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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o64.
Published online 2007 December 6. doi:  10.1107/S1600536807057297
PMCID: PMC2915022

Ethyl 5-(ethoxy­carbon­yl)-3-(4-methoxy­phen­yl)-1H-pyrazole-1-acetate

Abstract

In the title compound, C17H20N2O5, all bond lengths and angles show normal values. The dihedral angle between the pyrazole ring and the benzene ring is 6.98 (11)°. The mol­ecules are linked by inter­molecular C—H(...)π inter­actions.

Related literature

For related literature, see: Allen et al. (1987 [triangle]); Brough et al. (2005 [triangle]); Cheng et al. (2006 [triangle]); Dong et al. (2007 [triangle]); Sehon et al. (2006 [triangle]); Wei et al. (2006 [triangle]); Xia et al. (2007 [triangle]).

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Object name is e-64-00o64-scheme1.jpg

Experimental

Crystal data

  • C17H20N2O5
  • M r = 332.35
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o64-efi1.jpg
  • a = 7.4267 (1) Å
  • b = 11.0511 (2) Å
  • c = 11.7139 (2) Å
  • α = 106.721 (1)°
  • β = 97.898 (1)°
  • γ = 106.796 (1)°
  • V = 855.59 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 296 (2) K
  • 0.45 × 0.39 × 0.28 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.846, T max = 0.974
  • 13041 measured reflections
  • 3806 independent reflections
  • 2376 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.166
  • S = 1.06
  • 3806 reflections
  • 221 parameters
  • 3 restraints
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
X—H(...)π-ring interactions calculated by PLATON (Spek, 2003 [triangle]). Cg i is a centroid of the pyrazole ring N1/N2/C8/C9/C10

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807057297/fj2063sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807057297/fj2063Isup2.hkl

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

Acknowledgments

This study was supported by the Natural Science Foundation of Shandong Province (grant No. Y2005B12).

supplementary crystallographic information

Comment

The pyrazole unit is one of the core structures in a number of natural products. Many pyrazole derivatives are known to exhibit a wide range of biological properties such as antagonists (Sehon et al., 2006), anti-inflammatory (Cheng et al., 2006), inhibitors of the Hsp90 (Brough et al., 2005), antitumor (Wei et al., 2006; Xia et al., 2007). In our previous paper, we reported the crystal structure of ethyl 3-(4-chlorophenyl)-5-(ethoxycarbonyl)-1H-pyrazole-1-acetate (Dong et al., 2007). We report here the crystal structure of the title compound, (I).

In compound (I) (Fig. 1), all bond lengths and angles are normal (Allen et al., 1987). The dihedral angles between the rings of the pyrazole and the benzene ring is 6.98 (11)o. The two ethyl carboxylate groups are inclined to the attached pyrazole ring by 2.16 (9)o and 75.95 (11)o, respectively. The molecules are linked into a network parallel by C—H···π interactions (Table 1) involving the pyrazole ring (centroid Cg1). We report here the crystal structure of the title compound, (I).

Experimental

A mixture of ethyl 3-(4-methoxyphenyl)-1H-pyrazole-5-carboxylate (0.01 mol), ethyl chloroacetate (0.015 mol) and potassium carbonate (0.02 mol) in acetonitrile (50 ml) was heated to reflux for 15 h. The solvent was removed under reduced pressure, and the residue was dissolved in the mixture of water (50 ml) and ethyl acetate (50 ml). After separated, the water phase was extracted with ethyl acetate (25 ml), and then the organic phase was combined, dried over anhydrous magnesium sulfate and filtered. The solvent was removed under reduced pressure. The solid product was recrystallized from ethyl acetate (yield 55%). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in ethyl acetate at room temperature for 6 d.

Refinement

All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.97 Å (for CH2 groups) and 0.96 Å (for CH3 groups), their isotropic displacement parameters were set to 1.2 times (1.5times for CH3 groups) the equivalent displacement parameter of their parent atoms.

Figures

Fig. 1.
The structure of the title molecule showing displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
Packing view of (I), shown down the a axis.

Crystal data

C17H20N2O5Z = 2
Mr = 332.35F000 = 352
Triclinic, P1Dx = 1.290 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.4267 (1) ÅCell parameters from 3567 reflections
b = 11.0511 (2) Åθ = 3.0–24.5º
c = 11.7139 (2) ŵ = 0.10 mm1
α = 106.721 (1)ºT = 296 (2) K
β = 97.898 (1)ºPrism, colourless
γ = 106.796 (1)º0.45 × 0.39 × 0.28 mm
V = 855.59 (3) Å3

Data collection

Bruker APEXII CCD area-detector diffractometer3806 independent reflections
Radiation source: fine-focus sealed tube2376 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 296(2) Kθmax = 27.5º
[var phi] and ω scansθmin = 2.3º
Absorption correction: multi-scan(SADABS; Bruker, 2005)h = −9→9
Tmin = 0.846, Tmax = 0.974k = −14→14
13041 measured reflectionsl = −15→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.166  w = 1/[σ2(Fo2) + (0.0775P)2 + 0.1127P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
3806 reflectionsΔρmax = 0.32 e Å3
221 parametersΔρmin = −0.16 e Å3
3 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.016 (4)

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
C1−0.7281 (3)0.0919 (3)0.9802 (3)0.1071 (8)
H1A−0.78150.09970.90430.161*
H1B−0.81480.09901.03340.161*
H1C−0.71100.00620.96390.161*
C2−0.4043 (3)0.2015 (2)0.9716 (2)0.0792 (5)
C3−0.2328 (3)0.3033 (2)1.0311 (2)0.0871 (6)
H3−0.21830.36261.10910.104*
C4−0.0829 (3)0.3176 (2)0.9754 (2)0.0815 (6)
H40.03390.38721.01700.098*
C5−0.0974 (3)0.23132 (17)0.85765 (17)0.0676 (5)
C6−0.2716 (3)0.1283 (2)0.7993 (2)0.0783 (6)
H6−0.28650.06850.72140.094*
C7−0.4285 (3)0.1127 (2)0.8567 (2)0.0823 (6)
H7−0.54620.04320.81710.099*
C80.0682 (3)0.25088 (16)0.80054 (16)0.0645 (5)
C90.0946 (3)0.17110 (17)0.69185 (17)0.0674 (5)
H90.00620.08980.63650.081*
C100.2765 (3)0.23673 (16)0.68338 (16)0.0640 (5)
C110.5351 (3)0.46068 (18)0.81994 (17)0.0722 (5)
H11A0.63970.42480.81650.087*
H11B0.55510.51870.90380.087*
C120.5401 (3)0.54247 (18)0.73607 (18)0.0744 (5)
C130.7510 (4)0.7109 (3)0.6817 (3)0.1111 (9)
H13A0.67550.76960.69770.133*
H13B0.71140.65740.59490.133*
C140.9606 (5)0.7918 (3)0.7167 (3)0.1405 (13)
H14A0.99960.84090.80340.211*
H14B0.98430.85390.67300.211*
H14C1.03350.73300.69630.211*
C150.3773 (3)0.19420 (18)0.58813 (18)0.0714 (5)
C160.6729 (3)0.2462 (3)0.5236 (2)0.0952 (7)
H16A0.60790.22750.43950.114*
H16B0.70060.16700.52870.114*
C170.8560 (4)0.3647 (3)0.5629 (3)0.1128 (9)
H17A0.82930.43830.54520.169*
H17B0.94830.34120.51930.169*
H17C0.90800.39090.64960.169*
N10.2268 (2)0.36044 (14)0.85650 (14)0.0697 (4)
N20.3521 (2)0.35071 (14)0.78541 (14)0.0664 (4)
O1−0.5490 (2)0.19486 (17)1.03670 (16)0.1040 (5)
O20.4038 (2)0.53626 (15)0.66541 (16)0.1015 (5)
O30.7201 (2)0.62366 (14)0.75458 (13)0.0866 (5)
O40.3061 (2)0.08992 (16)0.50282 (15)0.1068 (6)
O50.55182 (19)0.28057 (13)0.60626 (13)0.0793 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0884 (16)0.0961 (16)0.127 (2)0.0173 (13)0.0019 (14)0.0497 (15)
C20.0858 (13)0.0741 (12)0.0800 (12)0.0337 (11)0.0114 (10)0.0275 (9)
C30.0879 (15)0.0757 (13)0.0808 (14)0.0253 (11)0.0101 (12)0.0105 (10)
C40.0789 (13)0.0690 (12)0.0812 (14)0.0205 (10)0.0088 (11)0.0137 (10)
C50.0714 (11)0.0561 (9)0.0686 (11)0.0195 (8)0.0012 (9)0.0217 (8)
C60.0816 (13)0.0689 (11)0.0720 (12)0.0169 (10)0.0042 (10)0.0220 (9)
C70.0760 (12)0.0665 (11)0.0860 (13)0.0112 (9)−0.0028 (10)0.0234 (9)
C80.0682 (11)0.0522 (9)0.0622 (10)0.0151 (8)−0.0010 (8)0.0176 (8)
C90.0697 (11)0.0500 (9)0.0656 (11)0.0123 (8)−0.0031 (9)0.0129 (8)
C100.0688 (11)0.0497 (8)0.0575 (10)0.0127 (8)−0.0034 (8)0.0119 (7)
C110.0730 (11)0.0625 (10)0.0548 (10)0.0035 (8)−0.0051 (8)0.0118 (8)
C120.0791 (12)0.0573 (10)0.0655 (11)0.0093 (9)−0.0017 (10)0.0136 (8)
C130.129 (2)0.0820 (15)0.1059 (19)0.0067 (14)0.0078 (16)0.0480 (14)
C140.146 (3)0.106 (2)0.127 (2)−0.0186 (19)0.021 (2)0.0466 (18)
C150.0744 (12)0.0624 (10)0.0650 (11)0.0193 (9)0.0023 (9)0.0152 (9)
C160.0941 (16)0.1076 (17)0.0903 (16)0.0433 (14)0.0266 (13)0.0332 (13)
C170.0953 (17)0.1129 (19)0.150 (3)0.0370 (15)0.0466 (17)0.0653 (19)
N10.0757 (10)0.0590 (8)0.0591 (9)0.0129 (7)0.0038 (8)0.0144 (7)
N20.0691 (9)0.0556 (8)0.0563 (8)0.0093 (7)−0.0014 (7)0.0127 (6)
O10.0940 (11)0.0954 (11)0.1023 (12)0.0215 (9)0.0206 (9)0.0175 (9)
O20.0943 (10)0.0906 (10)0.1036 (12)0.0156 (8)−0.0142 (9)0.0441 (9)
O30.0868 (9)0.0727 (8)0.0778 (9)0.0016 (7)0.0001 (7)0.0287 (7)
O40.0975 (11)0.0835 (10)0.0917 (11)0.0104 (8)0.0154 (9)−0.0146 (8)
O50.0756 (8)0.0742 (8)0.0753 (9)0.0172 (7)0.0137 (7)0.0178 (7)

Geometric parameters (Å, °)

C1—O11.397 (3)C11—C121.512 (3)
C1—H1A0.9600C11—H11A0.9700
C1—H1B0.9600C11—H11B0.9700
C1—H1C0.9600C12—O21.188 (2)
C2—C31.360 (3)C12—O31.325 (2)
C2—C71.370 (3)C13—O31.452 (3)
C2—O11.398 (3)C13—C141.483 (4)
C3—C41.359 (3)C13—H13A0.9700
C3—H30.9300C13—H13B0.9700
C4—C51.402 (3)C14—H14A0.9600
C4—H40.9300C14—H14B0.9600
C5—C61.377 (2)C14—H14C0.9600
C5—C81.470 (3)C15—O41.203 (2)
C6—C71.417 (3)C15—O51.315 (2)
C6—H60.9300C16—O51.455 (3)
C7—H70.9300C16—C171.492 (3)
C8—N11.338 (2)C16—H16A0.9700
C8—C91.400 (3)C16—H16B0.9700
C9—C101.369 (3)C17—H17A0.9600
C9—H90.9300C17—H17B0.9600
C10—N21.368 (2)C17—H17C0.9600
C10—C151.469 (3)N1—N21.338 (2)
C11—N21.449 (2)
O1—C1—H1A109.5H11A—C11—H11B108.0
O1—C1—H1B109.5O2—C12—O3125.12 (19)
H1A—C1—H1B109.5O2—C12—C11125.49 (19)
O1—C1—H1C109.5O3—C12—C11109.39 (16)
H1A—C1—H1C109.5O3—C13—C14107.6 (2)
H1B—C1—H1C109.5O3—C13—H13A110.2
C3—C2—C7121.2 (2)C14—C13—H13A110.2
C3—C2—O1115.1 (2)O3—C13—H13B110.2
C7—C2—O1123.7 (2)C14—C13—H13B110.2
C4—C3—C2119.4 (2)H13A—C13—H13B108.5
C4—C3—H3120.3C13—C14—H14A109.5
C2—C3—H3120.3C13—C14—H14B109.5
C3—C4—C5122.6 (2)H14A—C14—H14B109.5
C3—C4—H4118.7C13—C14—H14C109.5
C5—C4—H4118.7H14A—C14—H14C109.5
C6—C5—C4117.2 (2)H14B—C14—H14C109.5
C6—C5—C8122.06 (18)O4—C15—O5123.9 (2)
C4—C5—C8120.78 (17)O4—C15—C10122.73 (19)
C5—C6—C7120.6 (2)O5—C15—C10113.38 (15)
C5—C6—H6119.7O5—C16—C17106.8 (2)
C7—C6—H6119.7O5—C16—H16A110.4
C2—C7—C6119.0 (2)C17—C16—H16A110.4
C2—C7—H7120.5O5—C16—H16B110.4
C6—C7—H7120.5C17—C16—H16B110.4
N1—C8—C9110.03 (17)H16A—C16—H16B108.6
N1—C8—C5119.14 (17)C16—C17—H17A109.5
C9—C8—C5130.83 (16)C16—C17—H17B109.5
C10—C9—C8106.19 (15)H17A—C17—H17B109.5
C10—C9—H9126.9C16—C17—H17C109.5
C8—C9—H9126.9H17A—C17—H17C109.5
N2—C10—C9106.01 (17)H17B—C17—H17C109.5
N2—C10—C15125.70 (17)C8—N1—N2105.97 (15)
C9—C10—C15128.25 (16)N1—N2—C10111.79 (15)
N2—C11—C12111.51 (14)N1—N2—C11118.33 (14)
N2—C11—H11A109.3C10—N2—C11129.73 (18)
C12—C11—H11A109.3C1—O1—C2117.6 (2)
N2—C11—H11B109.3C12—O3—C13116.71 (17)
C12—C11—H11B109.3C15—O5—C16118.99 (16)
C7—C2—C3—C40.2 (3)C9—C10—C15—O4−0.7 (3)
O1—C2—C3—C4179.65 (19)N2—C10—C15—O5−2.6 (3)
C2—C3—C4—C50.3 (3)C9—C10—C15—O5179.77 (16)
C3—C4—C5—C6−0.7 (3)C9—C8—N1—N2−0.21 (18)
C3—C4—C5—C8179.64 (18)C5—C8—N1—N2179.32 (14)
C4—C5—C6—C70.6 (3)C8—N1—N2—C100.48 (19)
C8—C5—C6—C7−179.75 (16)C8—N1—N2—C11176.47 (14)
C3—C2—C7—C6−0.3 (3)C9—C10—N2—N1−0.56 (19)
O1—C2—C7—C6−179.68 (18)C15—C10—N2—N1−178.58 (15)
C5—C6—C7—C2−0.1 (3)C9—C10—N2—C11−175.96 (16)
C6—C5—C8—N1173.34 (16)C15—C10—N2—C116.0 (3)
C4—C5—C8—N1−7.0 (2)C12—C11—N2—N1−106.75 (19)
C6—C5—C8—C9−7.2 (3)C12—C11—N2—C1068.4 (2)
C4—C5—C8—C9172.38 (18)C3—C2—O1—C1−179.77 (19)
N1—C8—C9—C10−0.12 (19)C7—C2—O1—C1−0.4 (3)
C5—C8—C9—C10−179.58 (16)O2—C12—O3—C13−0.3 (3)
C8—C9—C10—N20.40 (18)C11—C12—O3—C13−179.51 (19)
C8—C9—C10—C15178.35 (16)C14—C13—O3—C12−179.8 (2)
N2—C11—C12—O213.2 (3)O4—C15—O5—C16−4.0 (3)
N2—C11—C12—O3−167.54 (16)C10—C15—O5—C16175.57 (16)
N2—C10—C15—O4176.88 (19)C17—C16—O5—C15177.34 (17)

Table 1 X—H···π-ring interactions calculated by PLATON (Spek, 2003). Cgi is a centroid of the pyrazole ring N1/N2/C8/C9/C10.

X—H···CgX—HH···CgX···CgX—H···Cg
C1—H1A···Cg1i0.962.893.731 (3)147

Symmetry code: (i) 1+x,y,z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2063).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
  • Brough, P. A., Barril, X. & Beswick, M. (2005). Bioorg. Med. Chem. Lett.15, 5197–5201. [PubMed]
  • Bruker (1997). SHELXTL Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2005). APEX2 and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cheng, H., Lundy DeMello, K. M., Li, J. & Sakya, S. M. (2006). Bioorg. Med. Chem. Lett.16, 2076–2080. [PubMed]
  • Dong, W.-L., Dong, W.-L., Xia, Y., Ge, Y.-Q. & Zhao, B.-X. (2007). Acta Cryst. E63, o4468.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Sehon, C., McClure, K., Hack, M., Morton, M., Gomez, L. & Li, L. (2006). Bioorg. Med. Chem. Lett.15, 1677–1680.
  • Sheldrick, G. M. (1997). SHELXL97 University of Göttingen, Germany. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Wei, F., Zhao, B. X., Huang, B., Zhang, L., Sun, C. H., Dong, W. L., Shin, D. S. & Miao, J. Y. (2006). Bioorg. Med. Chem. Lett.16, 6342–6347. [PubMed]
  • Xia, Y., Dong, Z. W., Zhao, B. X., Ge, X., Meng, N., Shin, D. S. & Miao, J. Y. (2007). Bioorg. Med. Chem.15, 6893–6899. [PubMed]

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