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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2372.
Published online 2009 September 9. doi:  10.1107/S1600536809035314
PMCID: PMC2970404

Ethyl 6-methyl-2-p-tolyl­pyrazolo[1,5-a]pyridine-5-carboxyl­ate

Abstract

In the title mol­ecule, C18H18N2O2, the bicyclic ring system and the benzene ring form a dihedral angle of 13.45 (3)°. In the crystal structure, weak inter­molecular C—H(...)O hydrogen bonds link mol­ecules into chains propagated along [201].

Related literature

For novel pyrazolo[1,5-a]pyridine compounds, see: Ge et al. (2009 [triangle]). For a related structure, see: Shao et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2372-scheme1.jpg

Experimental

Crystal data

  • C18H18N2O2
  • M r = 294.34
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2372-efi1.jpg
  • a = 6.8352 (3) Å
  • b = 30.3999 (11) Å
  • c = 7.5409 (3) Å
  • β = 97.375 (2)°
  • V = 1553.96 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 293 K
  • 0.43 × 0.32 × 0.21 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.965, T max = 0.983
  • 18651 measured reflections
  • 3181 independent reflections
  • 2166 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.148
  • S = 1.07
  • 3181 reflections
  • 199 parameters
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035314/cv2611sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035314/cv2611Isup2.hkl

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

supplementary crystallographic information

Comment

The pyrazolo[1,5-a]pyridine derivatives have been of interest for their pharmacological and biological activities. Considerable efforts of our group have been devoted to the development of novel pyrazolo[1,5-a]pyridine compounds(Ge et al., 2009). In continuation of this work, we report here the crystal structure of the title compound, (I) (Fig. 1).

In (I), all bond lengths are normal and in a good agreement with those reported previously (Shao et al., 2009). Atoms O2/O3/C15/C16/C17/C18 lie in 1H-pyrazolo[1,5-a]pyridine (C8—C14/N1/N2) plane with the maximum deviation of 0.065 (3) Å for O2. The 1H-pyrazolo[1,5-a]pyridine plane forms dihedral angle of 13.45 (3)° with the benzene ring (C2—C7).

In the crystal structure, weak intermolecular C–H···O hydrogen bond (Table 1) link the molecules into chains propagated in direction [201].

Experimental

To a 50-ml round-bottomed flask were added 3-p-tolyl-1H-pyrazole-5-carbaldehyde(6.0 mmol), ethyl 4-bromo-3-methylbut-2-enoate (7.2 mmol), potassium carbonate (1.60 g, 12.5 mmol) and DMF (10 mL). The mixture was stirred at rt for 8 h and then filtered. The filtrate was poured into water (100 ml) and extracted with CH2Cl2 (3 x 30 ml). The combined extracts were washed with water (2 x 50 ml), dried over anhydrous MgSO4 and filtered, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography (yield 75%). Crystals of (I) suitable for X-ray diffraction were obtained by slow cooling of the refluxed solution of the product in ethyl acetate at room temperature for 2 d.

Refinement

All H atoms were placed in calculated positions [C–H = 0.93–0.97 Å], and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C) for the methyl H atoms.

Figures

Fig. 1.
View of the title compound, with displacement ellipsoids drawn at the 40% probability level.

Crystal data

C18H18N2O2F(000) = 624
Mr = 294.34Dx = 1.258 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4574 reflections
a = 6.8352 (3) Åθ = 2.7–24.2°
b = 30.3999 (11) ŵ = 0.08 mm1
c = 7.5409 (3) ÅT = 293 K
β = 97.375 (2)°Block, colourless
V = 1553.96 (11) Å30.43 × 0.32 × 0.21 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer3181 independent reflections
Radiation source: fine-focus sealed tube2166 reflections with I > 2σ(I)
graphiteRint = 0.036
[var phi] and ω scansθmax = 26.3°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −8→8
Tmin = 0.965, Tmax = 0.983k = −37→37
18651 measured reflectionsl = −9→9

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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0589P)2 + 0.5452P] where P = (Fo2 + 2Fc2)/3
3181 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.22 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
N10.3372 (2)0.65607 (5)0.5370 (2)0.0429 (4)
N20.3988 (2)0.61395 (6)0.5589 (2)0.0482 (4)
O20.3651 (2)0.81645 (4)0.5569 (2)0.0561 (4)
O30.0666 (3)0.80858 (6)0.4073 (3)0.0806 (6)
C11.0771 (5)0.46224 (8)0.7690 (4)0.0820 (8)
H1A1.21230.47110.79750.123*
H1B1.06270.44500.66150.123*
H1C1.03860.44500.86540.123*
C20.9475 (4)0.50258 (8)0.7418 (3)0.0589 (6)
C31.0264 (4)0.54415 (8)0.7553 (3)0.0638 (6)
H3A1.16190.54740.78520.077*
C40.9101 (3)0.58130 (7)0.7255 (3)0.0563 (6)
H4A0.96830.60900.73660.068*
C50.7080 (3)0.57786 (6)0.6794 (3)0.0460 (5)
C60.6282 (4)0.53587 (7)0.6683 (3)0.0636 (6)
H6A0.49270.53240.63920.076*
C70.7463 (4)0.49920 (8)0.6995 (4)0.0695 (7)
H7A0.68850.47150.69180.083*
C80.5871 (3)0.61754 (6)0.6386 (3)0.0435 (5)
C90.6428 (3)0.66109 (7)0.6684 (3)0.0464 (5)
H9A0.76430.67140.72210.056*
C100.4813 (3)0.68603 (6)0.6023 (3)0.0423 (5)
C110.4335 (3)0.73089 (6)0.5842 (3)0.0440 (5)
H11A0.52600.75190.62880.053*
C120.2535 (3)0.74423 (7)0.5024 (2)0.0412 (5)
C130.1075 (3)0.71204 (7)0.4353 (3)0.0441 (5)
C140.1553 (3)0.66890 (7)0.4564 (3)0.0473 (5)
H14A0.06280.64760.41530.057*
C15−0.0942 (3)0.72349 (8)0.3412 (3)0.0557 (6)
H15A−0.16600.69700.30830.084*
H15B−0.08070.74030.23570.084*
H15C−0.16440.74050.41970.084*
C160.2140 (3)0.79236 (7)0.4827 (3)0.0476 (5)
C170.3473 (4)0.86376 (7)0.5387 (3)0.0624 (6)
H17A0.24080.87440.60070.075*
H17B0.31900.87180.41350.075*
C180.5387 (4)0.88348 (8)0.6182 (3)0.0757 (8)
H18A0.53130.91490.60780.114*
H18B0.64290.87270.55570.114*
H18C0.56490.87550.74210.114*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0375 (9)0.0432 (10)0.0472 (9)−0.0043 (7)0.0016 (7)−0.0009 (7)
N20.0473 (10)0.0404 (10)0.0560 (10)−0.0027 (8)0.0035 (8)−0.0002 (8)
O20.0546 (9)0.0407 (9)0.0710 (10)−0.0009 (7)0.0008 (7)0.0056 (7)
O30.0562 (10)0.0558 (11)0.1210 (15)0.0076 (8)−0.0225 (10)0.0140 (10)
C10.101 (2)0.0602 (17)0.0863 (19)0.0314 (15)0.0167 (16)0.0084 (14)
C20.0711 (17)0.0490 (14)0.0574 (13)0.0134 (12)0.0116 (11)0.0033 (10)
C30.0520 (14)0.0598 (16)0.0790 (17)0.0093 (12)0.0058 (12)0.0061 (12)
C40.0516 (13)0.0448 (13)0.0719 (15)0.0004 (10)0.0062 (11)0.0037 (11)
C50.0476 (12)0.0423 (12)0.0487 (11)0.0007 (9)0.0078 (9)−0.0003 (9)
C60.0553 (14)0.0488 (14)0.0850 (17)−0.0039 (11)0.0027 (12)−0.0019 (12)
C70.0785 (18)0.0384 (13)0.0909 (19)−0.0012 (12)0.0081 (14)0.0013 (12)
C80.0414 (11)0.0436 (12)0.0454 (11)−0.0024 (9)0.0050 (9)0.0006 (9)
C90.0388 (11)0.0441 (12)0.0547 (12)−0.0031 (9)−0.0007 (9)0.0001 (9)
C100.0372 (10)0.0432 (12)0.0455 (11)−0.0049 (9)0.0022 (8)−0.0004 (8)
C110.0405 (11)0.0407 (11)0.0500 (11)−0.0051 (9)0.0022 (9)−0.0001 (9)
C120.0374 (10)0.0451 (12)0.0411 (10)−0.0001 (9)0.0045 (8)0.0038 (8)
C130.0361 (10)0.0534 (13)0.0425 (11)−0.0011 (9)0.0036 (8)0.0030 (9)
C140.0367 (11)0.0533 (13)0.0502 (12)−0.0071 (9)−0.0008 (9)−0.0013 (9)
C150.0408 (12)0.0626 (14)0.0609 (14)−0.0007 (10)−0.0042 (10)0.0036 (11)
C160.0406 (11)0.0510 (13)0.0512 (12)0.0006 (10)0.0055 (9)0.0055 (10)
C170.0741 (17)0.0418 (13)0.0731 (16)0.0030 (12)0.0157 (13)0.0056 (11)
C180.094 (2)0.0588 (16)0.0740 (17)−0.0194 (14)0.0101 (15)−0.0054 (13)

Geometric parameters (Å, °)

N1—N21.351 (2)C7—H7A0.9300
N1—C141.369 (2)C8—C91.388 (3)
N1—C101.385 (2)C9—C101.379 (3)
N2—C81.353 (2)C9—H9A0.9300
O2—C161.330 (2)C10—C111.405 (3)
O2—C171.448 (3)C11—C121.365 (3)
O3—C161.198 (2)C11—H11A0.9300
C1—C21.511 (3)C12—C131.442 (3)
C1—H1A0.9600C12—C161.492 (3)
C1—H1B0.9600C13—C141.356 (3)
C1—H1C0.9600C13—C151.508 (3)
C2—C31.373 (3)C14—H14A0.9300
C2—C71.375 (4)C15—H15A0.9600
C3—C41.383 (3)C15—H15B0.9600
C3—H3A0.9300C15—H15C0.9600
C4—C51.384 (3)C17—C181.493 (3)
C4—H4A0.9300C17—H17A0.9700
C5—C61.386 (3)C17—H17B0.9700
C5—C81.472 (3)C18—H18A0.9600
C6—C71.379 (3)C18—H18B0.9600
C6—H6A0.9300C18—H18C0.9600
N2—N1—C14125.13 (17)C9—C10—C11137.25 (19)
N2—N1—C10112.56 (16)N1—C10—C11117.27 (17)
C14—N1—C10122.30 (17)C12—C11—C10121.13 (18)
N1—N2—C8103.98 (15)C12—C11—H11A119.4
C16—O2—C17117.10 (17)C10—C11—H11A119.4
C2—C1—H1A109.5C11—C12—C13120.00 (19)
C2—C1—H1B109.5C11—C12—C16118.51 (18)
H1A—C1—H1B109.5C13—C12—C16121.49 (17)
C2—C1—H1C109.5C14—C13—C12117.99 (18)
H1A—C1—H1C109.5C14—C13—C15118.08 (18)
H1B—C1—H1C109.5C12—C13—C15123.93 (19)
C3—C2—C7117.3 (2)C13—C14—N1121.30 (19)
C3—C2—C1121.3 (2)C13—C14—H14A119.3
C7—C2—C1121.5 (2)N1—C14—H14A119.3
C2—C3—C4121.8 (2)C13—C15—H15A109.5
C2—C3—H3A119.1C13—C15—H15B109.5
C4—C3—H3A119.1H15A—C15—H15B109.5
C3—C4—C5120.9 (2)C13—C15—H15C109.5
C3—C4—H4A119.6H15A—C15—H15C109.5
C5—C4—H4A119.6H15B—C15—H15C109.5
C4—C5—C6117.2 (2)O3—C16—O2122.3 (2)
C4—C5—C8120.38 (19)O3—C16—C12125.6 (2)
C6—C5—C8122.4 (2)O2—C16—C12112.17 (17)
C7—C6—C5121.1 (2)O2—C17—C18107.6 (2)
C7—C6—H6A119.4O2—C17—H17A110.2
C5—C6—H6A119.4C18—C17—H17A110.2
C2—C7—C6121.7 (2)O2—C17—H17B110.2
C2—C7—H7A119.2C18—C17—H17B110.2
C6—C7—H7A119.2H17A—C17—H17B108.5
N2—C8—C9111.98 (17)C17—C18—H18A109.5
N2—C8—C5120.22 (18)C17—C18—H18B109.5
C9—C8—C5127.78 (18)H18A—C18—H18B109.5
C10—C9—C8106.01 (17)C17—C18—H18C109.5
C10—C9—H9A127.0H18A—C18—H18C109.5
C8—C9—H9A127.0H18B—C18—H18C109.5
C9—C10—N1105.47 (17)
C14—N1—N2—C8178.09 (17)C14—N1—C10—C9−178.47 (17)
C10—N1—N2—C8−0.5 (2)N2—N1—C10—C11179.20 (16)
C7—C2—C3—C4−0.8 (4)C14—N1—C10—C110.5 (3)
C1—C2—C3—C4178.1 (2)C9—C10—C11—C12177.3 (2)
C2—C3—C4—C5−0.5 (4)N1—C10—C11—C12−1.3 (3)
C3—C4—C5—C61.3 (3)C10—C11—C12—C131.0 (3)
C3—C4—C5—C8−176.7 (2)C10—C11—C12—C16−178.23 (18)
C4—C5—C6—C7−0.9 (4)C11—C12—C13—C140.0 (3)
C8—C5—C6—C7177.0 (2)C16—C12—C13—C14179.22 (18)
C3—C2—C7—C61.2 (4)C11—C12—C13—C15−179.27 (19)
C1—C2—C7—C6−177.6 (2)C16—C12—C13—C15−0.1 (3)
C5—C6—C7—C2−0.4 (4)C12—C13—C14—N1−0.7 (3)
N1—N2—C8—C90.7 (2)C15—C13—C14—N1178.58 (18)
N1—N2—C8—C5−178.00 (17)N2—N1—C14—C13−178.02 (18)
C4—C5—C8—N2166.40 (19)C10—N1—C14—C130.5 (3)
C6—C5—C8—N2−11.4 (3)C17—O2—C16—O3−1.8 (3)
C4—C5—C8—C9−12.0 (3)C17—O2—C16—C12177.15 (17)
C6—C5—C8—C9170.1 (2)C11—C12—C16—O3176.6 (2)
N2—C8—C9—C10−0.6 (2)C13—C12—C16—O3−2.6 (3)
C5—C8—C9—C10177.97 (19)C11—C12—C16—O2−2.3 (3)
C8—C9—C10—N10.2 (2)C13—C12—C16—O2178.51 (17)
C8—C9—C10—C11−178.5 (2)C16—O2—C17—C18−175.41 (18)
N2—N1—C10—C90.2 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C9—H9A···O3i0.932.423.339 (3)170

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2611).

References

  • Bruker (1998). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (1999). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ge, Y. Q., Jia, J., Li, Y., Yin, L. & Wang, J. W. (2009). Heterocycles, 78, 197–206.
  • Shao, T., Zhao, G. & Wang, J. (2009). Acta Cryst. E65, o923. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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