2-hydroxy-3-methylbenzadehyde (1.60 g, 10 mmol) in absolute ethanol (20 ml) was refluxed for about 12 h to yield a yellow precipitate. The product was collected by vacuum filtration and washed with ethanol. The crude solid was redissolved in CH₂Cl₂ (100 ml) and washed with water (2 x 15 ml) and brine (8 ml). After drying over Na₂SO₄, the solvent was removed under vacuum, and a yellow solid was isolated in 92% yield (3.1 g). Colourless single crystals of the title Schiff base suitable for X-ray analysis were grown from CH₂Cl₂ and absolute ethanol (4:1) by slow evaporation of the solvents at room temperature over a period of about one week.

Structure description top

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); 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, 1998); software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

4-(2-Hydroxy-3-methylbenzylideneamino)-2,3-dimethyl-1-phenyl-1H-pyrazol- 5(2H)-one top

Crystal data top

C₁₉H₁₉N₃O₂	F(000) = 680
M_r = 321.37	D_x = 1.279 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2820 reflections
a = 7.5655 (19) Å	θ = 2.8–25.1°
b = 7.5713 (19) Å	µ = 0.09 mm⁻¹
c = 29.146 (7) Å	T = 298 K
β = 92.006 (4)°	Block, colourless
V = 1668.5 (7) Å³	0.34 × 0.28 × 0.17 mm
Z = 4

Data collection top

Bruker APEX area-detector diffractometer	2820 independent reflections
Radiation source: fine-focus sealed tube	1464 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ and ω scans	θ_max = 25.1°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.972, T_max = 0.986	k = −9→8
9793 measured reflections	l = −32→34

Refinement top

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)] = 0.033	H-atom parameters constrained
wR(F²) = 0.063	w = 1/[σ²(F_o²) + (0.0105P)² + 0.28P] where P = (F_o² + 2F_c²)/3
S = 0.88	(Δ/σ)_max = 0.001
2820 reflections	Δρ_max = 0.14 e Å⁻³
219 parameters	Δρ_min = −0.12 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0221 (6)

Crystal data top

C₁₉H₁₉N₃O₂	V = 1668.5 (7) Å³
M_r = 321.37	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5655 (19) Å	µ = 0.09 mm⁻¹
b = 7.5713 (19) Å	T = 298 K
c = 29.146 (7) Å	0.34 × 0.28 × 0.17 mm
β = 92.006 (4)°

Data collection top

Bruker APEX area-detector diffractometer	2820 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1464 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.986	R_int = 0.039
9793 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.063	H-atom parameters constrained
S = 0.88	Δρ_max = 0.14 e Å⁻³
2820 reflections	Δρ_min = −0.12 e Å⁻³
219 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
O1	1.08050 (14)	0.08844 (16)	0.90981 (4)	0.0604 (4)
N1	0.84312 (18)	0.21964 (18)	0.98889 (5)	0.0519 (4)
O2	0.74420 (14)	0.3600 (2)	1.06511 (4)	0.0747 (4)
H2	0.7338	0.3083	1.0404	0.112*
N3	0.80598 (16)	0.04599 (19)	0.87312 (5)	0.0514 (4)
C7	0.9180 (2)	0.0935 (2)	0.91056 (6)	0.0487 (5)
N2	0.62994 (16)	0.0906 (2)	0.88302 (5)	0.0561 (4)
C9	0.6328 (2)	0.1404 (2)	0.92814 (6)	0.0535 (5)
C8	0.8009 (2)	0.1501 (2)	0.94558 (6)	0.0478 (5)
C17	0.9636 (3)	0.4604 (2)	1.11831 (7)	0.0597 (5)
C13	1.0482 (2)	0.3261 (2)	1.04663 (6)	0.0487 (5)
C12	1.0043 (2)	0.2453 (2)	1.00277 (6)	0.0528 (5)
H14	1.0952	0.2108	0.9841	0.063*
C1	0.7648 (2)	0.1442 (2)	0.79366 (7)	0.0610 (5)
H1	0.6630	0.2052	0.8011	0.073*
C19	0.9186 (2)	0.3813 (2)	1.07651 (6)	0.0534 (5)
C14	1.2249 (2)	0.3531 (2)	1.05965 (7)	0.0616 (5)
H16	1.3127	0.3181	1.0400	0.074*
C6	0.8584 (2)	0.0497 (2)	0.82697 (6)	0.0504 (5)
C15	1.2716 (3)	0.4302 (3)	1.10085 (7)	0.0688 (6)
H17	1.3901	0.4477	1.1092	0.083*
C5	1.0092 (2)	−0.0415 (2)	0.81610 (7)	0.0627 (6)
H5	1.0710	−0.1072	0.8383	0.075*
C16	1.1401 (3)	0.4819 (2)	1.12984 (7)	0.0675 (6)
H18	1.1720	0.5326	1.1580	0.081*
C2	0.8231 (3)	0.1476 (3)	0.74941 (7)	0.0770 (6)
H2A	0.7597	0.2103	0.7269	0.092*
C10	0.4910 (2)	−0.0260 (3)	0.86365 (6)	0.0729 (6)
H10A	0.4995	−0.1397	0.8782	0.109*
H10B	0.5057	−0.0390	0.8312	0.109*
H10C	0.3771	0.0245	0.8689	0.109*
C11	0.4661 (2)	0.1818 (3)	0.95186 (6)	0.0783 (7)
H11A	0.3910	0.0796	0.9514	0.117*
H11B	0.4062	0.2777	0.9364	0.117*
H11C	0.4939	0.2148	0.9831	0.117*
C4	1.0673 (3)	−0.0339 (3)	0.77143 (8)	0.0809 (7)
H4	1.1704	−0.0924	0.7639	0.097*
C3	0.9731 (3)	0.0598 (3)	0.73841 (7)	0.0856 (7)
H3	1.0118	0.0632	0.7085	0.103*
C18	0.8224 (3)	0.5192 (3)	1.14998 (7)	0.0898 (7)
H18A	0.8763	0.5584	1.1785	0.135*
H18B	0.7443	0.4222	1.1556	0.135*
H18C	0.7563	0.6146	1.1360	0.135*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0383 (7)	0.0868 (10)	0.0559 (9)	0.0026 (7)	−0.0011 (6)	−0.0061 (7)
N1	0.0470 (9)	0.0637 (11)	0.0449 (11)	0.0013 (8)	−0.0014 (8)	0.0021 (8)
O2	0.0535 (8)	0.1054 (12)	0.0656 (11)	−0.0024 (8)	0.0083 (7)	−0.0188 (9)
N3	0.0375 (8)	0.0723 (11)	0.0443 (11)	0.0028 (8)	−0.0002 (7)	−0.0027 (8)
C7	0.0435 (11)	0.0596 (13)	0.0427 (12)	0.0000 (9)	−0.0037 (9)	0.0042 (9)
N2	0.0362 (8)	0.0804 (12)	0.0515 (11)	−0.0010 (8)	−0.0025 (7)	−0.0059 (9)
C9	0.0435 (11)	0.0712 (14)	0.0458 (13)	0.0027 (10)	0.0041 (9)	−0.0014 (10)
C8	0.0415 (11)	0.0601 (13)	0.0417 (13)	0.0004 (9)	0.0002 (9)	0.0020 (10)
C17	0.0706 (14)	0.0623 (14)	0.0465 (14)	−0.0018 (11)	0.0083 (11)	−0.0014 (11)
C13	0.0492 (11)	0.0546 (12)	0.0421 (13)	0.0008 (9)	−0.0003 (10)	0.0003 (9)
C12	0.0488 (11)	0.0602 (13)	0.0496 (13)	0.0036 (9)	0.0046 (9)	0.0009 (10)
C1	0.0650 (13)	0.0713 (14)	0.0461 (14)	0.0038 (11)	−0.0034 (11)	−0.0037 (11)
C19	0.0524 (12)	0.0605 (13)	0.0474 (13)	−0.0026 (10)	0.0021 (10)	0.0013 (10)
C14	0.0537 (12)	0.0725 (14)	0.0583 (15)	0.0012 (11)	−0.0034 (10)	−0.0061 (11)
C6	0.0483 (11)	0.0612 (13)	0.0417 (13)	−0.0036 (10)	0.0009 (9)	−0.0042 (10)
C15	0.0636 (13)	0.0725 (15)	0.0694 (16)	−0.0046 (12)	−0.0116 (12)	−0.0056 (12)
C5	0.0533 (12)	0.0781 (15)	0.0567 (15)	0.0030 (11)	0.0015 (10)	−0.0079 (12)
C16	0.0856 (15)	0.0650 (14)	0.0512 (14)	−0.0054 (12)	−0.0083 (12)	−0.0066 (11)
C2	0.0888 (16)	0.0906 (17)	0.0511 (17)	−0.0013 (14)	−0.0041 (13)	0.0049 (12)
C10	0.0476 (11)	0.0952 (16)	0.0749 (15)	−0.0097 (11)	−0.0093 (10)	−0.0093 (12)
C11	0.0466 (12)	0.1223 (19)	0.0664 (15)	0.0070 (12)	0.0074 (10)	−0.0118 (13)
C4	0.0611 (14)	0.115 (2)	0.0670 (17)	0.0036 (13)	0.0129 (13)	−0.0166 (15)
C3	0.0867 (17)	0.121 (2)	0.0496 (16)	−0.0080 (16)	0.0126 (13)	−0.0039 (14)
C18	0.0988 (17)	0.1070 (19)	0.0649 (16)	−0.0019 (14)	0.0202 (13)	−0.0184 (13)

Geometric parameters (Å, º) top

O1—C7	1.2308 (17)	C14—C15	1.371 (2)
N1—C12	1.2858 (19)	C14—H16	0.9300
N1—C8	1.3942 (19)	C6—C5	1.380 (2)
O2—C19	1.3588 (18)	C15—C16	1.384 (2)
O2—H2	0.8200	C15—H17	0.9300
N3—C7	1.4050 (19)	C5—C4	1.390 (2)
N3—N2	1.4136 (16)	C5—H5	0.9300
N3—C6	1.416 (2)	C16—H18	0.9300
C7—C8	1.440 (2)	C2—C3	1.363 (3)
N2—C9	1.368 (2)	C2—H2A	0.9300
N2—C10	1.470 (2)	C10—H10A	0.9600
C9—C8	1.355 (2)	C10—H10B	0.9600
C9—C11	1.493 (2)	C10—H10C	0.9600
C17—C16	1.375 (2)	C11—H11A	0.9600
C17—C19	1.389 (2)	C11—H11B	0.9600
C17—C18	1.504 (2)	C11—H11C	0.9600
C13—C14	1.392 (2)	C4—C3	1.374 (3)
C13—C19	1.398 (2)	C4—H4	0.9300
C13—C12	1.445 (2)	C3—H3	0.9300
C12—H14	0.9300	C18—H18A	0.9600
C1—C2	1.378 (2)	C18—H18B	0.9600
C1—C6	1.381 (2)	C18—H18C	0.9600
C1—H1	0.9300

C12—N1—C8	121.75 (15)	C1—C6—N3	121.64 (17)
C19—O2—H2	109.5	C14—C15—C16	119.08 (18)
C7—N3—N2	109.11 (13)	C14—C15—H17	120.5
C7—N3—C6	123.46 (14)	C16—C15—H17	120.5
N2—N3—C6	119.10 (14)	C6—C5—C4	119.04 (19)
O1—C7—N3	123.64 (16)	C6—C5—H5	120.5
O1—C7—C8	131.41 (16)	C4—C5—H5	120.5
N3—C7—C8	104.92 (14)	C17—C16—C15	122.01 (18)
C9—N2—N3	106.19 (13)	C17—C16—H18	119.0
C9—N2—C10	121.46 (15)	C15—C16—H18	119.0
N3—N2—C10	116.36 (14)	C3—C2—C1	120.5 (2)
C8—C9—N2	111.03 (15)	C3—C2—H2A	119.7
C8—C9—C11	127.75 (18)	C1—C2—H2A	119.7
N2—C9—C11	121.19 (15)	N2—C10—H10A	109.5
C9—C8—N1	122.83 (16)	N2—C10—H10B	109.5
C9—C8—C7	108.10 (16)	H10A—C10—H10B	109.5
N1—C8—C7	128.84 (15)	N2—C10—H10C	109.5
C16—C17—C19	118.14 (18)	H10A—C10—H10C	109.5
C16—C17—C18	121.31 (19)	H10B—C10—H10C	109.5
C19—C17—C18	120.55 (18)	C9—C11—H11A	109.5
C14—C13—C19	118.29 (17)	C9—C11—H11B	109.5
C14—C13—C12	119.47 (16)	H11A—C11—H11B	109.5
C19—C13—C12	122.23 (16)	C9—C11—H11C	109.5
N1—C12—C13	121.88 (16)	H11A—C11—H11C	109.5
N1—C12—H14	119.1	H11B—C11—H11C	109.5
C13—C12—H14	119.1	C3—C4—C5	120.26 (19)
C2—C1—C6	119.64 (18)	C3—C4—H4	119.9
C2—C1—H1	120.2	C5—C4—H4	119.9
C6—C1—H1	120.2	C2—C3—C4	120.2 (2)
O2—C19—C17	118.16 (16)	C2—C3—H3	119.9
O2—C19—C13	120.54 (16)	C4—C3—H3	119.9
C17—C19—C13	121.30 (17)	C17—C18—H18A	109.5
C15—C14—C13	121.16 (18)	C17—C18—H18B	109.5
C15—C14—H16	119.4	H18A—C18—H18B	109.5
C13—C14—H16	119.4	C17—C18—H18C	109.5
C5—C6—C1	120.36 (18)	H18A—C18—H18C	109.5
C5—C6—N3	117.99 (17)	H18B—C18—H18C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.87	2.596 (2)	148

Experimental details

Crystal data
Chemical formula	C₁₉H₁₉N₃O₂
M_r	321.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.5655 (19), 7.5713 (19), 29.146 (7)
β (°)	92.006 (4)
V (Å³)	1668.5 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.34 × 0.28 × 0.17

Data collection
Diffractometer	Bruker APEX area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.972, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	9793, 2820, 1464
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.063, 0.88
No. of reflections	2820
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.12

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.82	1.87	2.596 (2)	147.9

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