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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o1889.
Published online 2008 September 6. doi:  10.1107/S1600536808027694
PMCID: PMC2959333

1-[(E)-2-Formyl-1-(4-methyl­phen­yl)ethen­yl]-3-(4-methyl­phen­yl)pyrazole-4-carbaldehyde

Abstract

In the crystal structure of the title compound, C21H18N2O2, mol­ecules are linked through C—H(...)O inter­actions. Two symmetry-related mol­ecules form a cyclic centrosymmetric R 2 2(20) dimer. These dimers are further connected into chains running along the b axis.

Related literature

For related literature, see: Baraldi et al. (1998 [triangle]); Bernstein et al. (1995 [triangle]); Bruno et al. (1990 [triangle]); Chen & Li (1998 [triangle]); Cottineau et al. (2002 [triangle]); Londershausen (1996 [triangle]); Mishra et al. (1998 [triangle]); Smith et al. (2001 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1889-scheme1.jpg

Experimental

Crystal data

  • C21H18N2O2
  • M r = 330.37
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1889-efi1.jpg
  • a = 10.2914 (4) Å
  • b = 15.3618 (5) Å
  • c = 11.0271 (4) Å
  • β = 98.778 (1)°
  • V = 1722.90 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 (2) K
  • 0.30 × 0.20 × 0.16 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2001 [triangle]) T min = 0.980, T max = 0.987
  • 24747 measured reflections
  • 6019 independent reflections
  • 3731 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.174
  • S = 1.04
  • 6019 reflections
  • 228 parameters
  • H-atom parameters constrained
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027694/bt2774sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808027694/bt2774Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

PR thanks Dr Babu Varghese, SAIF, IIT, Madras, India, for his help with the data collection.

supplementary crystallographic information

Comment

Pyrazoles and its derivatives have been reported to possess significant antiarrhythmic and sedative (Bruno et al., 1990), hypoglycemic (Cottineau et al., 2002), antiviral (Baraldi et al., 1998), and pesticidal (Londershausen,1996) activities. Some of their derivatives have also been successfully tested for their antifungal (Chen & Li, 1998), antihistaminic (Mishra et al., 1998) and anti-inflammatory (Smith et al., 2001) properties.

The pyrazole ring A and methylphenyl ring C are near-coplanar with the inter-ring dihedral angle of 17.08 (7)°, whereas the pyrazole ring is twisted from the methylphenyl ring B as can be seen from the dihedral angle of 79.70 (8)°. The propenal group assumes an extended conformation which is evidenced from the torsion angle of [N1—C6—C14—C15] -175.47 (12)°.

The crystal structure is stabilized by C—H···O type of intermolecular interactions. Atom C5 at (x, y, z) donates a proton to atom O1 at (3/2 - x,-1/2 + y,1/2 - z) form a one dimensional C7 chain (Bernstein et al. 1995) running along b axis. The molecules at positions (x, y, z) and (3 - x, -y, -z) form a cyclic centrosymmetric R22(20) dimer through C22—H22A···O2 hydrogen bonds.

Experimental

A mixture of 1-(4-methylphenyl)-1-ethanone N-[(E)-1-phenylethylidene] hydrazone (0.003 mole) and 3 ml of dimethyl formamide kept in an ice bath at 0° C, phosphorus oxycholride (0.024 mole) was added dropwise for 5–10 minutes. The reaction mixture was then kept in a microwave oven at 600 W for 30–60 sec. The process of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was poured into crushed ice and extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulfate. The different compounds present in the mixture were separated by column chromatography using petroleum ether and ethyl acetate mixture as eluent. This isolated compound was rectystalized in dichloromethane to obtain 3-(4-methylphenyl)-1-[(E)-1-(4-methylphenyl) -3-oxo-1-propenyl]-1H-pyrazole-4-carbaldehyde in 57% yield.

Refinement

H atoms were positioned geometrically (C—H=0.93–0.96 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl H 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate but not to tip.

Figures

Fig. 1.
Perspective view of the molecules showing the thermal ellipsoids are drawn at 50% probability level. The H atoms are shown as small circles of arbitrary radii.
Fig. 2.
Perspective view of the crystal packing showing hydrogen-bond interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C21H18N2O2F(000) = 696
Mr = 330.37Dx = 1.274 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4580 reflections
a = 10.2914 (4) Åθ = 2.3–32.2°
b = 15.3618 (5) ŵ = 0.08 mm1
c = 11.0271 (4) ÅT = 293 K
β = 98.778 (1)°Block, colorless
V = 1722.90 (11) Å30.30 × 0.20 × 0.16 mm
Z = 4

Data collection

Bruker APEX2 CCD area-detector diffractometer6019 independent reflections
Radiation source: fine-focus sealed tube3731 reflections with I > 2σ(I)
graphiteRint = 0.025
ω and [var phi] scansθmax = 32.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)h = −9→15
Tmin = 0.980, Tmax = 0.987k = −22→19
24747 measured reflectionsl = −16→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.174H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0833P)2 + 0.2417P] where P = (Fo2 + 2Fc2)/3
6019 reflections(Δ/σ)max = 0.037
228 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = −0.30 e Å3

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 (Å2)

xyzUiso*/Ueq
O10.65358 (11)0.31462 (7)0.28639 (13)0.0678 (3)
O21.23915 (18)−0.09914 (9)0.0928 (2)0.1340 (9)
N10.93785 (9)0.08384 (7)0.22048 (10)0.0378 (2)
N21.03155 (10)0.13820 (7)0.18711 (10)0.0395 (2)
C31.12006 (11)0.08674 (8)0.14811 (11)0.0367 (3)
C41.08139 (12)−0.00258 (8)0.15437 (12)0.0413 (3)
C50.96509 (12)−0.00004 (8)0.20099 (12)0.0401 (3)
H50.9144−0.04780.21630.048*
C60.82656 (11)0.11747 (8)0.26494 (11)0.0367 (3)
C70.75369 (11)0.05214 (8)0.32683 (12)0.0381 (3)
C80.80708 (14)0.01954 (10)0.44021 (14)0.0509 (3)
H80.88840.03960.47840.061*
C90.74082 (17)−0.04269 (11)0.49748 (15)0.0593 (4)
H90.7777−0.06320.57440.071*
C100.62160 (17)−0.07477 (10)0.44295 (16)0.0594 (4)
C110.56858 (16)−0.04197 (12)0.33110 (18)0.0648 (5)
H110.4876−0.06270.29310.078*
C120.63277 (14)0.02175 (11)0.27265 (14)0.0527 (4)
H120.59400.04370.19710.063*
C130.5526 (2)−0.14496 (13)0.5044 (2)0.0956 (8)
H13A0.4601−0.14320.47410.143*
H13B0.5667−0.13560.59150.143*
H13C0.5872−0.20080.48670.143*
C140.79599 (12)0.20179 (9)0.25103 (13)0.0438 (3)
H140.84540.23690.20660.053*
C150.68876 (13)0.24017 (10)0.30271 (14)0.0487 (3)
H150.64410.20530.35160.058*
C161.23610 (11)0.12790 (9)0.10905 (12)0.0386 (3)
C171.26700 (13)0.21329 (10)0.14214 (14)0.0497 (3)
H171.21590.24310.19110.060*
C181.37242 (14)0.25480 (10)0.10352 (15)0.0527 (4)
H181.39100.31220.12680.063*
C191.45103 (12)0.21259 (10)0.03075 (13)0.0454 (3)
C201.42132 (13)0.12763 (10)−0.00071 (14)0.0503 (3)
H201.47360.0978−0.04860.060*
C211.31552 (13)0.08512 (10)0.03692 (13)0.0475 (3)
H211.29760.02760.01370.057*
C221.56456 (14)0.25876 (12)−0.01291 (16)0.0582 (4)
H22A1.64250.22400.00570.087*
H22B1.57830.31400.02770.087*
H22C1.54510.2677−0.10000.087*
C231.13601 (18)−0.08585 (10)0.12661 (19)0.0684 (5)
H231.0849−0.13460.13620.082*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0641 (7)0.0420 (7)0.0968 (9)0.0162 (5)0.0110 (6)−0.0076 (6)
O20.1215 (13)0.0506 (8)0.263 (2)0.0205 (8)0.1355 (15)0.0071 (11)
N10.0371 (5)0.0308 (5)0.0488 (6)0.0001 (4)0.0169 (4)0.0010 (4)
N20.0387 (5)0.0325 (6)0.0508 (6)−0.0020 (4)0.0180 (4)0.0002 (4)
C30.0366 (5)0.0355 (7)0.0399 (6)0.0009 (4)0.0117 (4)0.0008 (5)
C40.0424 (6)0.0353 (7)0.0493 (7)0.0019 (5)0.0171 (5)−0.0013 (5)
C50.0433 (6)0.0298 (6)0.0502 (7)−0.0006 (5)0.0167 (5)−0.0007 (5)
C60.0337 (5)0.0343 (6)0.0442 (6)0.0010 (4)0.0129 (5)0.0013 (5)
C70.0373 (5)0.0332 (6)0.0470 (7)0.0008 (4)0.0166 (5)0.0000 (5)
C80.0489 (7)0.0486 (8)0.0561 (8)0.0020 (6)0.0110 (6)0.0086 (6)
C90.0766 (10)0.0492 (9)0.0572 (9)0.0087 (8)0.0266 (8)0.0136 (7)
C100.0757 (10)0.0409 (8)0.0730 (11)−0.0059 (7)0.0476 (8)−0.0042 (7)
C110.0556 (8)0.0655 (11)0.0784 (12)−0.0242 (8)0.0266 (8)−0.0120 (9)
C120.0471 (7)0.0578 (9)0.0545 (8)−0.0103 (6)0.0115 (6)0.0000 (7)
C130.1297 (19)0.0620 (12)0.1154 (18)−0.0239 (12)0.0837 (15)−0.0010 (11)
C140.0411 (6)0.0357 (7)0.0578 (8)0.0027 (5)0.0176 (6)0.0040 (6)
C150.0424 (6)0.0409 (8)0.0647 (9)0.0053 (5)0.0145 (6)−0.0028 (6)
C160.0360 (5)0.0412 (7)0.0404 (6)−0.0007 (5)0.0113 (5)0.0016 (5)
C170.0474 (7)0.0471 (8)0.0599 (9)−0.0060 (6)0.0247 (6)−0.0076 (6)
C180.0500 (7)0.0461 (8)0.0661 (9)−0.0105 (6)0.0221 (7)−0.0054 (7)
C190.0356 (6)0.0564 (9)0.0455 (7)−0.0020 (5)0.0102 (5)0.0086 (6)
C200.0445 (7)0.0573 (9)0.0537 (8)0.0025 (6)0.0216 (6)−0.0006 (6)
C210.0459 (7)0.0447 (8)0.0556 (8)−0.0015 (5)0.0198 (6)−0.0052 (6)
C220.0425 (7)0.0709 (11)0.0644 (9)−0.0070 (7)0.0180 (6)0.0116 (8)
C230.0755 (11)0.0359 (8)0.1052 (14)0.0070 (7)0.0502 (10)0.0005 (8)

Geometric parameters (Å, °)

O1—C151.2048 (17)C12—H120.9300
O2—C231.1949 (19)C13—H13A0.9600
N1—C51.3429 (16)C13—H13B0.9600
N1—N21.3679 (13)C13—H13C0.9600
N1—C61.4108 (14)C14—C151.4429 (17)
N2—C31.3263 (15)C14—H140.9300
C3—C41.4332 (18)C15—H150.9300
C3—C161.4726 (16)C16—C171.386 (2)
C4—C51.3734 (16)C16—C211.3896 (17)
C4—C231.449 (2)C17—C181.3806 (18)
C5—H50.9300C17—H170.9300
C6—C141.3364 (18)C18—C191.384 (2)
C6—C71.4804 (16)C18—H180.9300
C7—C121.3771 (19)C19—C201.373 (2)
C7—C81.3807 (19)C19—C221.5072 (17)
C8—C91.382 (2)C20—C211.3864 (18)
C8—H80.9300C20—H200.9300
C9—C101.373 (3)C21—H210.9300
C9—H90.9300C22—H22A0.9600
C10—C111.367 (3)C22—H22B0.9600
C10—C131.507 (2)C22—H22C0.9600
C11—C121.393 (2)C23—H230.9300
C11—H110.9300
C5—N1—N2111.71 (9)C10—C13—H13C109.5
C5—N1—C6127.40 (10)H13A—C13—H13C109.5
N2—N1—C6120.86 (10)H13B—C13—H13C109.5
C3—N2—N1105.69 (10)C6—C14—C15122.12 (12)
N2—C3—C4110.22 (10)C6—C14—H14118.9
N2—C3—C16117.81 (11)C15—C14—H14118.9
C4—C3—C16131.96 (11)O1—C15—C14124.02 (14)
C5—C4—C3104.78 (11)O1—C15—H15118.0
C5—C4—C23119.51 (13)C14—C15—H15118.0
C3—C4—C23135.70 (12)C17—C16—C21117.85 (11)
N1—C5—C4107.59 (11)C17—C16—C3119.56 (11)
N1—C5—H5126.2C21—C16—C3122.58 (12)
C4—C5—H5126.2C18—C17—C16121.04 (12)
C14—C6—N1120.30 (11)C18—C17—H17119.5
C14—C6—C7125.66 (10)C16—C17—H17119.5
N1—C6—C7114.03 (10)C17—C18—C19121.24 (14)
C12—C7—C8118.58 (12)C17—C18—H18119.4
C12—C7—C6121.17 (12)C19—C18—H18119.4
C8—C7—C6120.25 (11)C20—C19—C18117.67 (12)
C7—C8—C9120.59 (14)C20—C19—C22121.35 (13)
C7—C8—H8119.7C18—C19—C22120.99 (14)
C9—C8—H8119.7C19—C20—C21121.80 (12)
C10—C9—C8121.24 (15)C19—C20—H20119.1
C10—C9—H9119.4C21—C20—H20119.1
C8—C9—H9119.4C20—C21—C16120.39 (14)
C11—C10—C9118.04 (14)C20—C21—H21119.8
C11—C10—C13121.26 (18)C16—C21—H21119.8
C9—C10—C13120.70 (19)C19—C22—H22A109.5
C10—C11—C12121.64 (15)C19—C22—H22B109.5
C10—C11—H11119.2H22A—C22—H22B109.5
C12—C11—H11119.2C19—C22—H22C109.5
C7—C12—C11119.90 (15)H22A—C22—H22C109.5
C7—C12—H12120.1H22B—C22—H22C109.5
C11—C12—H12120.1O2—C23—C4127.49 (16)
C10—C13—H13A109.5O2—C23—H23116.3
C10—C13—H13B109.5C4—C23—H23116.3
H13A—C13—H13B109.5
C5—N1—N2—C3−1.10 (14)C9—C10—C11—C120.4 (2)
C6—N1—N2—C3−178.96 (11)C13—C10—C11—C12−178.80 (16)
N1—N2—C3—C41.07 (14)C8—C7—C12—C11−1.4 (2)
N1—N2—C3—C16−178.26 (10)C6—C7—C12—C11177.74 (13)
N2—C3—C4—C5−0.68 (15)C10—C11—C12—C71.0 (3)
C16—C3—C4—C5178.52 (13)N1—C6—C14—C15−175.47 (12)
N2—C3—C4—C23−179.31 (18)C7—C6—C14—C153.5 (2)
C16—C3—C4—C23−0.1 (3)C6—C14—C15—O1−175.65 (15)
N2—N1—C5—C40.69 (15)N2—C3—C16—C1716.27 (18)
C6—N1—C5—C4178.37 (12)C4—C3—C16—C17−162.88 (14)
C3—C4—C5—N1−0.02 (15)N2—C3—C16—C21−162.11 (13)
C23—C4—C5—N1178.89 (14)C4—C3—C16—C2118.7 (2)
C5—N1—C6—C14−163.17 (14)C21—C16—C17—C180.7 (2)
N2—N1—C6—C1414.31 (18)C3—C16—C17—C18−177.75 (13)
C5—N1—C6—C717.72 (18)C16—C17—C18—C19−0.2 (2)
N2—N1—C6—C7−164.79 (11)C17—C18—C19—C20−0.7 (2)
C14—C6—C7—C1272.91 (19)C17—C18—C19—C22178.93 (14)
N1—C6—C7—C12−108.04 (14)C18—C19—C20—C210.9 (2)
C14—C6—C7—C8−107.93 (16)C22—C19—C20—C21−178.68 (13)
N1—C6—C7—C871.12 (15)C19—C20—C21—C16−0.4 (2)
C12—C7—C8—C90.5 (2)C17—C16—C21—C20−0.5 (2)
C6—C7—C8—C9−178.73 (13)C3—C16—C21—C20177.95 (12)
C7—C8—C9—C101.0 (2)C5—C4—C23—O2−175.2 (2)
C8—C9—C10—C11−1.4 (2)C3—C4—C23—O23.3 (4)
C8—C9—C10—C13177.79 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C22—H22A···O2i0.962.603.378 (2)139.
C5—H5···O1ii0.932.233.1094 (17)159.

Symmetry codes: (i) −x+3, −y, −z; (ii) −x+3/2, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2774).

References

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