4-[(2-Hydr­oxy-3-methoxy­benzyl­idene)amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

The title compound, C₁₉H₁₉N₃O₃, was prepared by the reaction of 2-hydr­oxy-3-methoxy­benzaldehyde (o-vanillin) and 4-amino-1,5-dimethyl-2-phenyl­pyrazol-3-one. The crystal structure shows that a strong intra­molecular O—H...N hydrogen bond stabilizes the conformation of the mol­ecule, while inter­molecular C—H...O hydrogen bonds give rise to a stable structure in the solid state.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.047
• wR factor = 0.128
• Data-to-parameter ratio = 14.8

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S1. Comment

The synthesis of new and designed crystal structures is part of a major strand of modern chemistry. One of the aims of crystal engineering is to establish control over the preparation of crystalline solid materials, so that their architecture and properties are predictable (Parashar et al., 1988; Tynan et al., 2005). In the present study, we report the synthesis and structure of the title compound, (I) (Fig. 1 and Table 1), which will provide useful information on its physical and chemical properties.

The central system, N1/N2/C7/O1/C9/C10/N3/C8, is planar, with an r.m.s. deviation for fitted atoms of 0.038 Å, and the dihedral angle with the phenyl ring (C1–C6) is 55.17 (5)°. The o-vanillin moiety (N3/C12–C19/O2/O3) is planar, with an r.m.s. deviation for fitted atoms of 0.021 Å. The dihedral angle between the central system and the o-vanillin moiety is 7.01 (6)°. Intramolecular O—H···N and C—H···O hydrogen bonds (Table 2) stabilize the conformation of the molecule. The molecules are associated via weak C—H···O intermolecular hydrogen bonds (Table 2) to form a supramolecular structure (Fig. 2).

S2. Experimental

An anhydrous ethanol solution of 2-hydroxy-3-methoxybenzaldehyde (o-vanillin, 1.52 g, 10 mmol) was added to an anhydrous ethanol solution of 4-amino-1,5-dimethyl-2-phenylpyrazol-3-one (4-aminoantipyrine, 2.03 g, 10 mmol) and the mixture was stirred at 350 K for 5 h under nitrogen, whereupon a yellow precipitate appeared. The product was isolated and recrystallized from ethanol, and then dried in vacuo to give pure (I) in 89% yield. Bright yellow single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

S3. Refinement

The H atom of the hydroxy group was found in a difference map and refined with free coordinates and isotropic U parameter. Other H atoms were included in calculated positions and refined using a riding model approximation. Constrained C—H bond lengths and U_iso parameters were 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic CH, and 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl CH₃.

Computing details

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

Figures

	Fig. 1. The structure of (I), with displacement ellipsoids for non-H atoms drawn at the 30% probability level.
	Fig. 2. Intermolecular hydrogen-bonding interactions (dashed lines) in the crystal structure of (I). H atoms have been omitted.

4-[(2-Hydroxy-3-methoxybenzylidene)amino]-1,5-dimethyl-2-phenyl-1H- pyrazol-3(2H)-one

Crystal data

C19H19N3O3	F(000) = 1424
Mr = 337.37	Dx = 1.321 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1997 reflections
a = 27.920 (6) Å	θ = 2.8–24.2°
b = 7.5547 (15) Å	µ = 0.09 mm^−1
c = 16.712 (3) Å	T = 294 K
β = 105.753 (4)°	Block, yellow
V = 3392.6 (12) Å^3	0.26 × 0.24 × 0.16 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	3449 independent reflections
Radiation source: fine-focus sealed tube	2024 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ϕ and ω scans	θmax = 26.3°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −34→32
Tmin = 0.970, Tmax = 0.986	k = −8→9
9165 measured reflections	l = −20→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 0.5212P] where P = (Fo^2 + 2Fc^2)/3
3449 reflections	(Δ/σ)max = 0.001
233 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.41761 (5)	0.56172 (17)	0.68922 (9)	0.0447 (4)
O2	0.56334 (6)	0.18800 (18)	0.57666 (9)	0.0508 (4)
H2	0.5332 (10)	0.197 (3)	0.5971 (15)	0.084 (8)*
O3	0.64031 (5)	0.2462 (2)	0.51859 (10)	0.0566 (4)
N1	0.37966 (6)	0.2932 (2)	0.70078 (10)	0.0378 (4)
N2	0.38624 (6)	0.1157 (2)	0.67788 (10)	0.0408 (4)
N3	0.49232 (6)	0.3105 (2)	0.63286 (9)	0.0353 (4)
C1	0.33016 (7)	0.3580 (2)	0.68750 (12)	0.0355 (5)
C2	0.29110 (8)	0.2895 (3)	0.62557 (12)	0.0460 (6)
H2A	0.2963	0.1937	0.5940	0.055*
C3	0.24436 (9)	0.3643 (3)	0.61092 (14)	0.0572 (6)
H3	0.2180	0.3180	0.5696	0.069*
C4	0.23651 (9)	0.5062 (4)	0.65685 (16)	0.0611 (7)
H4	0.2051	0.5573	0.6460	0.073*
C5	0.27526 (9)	0.5728 (3)	0.71912 (15)	0.0574 (7)
H5	0.2698	0.6687	0.7504	0.069*
C6	0.32231 (8)	0.4983 (3)	0.73574 (13)	0.0439 (5)
H6	0.3482	0.5420	0.7787	0.053*
C7	0.41735 (7)	0.3991 (2)	0.68420 (11)	0.0338 (5)
C8	0.45023 (7)	0.2757 (2)	0.65975 (11)	0.0322 (4)
C9	0.43136 (7)	0.1105 (2)	0.65972 (12)	0.0369 (5)
C10	0.45283 (9)	−0.0587 (3)	0.63965 (15)	0.0543 (6)
H10A	0.4352	−0.0958	0.5846	0.081*
H10B	0.4498	−0.1479	0.6789	0.081*
H10C	0.4873	−0.0416	0.6425	0.081*
C11	0.37116 (9)	−0.0189 (3)	0.72999 (15)	0.0564 (6)
H11A	0.3804	−0.1342	0.7151	0.085*
H11B	0.3358	−0.0141	0.7214	0.085*
H11C	0.3875	0.0039	0.7874	0.085*
C12	0.50765 (7)	0.4695 (3)	0.62506 (11)	0.0364 (5)
H12	0.4911	0.5653	0.6401	0.044*
C13	0.55036 (7)	0.5004 (3)	0.59315 (11)	0.0343 (5)
C14	0.56541 (8)	0.6741 (3)	0.58343 (12)	0.0433 (5)
H14	0.5484	0.7685	0.5987	0.052*
C15	0.60496 (8)	0.7067 (3)	0.55159 (13)	0.0485 (6)
H15	0.6146	0.8225	0.5453	0.058*
C16	0.63050 (8)	0.5665 (3)	0.52878 (13)	0.0466 (6)
H16	0.6572	0.5893	0.5070	0.056*
C17	0.61697 (7)	0.3940 (3)	0.53794 (12)	0.0412 (5)
C18	0.57635 (7)	0.3590 (3)	0.56984 (12)	0.0364 (5)
C19	0.67991 (9)	0.2739 (4)	0.48141 (16)	0.0739 (8)
H19A	0.6678	0.3392	0.4306	0.111*
H19B	0.6926	0.1616	0.4696	0.111*
H19C	0.7060	0.3396	0.5189	0.111*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0508 (9)	0.0256 (8)	0.0618 (9)	−0.0034 (6)	0.0223 (7)	−0.0027 (7)
O2	0.0545 (10)	0.0364 (9)	0.0698 (10)	0.0017 (7)	0.0312 (9)	0.0012 (7)
O3	0.0493 (10)	0.0593 (10)	0.0699 (10)	0.0087 (8)	0.0310 (8)	0.0045 (8)
N1	0.0406 (10)	0.0256 (9)	0.0511 (11)	−0.0028 (7)	0.0192 (8)	−0.0023 (8)
N2	0.0461 (11)	0.0231 (9)	0.0594 (11)	−0.0039 (7)	0.0248 (9)	−0.0012 (8)
N3	0.0357 (10)	0.0320 (9)	0.0393 (9)	−0.0019 (7)	0.0120 (8)	0.0008 (7)
C1	0.0386 (12)	0.0338 (11)	0.0380 (11)	−0.0020 (9)	0.0171 (10)	0.0036 (9)
C2	0.0470 (14)	0.0487 (13)	0.0455 (13)	−0.0101 (11)	0.0181 (11)	−0.0073 (10)
C3	0.0427 (15)	0.0736 (17)	0.0545 (14)	−0.0091 (12)	0.0115 (11)	0.0043 (13)
C4	0.0429 (15)	0.0781 (18)	0.0667 (17)	0.0126 (13)	0.0222 (13)	0.0196 (15)
C5	0.0627 (17)	0.0559 (15)	0.0620 (16)	0.0152 (13)	0.0312 (14)	−0.0002 (12)
C6	0.0466 (13)	0.0444 (13)	0.0422 (12)	0.0026 (10)	0.0147 (10)	−0.0042 (10)
C7	0.0376 (12)	0.0285 (11)	0.0347 (11)	−0.0042 (9)	0.0089 (9)	0.0007 (9)
C8	0.0353 (11)	0.0284 (11)	0.0336 (11)	−0.0011 (9)	0.0106 (9)	0.0003 (8)
C9	0.0402 (12)	0.0299 (11)	0.0426 (12)	−0.0012 (9)	0.0144 (10)	−0.0002 (9)
C10	0.0589 (15)	0.0312 (12)	0.0804 (17)	0.0013 (11)	0.0318 (13)	−0.0059 (12)
C11	0.0678 (16)	0.0350 (13)	0.0758 (17)	−0.0068 (11)	0.0355 (14)	0.0072 (12)
C12	0.0374 (12)	0.0321 (12)	0.0395 (11)	0.0004 (9)	0.0100 (9)	−0.0014 (9)
C13	0.0324 (11)	0.0355 (11)	0.0338 (11)	−0.0052 (9)	0.0071 (9)	0.0010 (9)
C14	0.0434 (13)	0.0387 (13)	0.0482 (13)	−0.0041 (10)	0.0135 (10)	−0.0019 (10)
C15	0.0502 (14)	0.0442 (13)	0.0517 (13)	−0.0146 (11)	0.0146 (11)	0.0026 (11)
C16	0.0385 (13)	0.0575 (15)	0.0462 (13)	−0.0098 (11)	0.0154 (10)	0.0020 (11)
C17	0.0361 (12)	0.0496 (14)	0.0381 (12)	0.0033 (10)	0.0102 (10)	0.0008 (10)
C18	0.0350 (12)	0.0349 (12)	0.0386 (11)	−0.0021 (9)	0.0087 (9)	0.0022 (9)
C19	0.0634 (17)	0.091 (2)	0.0828 (18)	0.0222 (15)	0.0461 (15)	0.0181 (16)

Geometric parameters (Å, º)

O1—C7	1.232 (2)	C7—C8	1.443 (3)
O2—C18	1.355 (2)	C8—C9	1.354 (2)
O2—H2	0.99 (3)	C9—C10	1.488 (3)
O3—C17	1.375 (2)	C10—H10A	0.9600
O3—C19	1.423 (2)	C10—H10B	0.9600
N1—C7	1.408 (2)	C10—H10C	0.9600
N1—N2	1.420 (2)	C11—H11A	0.9600
N1—C1	1.426 (2)	C11—H11B	0.9600
N2—C9	1.374 (2)	C11—H11C	0.9600
N2—C11	1.472 (2)	C12—C13	1.451 (3)
N3—C12	1.293 (2)	C12—H12	0.9300
N3—C8	1.392 (2)	C13—C14	1.401 (3)
C1—C2	1.384 (3)	C13—C18	1.405 (3)
C1—C6	1.385 (3)	C14—C15	1.372 (3)
C2—C3	1.382 (3)	C14—H14	0.9300
C2—H2A	0.9300	C15—C16	1.387 (3)
C3—C4	1.370 (3)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.377 (3)
C4—C5	1.377 (3)	C16—H16	0.9300
C4—H4	0.9300	C17—C18	1.403 (3)
C5—C6	1.386 (3)	C19—H19A	0.9600
C5—H5	0.9300	C19—H19B	0.9600
C6—H6	0.9300	C19—H19C	0.9600
C18—O2—H2	103.6 (14)	H10A—C10—H10B	109.5
C17—O3—C19	117.20 (18)	C9—C10—H10C	109.5
C7—N1—N2	108.98 (14)	H10A—C10—H10C	109.5
C7—N1—C1	121.24 (15)	H10B—C10—H10C	109.5
N2—N1—C1	118.27 (15)	N2—C11—H11A	109.5
C9—N2—N1	106.23 (14)	N2—C11—H11B	109.5
C9—N2—C11	122.52 (17)	H11A—C11—H11B	109.5
N1—N2—C11	114.45 (15)	N2—C11—H11C	109.5
C12—N3—C8	122.63 (16)	H11A—C11—H11C	109.5
C2—C1—C6	120.3 (2)	H11B—C11—H11C	109.5
C2—C1—N1	121.44 (18)	N3—C12—C13	120.94 (18)
C6—C1—N1	118.20 (18)	N3—C12—H12	119.5
C3—C2—C1	119.6 (2)	C13—C12—H12	119.5
C3—C2—H2A	120.2	C14—C13—C18	119.13 (18)
C1—C2—H2A	120.2	C14—C13—C12	119.72 (18)
C4—C3—C2	120.5 (2)	C18—C13—C12	121.13 (17)
C4—C3—H3	119.7	C15—C14—C13	120.7 (2)
C2—C3—H3	119.7	C15—C14—H14	119.6
C3—C4—C5	119.8 (2)	C13—C14—H14	119.6
C3—C4—H4	120.1	C14—C15—C16	119.9 (2)
C5—C4—H4	120.1	C14—C15—H15	120.1
C4—C5—C6	120.7 (2)	C16—C15—H15	120.1
C4—C5—H5	119.6	C17—C16—C15	121.01 (19)
C6—C5—H5	119.6	C17—C16—H16	119.5
C1—C6—C5	119.0 (2)	C15—C16—H16	119.5
C1—C6—H6	120.5	O3—C17—C16	125.49 (18)
C5—C6—H6	120.5	O3—C17—C18	114.82 (18)
O1—C7—N1	122.98 (17)	C16—C17—C18	119.68 (19)
O1—C7—C8	132.17 (18)	O2—C18—C17	118.33 (18)
N1—C7—C8	104.81 (15)	O2—C18—C13	122.10 (17)
C9—C8—N3	122.41 (17)	C17—C18—C13	119.57 (18)
C9—C8—C7	108.54 (17)	O3—C19—H19A	109.5
N3—C8—C7	128.83 (16)	O3—C19—H19B	109.5
C8—C9—N2	110.72 (16)	H19A—C19—H19B	109.5
C8—C9—C10	127.66 (19)	O3—C19—H19C	109.5
N2—C9—C10	121.56 (16)	H19A—C19—H19C	109.5
C9—C10—H10A	109.5	H19B—C19—H19C	109.5
C9—C10—H10B	109.5
C7—N1—N2—C9	8.8 (2)	C7—C8—C9—N2	3.5 (2)
C1—N1—N2—C9	152.62 (16)	N3—C8—C9—C10	5.7 (3)
C7—N1—N2—C11	147.13 (17)	C7—C8—C9—C10	−179.19 (19)
C1—N1—N2—C11	−69.0 (2)	N1—N2—C9—C8	−7.6 (2)
C7—N1—C1—C2	112.1 (2)	C11—N2—C9—C8	−141.73 (19)
N2—N1—C1—C2	−27.2 (2)	N1—N2—C9—C10	174.98 (17)
C7—N1—C1—C6	−64.8 (2)	C11—N2—C9—C10	40.8 (3)
N2—N1—C1—C6	155.88 (17)	C8—N3—C12—C13	−177.11 (16)
C6—C1—C2—C3	1.4 (3)	N3—C12—C13—C14	178.43 (18)
N1—C1—C2—C3	−175.49 (18)	N3—C12—C13—C18	0.0 (3)
C1—C2—C3—C4	0.4 (3)	C18—C13—C14—C15	0.0 (3)
C2—C3—C4—C5	−1.2 (3)	C12—C13—C14—C15	−178.49 (18)
C3—C4—C5—C6	0.3 (4)	C13—C14—C15—C16	−0.1 (3)
C2—C1—C6—C5	−2.2 (3)	C14—C15—C16—C17	−0.3 (3)
N1—C1—C6—C5	174.70 (18)	C19—O3—C17—C16	−3.9 (3)
C4—C5—C6—C1	1.4 (3)	C19—O3—C17—C18	176.37 (18)
N2—N1—C7—O1	171.60 (17)	C15—C16—C17—O3	−178.85 (19)
C1—N1—C7—O1	29.0 (3)	C15—C16—C17—C18	0.8 (3)
N2—N1—C7—C8	−6.57 (19)	O3—C17—C18—O2	−1.5 (3)
C1—N1—C7—C8	−149.16 (16)	C16—C17—C18—O2	178.77 (18)
C12—N3—C8—C9	173.05 (19)	O3—C17—C18—C13	178.82 (17)
C12—N3—C8—C7	−1.0 (3)	C16—C17—C18—C13	−0.9 (3)
O1—C7—C8—C9	−176.0 (2)	C14—C13—C18—O2	−179.16 (18)
N1—C7—C8—C9	2.0 (2)	C12—C13—C18—O2	−0.7 (3)
O1—C7—C8—N3	−1.3 (4)	C14—C13—C18—C17	0.5 (3)
N1—C7—C8—N3	176.65 (17)	C12—C13—C18—C17	178.95 (17)
N3—C8—C9—N2	−171.54 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N3	0.99 (3)	1.66 (3)	2.585 (2)	153 (2)
C12—H12···O1	0.93	2.41	3.069 (2)	128
C10—H10B···O1^i	0.96	2.40	3.212 (3)	143
C10—H10A···O3^ii	0.96	2.60	3.468 (3)	151

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y, −z+1.