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Acta Cryst. (2008). E64, o1965-o1966    [ doi:10.1107/S1600536808029498 ]

A second monoclinic polymorph of 4-(2-hydroxy-4-methoxybenzylideneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

Z.-F. Zhu, X.-H. Shen and X.-G. Tang

Abstract top

The title compound, C19H19N3O3, prepared by condensing 4-aminoantipyrine and 4-methoxy-2-hydroxybenzaldehyde in methanol, is the second monoclinic polymorph of this compound which crystallizes in the space group C2/c. The structure was previously reported [Wang, Zhang, Yan, Zheng & Yang (2007). Acta Cryst. E63, o1245-o1246] in the space group P21/c. The hydroxyl group is disordered over two positions with occupancies of 0.787 (4) and 0.213 (4). The triply substituted benzene ring and the phenyl ring form dihedral angles of 12.2 (2) and 53.7 (2)°, respectively, with the pyrazolone ring; the corresponding values in the P21/c polymorph are 7.5 (2) and 42.6 (2)°. Intramolecular O-H...N and C-H...O hydrogen bonds are observed in the major disorder component. Adjacent molecules are linked through intermolecular O-H...O hydrogen bonds, forming dimers.

Comment top

The crystal structure of the title compound has been previously reported by Wang et al. (2007) in the monoclinic space group P21/c. We report here the structure of the second monoclinic polymorph of the title compound, in the space group C2/c.

In the title molecule (Fig. 1), the pyrazolone ring makes dihedral angles of 12.2 (2) and 53.7 (2)°, respectively, with the triply substituted C1–C6 benzene ring and the unsubstituted C13—C18 benzene ring; the corresponding values in the P21/c polymorph are 7.5 (2) and 42.6 (2)°. The bond lengths and angles are within normal ranges and comparable with those in related similar compounds (Duan et al., 2006; Jing et al., 2006; Zheng et al., 2006; Sun et al., 2006; Zhang et al., 2007; Wen, 2005). Intramolecular O—H···N and C—H···O hydrogen bonds (Table 1) are observed in the molecular structure.

Related literature top

For the P21/c polymorph of the title compound, see: Wang et al. (2007). For related literature, see: Duan et al. (2006); Jing et al. (2006); Sun et al. (2006); Wen (2005); Zhang et al. (2007); Zheng et al. (2006).

Experimental top

4-Methoxy-2-hydroxybenzaldehyde (152.1 mg, 1.0 mmol) and 4-aminoantipyrine (203.2 mg, 1.0 mmol) were added in methanol (60 ml). The mixture was refluxed for 30 min, then cooled to room temperature, yielding colourless solution. Colourless single crystals were formed when the solution was evaporated in air for several days.

Refinement top

The hydroxyl group is disordered over two positions with refined occupancies of 0.787 (4) and 0.213 (4). H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C–H distances of 0.93–0.96 Å, O–H distance of 0.82 Å, and with Uiso(H) set at 1.2Ueq(C) and 1.5Ueq(O and methyl C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellisoids. Only the major disorder component is shown. Intramolecular hydrogen bonds are shown as dashed lines.
4-(2-hydroxy-4-methoxybenzylideneamino)-1,5-dimethyl-2-phenyl-1H- pyrazol-3(2H)-one top
Crystal data top
C19H19N3O3F(000) = 1424
Mr = 337.37Dx = 1.328 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2554 reflections
a = 30.581 (3) Åθ = 2.4–25.6°
b = 6.906 (2) ŵ = 0.09 mm−1
c = 17.059 (3) ÅT = 298 K
β = 110.500 (2)°Block, colourless
V = 3374.6 (12) Å30.30 × 0.28 × 0.27 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer		3634 independent reflections
Radiation source: fine-focus sealed tube2355 reflections with I > 2σ(I)
graphiteRint = 0.037
ω scansθmax = 27.0°, θmin = 1.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −36→38
Tmin = 0.973, Tmax = 0.976k = −8→8
9315 measured reflectionsl = −20→21
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.145H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.071P)2 + 0.6977P]
where P = (Fo2 + 2Fc2)/3
3634 reflections(Δ/σ)max = 0.001
241 parametersΔρmax = 0.19 e Å−3
0 restraintsΔρmin = −0.20 e Å−3
Crystal data top
C19H19N3O3V = 3374.6 (12) Å3
Mr = 337.37Z = 8
Monoclinic, C2/cMo Kα radiation
a = 30.581 (3) ŵ = 0.09 mm−1
b = 6.906 (2) ÅT = 298 K
c = 17.059 (3) Å0.30 × 0.28 × 0.27 mm
β = 110.500 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3634 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2355 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.976Rint = 0.037
9315 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.145Δρmax = 0.19 e Å−3
S = 1.02Δρmin = −0.20 e Å−3
3634 reflectionsAbsolute structure: ?
241 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/UeqOcc. (<1)
O10.13337 (6)0.6567 (2)0.02029 (14)0.0720 (7)0.787 (4)
H10.16130.63370.04270.108*0.787 (4)
O1'0.1955 (2)1.2396 (10)−0.0333 (4)0.071 (3)0.213 (4)
H1'0.18911.3241−0.06930.106*0.213 (4)
O20.03260 (5)1.1507 (2)−0.13459 (11)0.0834 (5)
O30.31552 (5)0.96750 (18)0.13504 (9)0.0628 (4)
N10.22230 (5)0.7333 (2)0.08331 (9)0.0483 (4)
N20.32298 (5)0.5274 (2)0.23447 (9)0.0494 (4)
N30.34320 (5)0.6934 (2)0.21511 (9)0.0491 (4)
C10.16608 (6)0.9540 (2)−0.00342 (11)0.0450 (4)
C20.12777 (7)0.8350 (3)−0.01178 (12)0.0505 (5)
H20.13270.71250.01240.061*0.213 (4)
C30.08307 (7)0.8956 (3)−0.05505 (13)0.0586 (5)
H30.05800.8144−0.06010.070*
C40.07548 (7)1.0762 (3)−0.09092 (13)0.0573 (5)
C50.11288 (7)1.1968 (3)−0.08392 (12)0.0586 (5)
H50.10781.3190−0.10840.070*
C60.15705 (6)1.1355 (3)−0.04112 (12)0.0511 (5)
H60.18201.2171−0.03690.061*0.787 (4)
C70.21326 (6)0.8961 (2)0.04376 (11)0.0468 (4)
H70.23780.97800.04580.056*
C80.26761 (6)0.6861 (2)0.13421 (10)0.0437 (4)
C90.27825 (6)0.5207 (2)0.18071 (11)0.0458 (4)
C100.24772 (7)0.3533 (3)0.17836 (14)0.0658 (6)
H10A0.21790.37250.13510.099*
H10B0.24360.34110.23140.099*
H10C0.26180.23750.16700.099*
C110.35235 (7)0.3601 (3)0.26802 (13)0.0625 (6)
H11A0.33540.26770.28830.094*
H11B0.37980.40010.31320.094*
H11C0.36130.30190.22480.094*
C120.30866 (6)0.8026 (2)0.15627 (11)0.0468 (4)
C130.38321 (6)0.7784 (2)0.27470 (11)0.0460 (4)
C140.39069 (7)0.7743 (3)0.35949 (12)0.0559 (5)
H140.37030.70770.37950.067*
C150.42859 (8)0.8700 (3)0.41369 (14)0.0673 (6)
H150.43410.86650.47090.081*
C160.45828 (8)0.9701 (3)0.38483 (15)0.0717 (6)
H160.48361.03580.42210.086*
C170.45062 (7)0.9736 (3)0.30043 (15)0.0672 (6)
H170.47081.04240.28070.081*
C180.41342 (7)0.8764 (3)0.24504 (13)0.0545 (5)
H180.40870.87680.18810.065*
C19−0.00684 (9)1.0308 (4)−0.1448 (3)0.1287 (14)
H19A−0.00370.9120−0.17150.193*
H19B−0.03471.0966−0.17880.193*
H19C−0.00881.0030−0.09100.193*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0605 (11)0.0448 (11)0.1057 (17)−0.0043 (9)0.0229 (11)0.0205 (10)
O1'0.056 (4)0.064 (4)0.079 (5)−0.012 (3)0.005 (3)0.032 (4)
O20.0526 (8)0.0619 (9)0.1159 (14)0.0025 (7)0.0047 (8)0.0090 (9)
O30.0643 (8)0.0470 (8)0.0663 (9)−0.0092 (7)0.0094 (7)0.0151 (6)
N10.0518 (9)0.0447 (8)0.0470 (9)−0.0007 (7)0.0155 (7)0.0007 (7)
N20.0561 (9)0.0376 (8)0.0509 (9)−0.0017 (7)0.0142 (8)0.0053 (7)
N30.0541 (9)0.0402 (8)0.0483 (9)−0.0070 (7)0.0119 (7)0.0041 (7)
C10.0505 (10)0.0432 (9)0.0406 (10)−0.0025 (8)0.0150 (8)−0.0014 (8)
C20.0557 (11)0.0404 (10)0.0556 (11)−0.0029 (8)0.0197 (9)0.0005 (8)
C30.0488 (11)0.0479 (11)0.0750 (14)−0.0069 (9)0.0167 (10)−0.0035 (10)
C40.0524 (11)0.0494 (11)0.0630 (13)0.0029 (9)0.0114 (10)−0.0009 (9)
C50.0618 (12)0.0461 (11)0.0608 (13)−0.0010 (9)0.0125 (10)0.0087 (9)
C60.0530 (11)0.0479 (10)0.0497 (11)−0.0073 (9)0.0147 (9)0.0031 (8)
C70.0526 (10)0.0454 (10)0.0425 (10)−0.0047 (8)0.0167 (8)−0.0021 (8)
C80.0513 (10)0.0394 (9)0.0404 (9)−0.0015 (8)0.0162 (8)−0.0020 (7)
C90.0541 (10)0.0410 (9)0.0442 (10)−0.0015 (8)0.0195 (9)−0.0011 (8)
C100.0708 (13)0.0508 (11)0.0740 (14)−0.0116 (10)0.0229 (12)0.0091 (10)
C110.0688 (13)0.0471 (11)0.0632 (13)0.0063 (10)0.0127 (11)0.0108 (9)
C120.0562 (11)0.0402 (9)0.0413 (10)−0.0026 (8)0.0138 (9)0.0011 (8)
C130.0453 (10)0.0397 (9)0.0487 (11)0.0024 (8)0.0111 (9)−0.0004 (8)
C140.0554 (11)0.0612 (12)0.0505 (11)−0.0039 (10)0.0180 (10)0.0004 (9)
C150.0663 (13)0.0772 (14)0.0496 (12)−0.0062 (12)0.0091 (11)−0.0061 (10)
C160.0600 (13)0.0742 (15)0.0689 (15)−0.0139 (11)0.0075 (11)−0.0059 (12)
C170.0565 (12)0.0623 (13)0.0838 (16)−0.0101 (10)0.0255 (12)0.0009 (12)
C180.0590 (11)0.0527 (11)0.0536 (11)−0.0026 (9)0.0223 (10)0.0005 (9)
C190.0503 (14)0.087 (2)0.211 (4)−0.0084 (14)−0.0024 (18)0.023 (2)
Geometric parameters (Å, °) top
O1—C21.333 (2)C7—H70.93
O1—H10.82C8—C91.363 (2)
O1'—C61.345 (6)C8—C121.426 (2)
O1'—H1'0.82C9—C101.478 (2)
O2—C41.362 (2)C10—H10A0.96
O2—C191.422 (3)C10—H10B0.96
O3—C121.235 (2)C10—H10C0.96
N1—C71.291 (2)C11—H11A0.96
N1—C81.392 (2)C11—H11B0.96
N2—C91.355 (2)C11—H11C0.96
N2—N31.3959 (19)C13—C181.376 (3)
N2—C111.452 (2)C13—C141.383 (3)
N3—C121.396 (2)C14—C151.373 (3)
N3—C131.416 (2)C14—H140.93
C1—C61.392 (2)C15—C161.363 (3)
C1—C21.397 (2)C15—H150.93
C1—C71.441 (2)C16—C171.376 (3)
C2—C31.372 (3)C16—H160.93
C2—H20.93C17—C181.373 (3)
C3—C41.373 (3)C17—H170.93
C3—H30.93C18—H180.93
C4—C51.386 (3)C19—H19A0.96
C5—C61.359 (3)C19—H19B0.96
C5—H50.93C19—H19C0.96
C6—H60.93
C2—O1—H1109.5C8—C9—C10128.31 (17)
C6—O1'—H1'109.5C9—C10—H10A109.5
C4—O2—C19117.40 (17)C9—C10—H10B109.5
C7—N1—C8120.96 (15)H10A—C10—H10B109.5
C9—N2—N3107.07 (13)C9—C10—H10C109.5
C9—N2—C11125.34 (14)H10A—C10—H10C109.5
N3—N2—C11118.86 (14)H10B—C10—H10C109.5
N2—N3—C12109.12 (13)N2—C11—H11A109.5
N2—N3—C13120.92 (14)N2—C11—H11B109.5
C12—N3—C13122.55 (14)H11A—C11—H11B109.5
C6—C1—C2117.34 (16)N2—C11—H11C109.5
C6—C1—C7120.37 (16)H11A—C11—H11C109.5
C2—C1—C7122.27 (16)H11B—C11—H11C109.5
O1—C2—C3117.58 (18)O3—C12—N3123.06 (16)
O1—C2—C1121.24 (18)O3—C12—C8131.86 (17)
C3—C2—C1121.16 (17)N3—C12—C8105.01 (14)
C3—C2—H2119.4C18—C13—C14120.51 (17)
C1—C2—H2119.4C18—C13—N3117.56 (17)
C2—C3—C4119.87 (18)C14—C13—N3121.82 (17)
C2—C3—H3120.1C15—C14—C13119.09 (19)
C4—C3—H3120.1C15—C14—H14120.5
O2—C4—C3124.53 (18)C13—C14—H14120.5
O2—C4—C5115.33 (17)C16—C15—C14120.8 (2)
C3—C4—C5120.14 (18)C16—C15—H15119.6
C6—C5—C4119.62 (17)C14—C15—H15119.6
C6—C5—H5120.2C15—C16—C17119.7 (2)
C4—C5—H5120.2C15—C16—H16120.1
O1'—C6—C5123.9 (3)C17—C16—H16120.1
O1'—C6—C1114.2 (3)C18—C17—C16120.5 (2)
C5—C6—C1121.86 (17)C18—C17—H17119.7
C5—C6—H6119.1C16—C17—H17119.7
C1—C6—H6119.1C17—C18—C13119.2 (2)
N1—C7—C1121.53 (17)C17—C18—H18120.4
N1—C7—H7119.2C13—C18—H18120.4
C1—C7—H7119.2O2—C19—H19A109.5
C9—C8—N1122.81 (16)O2—C19—H19B109.5
C9—C8—C12108.09 (15)H19A—C19—H19B109.5
N1—C8—C12128.62 (15)O2—C19—H19C109.5
N2—C9—C8110.13 (15)H19A—C19—H19C109.5
N2—C9—C10121.55 (16)H19B—C19—H19C109.5
C9—N2—N3—C127.87 (18)C11—N2—C9—C8−153.47 (18)
C11—N2—N3—C12157.19 (16)N3—N2—C9—C10174.23 (17)
C9—N2—N3—C13158.51 (16)C11—N2—C9—C1027.5 (3)
C11—N2—N3—C13−52.2 (2)N1—C8—C9—N2−169.67 (15)
C6—C1—C2—O1178.03 (19)C12—C8—C9—N23.0 (2)
C7—C1—C2—O1−3.5 (3)N1—C8—C9—C109.3 (3)
C6—C1—C2—C3−0.4 (3)C12—C8—C9—C10−177.97 (18)
C7—C1—C2—C3178.12 (18)N2—N3—C12—O3171.32 (17)
O1—C2—C3—C4−178.5 (2)C13—N3—C12—O321.3 (3)
C1—C2—C3—C4−0.1 (3)N2—N3—C12—C8−5.92 (18)
C19—O2—C4—C3−1.2 (4)C13—N3—C12—C8−155.98 (16)
C19—O2—C4—C5178.8 (2)C9—C8—C12—O3−175.1 (2)
C2—C3—C4—O2−179.54 (19)N1—C8—C12—O3−2.9 (3)
C2—C3—C4—C50.4 (3)C9—C8—C12—N31.84 (19)
O2—C4—C5—C6179.70 (19)N1—C8—C12—N3174.00 (16)
C3—C4—C5—C6−0.2 (3)N2—N3—C13—C18150.64 (16)
C4—C5—C6—O1'177.8 (5)C12—N3—C13—C18−62.7 (2)
C4—C5—C6—C1−0.2 (3)N2—N3—C13—C14−33.2 (2)
C2—C1—C6—O1'−177.6 (4)C12—N3—C13—C14113.5 (2)
C7—C1—C6—O1'3.8 (5)C18—C13—C14—C150.2 (3)
C2—C1—C6—C50.6 (3)N3—C13—C14—C15−175.85 (18)
C7—C1—C6—C5−177.99 (18)C13—C14—C15—C160.8 (3)
C8—N1—C7—C1−174.67 (15)C14—C15—C16—C17−0.8 (3)
C6—C1—C7—N1175.94 (17)C15—C16—C17—C18−0.3 (3)
C2—C1—C7—N1−2.5 (3)C16—C17—C18—C131.3 (3)
C7—N1—C8—C9176.18 (17)C14—C13—C18—C17−1.3 (3)
C7—N1—C8—C125.1 (3)N3—C13—C18—C17174.94 (18)
N3—N2—C9—C8−6.7 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.882.605 (2)147
O1'—H1'···O3i0.821.802.609 (6)169
C7—H7···O30.932.333.006 (5)129
Symmetry codes: (i) −x+1/2, −y+5/2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.882.605 (2)147
O1'—H1'···O3i0.821.802.609 (6)169
C7—H7···O30.932.333.006 (5)129
Symmetry codes: (i) −x+1/2, −y+5/2, −z.
Acknowledgements top

No acknowledgements.

references
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