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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1158.
Published online 2009 April 30. doi:  10.1107/S1600536809015153
PMCID: PMC2977824

Dimethyl 1-(2-cyano­benz­yl)-1H-pyrazole-3,5-dicarboxyl­ate

Abstract

In the mol­ecule of the title compound, C15H13N3O4, the dihedral angle between the pyrazole and benzene rings is 79.89 (6)°. An intra­molecular C—H(...)O hydrogen bond is present. The crystal structure is stabilized by π–π stacking inter­actions between centrosymmetrically related pyrazole rings with a centroid–centroid distance of 3.500 (3) Å.

Related literature

For the use of pyrazoles as ligands, see: Dvorak et al. (2005 [triangle]). For the use of nitrile derivatives in the synthesis of heterocyclic compounds, see: Radl et al. (2000 [triangle]). For a related structure, see: Fu & Zhao (2007 [triangle]).

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Object name is e-65-o1158-scheme1.jpg

Experimental

Crystal data

  • C15H13N3O4
  • M r = 299.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1158-efi1.jpg
  • a = 7.2416 (19) Å
  • b = 10.977 (3) Å
  • c = 18.405 (4) Å
  • β = 100.670 (11)°
  • V = 1437.7 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 291 K
  • 0.35 × 0.30 × 0.25 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.968, T max = 0.980
  • 14431 measured reflections
  • 3287 independent reflections
  • 2452 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.130
  • S = 1.09
  • 3287 reflections
  • 201 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL/PC.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015153/rz2312sup1.cif

Structure factors: contains datablocks I, I. DOI: 10.1107/S1600536809015153/rz2312Isup2.hkl

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

Acknowledgments

This work was supported by the Southeast University Fund for Young Researchers (4007041027).

supplementary crystallographic information

Comment

Pyrazoles are considered as extremely versatile building blocks in organic chemistry. They constitute key fragments in active pharmaceutical and agrochemical ingredients, which have found widespread use as ligands for transition metals (Dvorak et al., 2005), In addition, nitrile derivatives are important materials in the synthesis of some heterocyclic molecules (Radl et al., 2000). Recently, we have reported a few benzonitrile compounds (Fu & Zhao, 2007). As an extension of our work on the structural characterization of nitrile compounds, the structure of the title compound is reported here.

In the molecule of the title compound (Fig. 1) bond lengths and angles have normal values. The dihedral angle between the planes of the pyrazole and phenyl rings is 79.89 (6) °. The molecular conformation is stabilized by an intramolecular C—H···O hydrogen bond (Table 1). In the crystal packing, centrosymmetrically related molecules at (x, y, z) and (2-x, -y, -z) are connected by a π-π stacking interaction involving the pyrazole rings, with a centroid-centroid separation of 3.500 (3) Å, a perpendicular interplanar distance of 3.382 (3) and a centroid-centroid offset of 0.901 (2) Å.

Experimental

1H-Pyrazole-3,5-dicarboxylic acid dimethyl ester (0.185 mg, 1 mmol) and 2-(bromomethyl)benzonitrile (0.196 mg, 1 mmol) were dissolved in acetone in the presence of K2CO3 (0.138 mg, 1 mmol) and heated under reflux for 1 day. After the mixture was cooled to room temperature, the solution was filtered and the solvents removed in vacuum to afford a white precipitate of the title compound. Colourless crystals suitable for X-ray diffraction were obtained after 9 days by slow evaporation of a diethylether solution.

Refinement

All H atoms were detected in a difference Fourier map, but were placed in calculated positions and refined using a riding motion approximation, with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C15H13N3O4F(000) = 624
Mr = 299.28Dx = 1.383 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3210 reflections
a = 7.2416 (19) Åθ = 2.9–27.5°
b = 10.977 (3) ŵ = 0.10 mm1
c = 18.405 (4) ÅT = 291 K
β = 100.670 (11)°Prism, colourless
V = 1437.7 (6) Å30.35 × 0.30 × 0.25 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer3287 independent reflections
Radiation source: fine-focus sealed tube2452 reflections with I > 2σ(I)
graphiteRint = 0.040
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 2.9°
ω scansh = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −14→14
Tmin = 0.968, Tmax = 0.980l = −23→23
14431 measured reflections

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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0618P)2 + 0.1406P] where P = (Fo2 + 2Fc2)/3
3287 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = −0.19 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
C10.7452 (2)−0.11741 (14)−0.00030 (8)0.0384 (4)
C20.7207 (2)0.00398 (14)−0.02209 (9)0.0384 (4)
H20.65930.0337−0.06750.046*
C30.8066 (2)0.07034 (14)0.03796 (9)0.0369 (4)
C40.6825 (2)−0.22943 (15)−0.04182 (9)0.0430 (4)
C50.5284 (3)−0.3033 (2)−0.15741 (12)0.0698 (6)
H5A0.6333−0.3544−0.16180.105*
H5B0.4715−0.2736−0.20540.105*
H5C0.4378−0.3494−0.13680.105*
C60.8293 (2)0.20236 (15)0.04805 (9)0.0419 (4)
C70.7579 (3)0.39182 (17)−0.01060 (12)0.0691 (6)
H7A0.69400.42590.02590.104*
H7B0.70380.4234−0.05840.104*
H7C0.88860.41320.00090.104*
C80.9833 (2)0.00848 (16)0.16631 (9)0.0438 (4)
H8A1.06960.07580.16550.053*
H8B1.0572−0.06350.18260.053*
C90.8571 (2)0.03652 (14)0.22102 (9)0.0409 (4)
C100.9142 (2)0.11795 (15)0.27911 (9)0.0455 (4)
C110.8042 (3)0.13819 (17)0.33260 (10)0.0572 (5)
H110.84470.19190.37140.069*
C120.6365 (3)0.0788 (2)0.32785 (11)0.0639 (5)
H120.56230.09240.36330.077*
C130.5775 (3)−0.0008 (2)0.27081 (12)0.0636 (5)
H130.4631−0.04080.26770.076*
C140.6869 (3)−0.02201 (17)0.21785 (10)0.0519 (4)
H140.6452−0.07640.17960.062*
C151.0869 (3)0.18543 (18)0.28545 (10)0.0560 (5)
N10.87843 (18)−0.01204 (12)0.09157 (7)0.0385 (3)
N20.84141 (19)−0.12686 (12)0.06921 (7)0.0414 (3)
N31.2207 (3)0.24250 (19)0.29236 (11)0.0811 (6)
O10.7088 (2)−0.33067 (12)−0.01849 (7)0.0649 (4)
O20.5924 (2)−0.20179 (11)−0.10967 (7)0.0574 (4)
O30.9169 (2)0.25110 (12)0.10214 (7)0.0645 (4)
O40.7390 (2)0.26063 (10)−0.01091 (7)0.0568 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0436 (9)0.0354 (8)0.0381 (9)0.0005 (7)0.0124 (7)0.0002 (6)
C20.0426 (9)0.0358 (8)0.0364 (8)0.0020 (6)0.0068 (7)−0.0002 (6)
C30.0405 (8)0.0315 (8)0.0404 (8)0.0021 (6)0.0121 (7)0.0012 (6)
C40.0520 (10)0.0354 (9)0.0437 (9)−0.0026 (7)0.0140 (8)−0.0022 (7)
C50.0987 (17)0.0559 (12)0.0525 (12)−0.0175 (11)0.0084 (11)−0.0181 (9)
C60.0468 (9)0.0367 (9)0.0433 (9)0.0000 (7)0.0112 (7)−0.0030 (7)
C70.1012 (17)0.0315 (10)0.0721 (14)−0.0033 (10)0.0092 (12)0.0056 (9)
C80.0463 (9)0.0459 (10)0.0377 (9)0.0035 (7)0.0041 (7)−0.0006 (7)
C90.0487 (9)0.0368 (8)0.0366 (8)0.0070 (7)0.0058 (7)0.0040 (6)
C100.0579 (10)0.0394 (9)0.0377 (9)0.0082 (7)0.0050 (8)0.0025 (7)
C110.0759 (13)0.0531 (12)0.0438 (10)0.0114 (9)0.0148 (10)−0.0049 (8)
C120.0738 (14)0.0707 (14)0.0537 (11)0.0150 (11)0.0288 (10)0.0053 (10)
C130.0589 (12)0.0713 (14)0.0646 (13)−0.0013 (10)0.0220 (10)0.0057 (10)
C140.0577 (11)0.0501 (11)0.0484 (10)−0.0008 (8)0.0114 (9)−0.0012 (8)
C150.0632 (12)0.0537 (12)0.0484 (10)0.0007 (9)0.0030 (9)−0.0093 (8)
N10.0453 (8)0.0350 (7)0.0356 (7)0.0015 (5)0.0089 (6)−0.0003 (5)
N20.0523 (8)0.0324 (7)0.0407 (7)0.0006 (6)0.0122 (6)0.0003 (5)
N30.0735 (13)0.0847 (14)0.0806 (14)−0.0193 (11)0.0024 (10)−0.0156 (11)
O10.0995 (11)0.0333 (7)0.0601 (8)−0.0036 (7)0.0103 (8)0.0019 (6)
O20.0811 (9)0.0403 (7)0.0458 (7)−0.0055 (6)−0.0011 (6)−0.0065 (5)
O30.0864 (10)0.0431 (7)0.0573 (8)−0.0058 (7)−0.0037 (7)−0.0088 (6)
O40.0792 (9)0.0307 (6)0.0555 (8)0.0007 (6)−0.0005 (7)0.0026 (5)

Geometric parameters (Å, °)

C1—N21.343 (2)C7—H7C0.9600
C1—C21.393 (2)C8—N11.460 (2)
C1—C41.474 (2)C8—C91.512 (2)
C2—C31.373 (2)C8—H8A0.9700
C2—H20.9300C8—H8B0.9700
C3—N11.368 (2)C9—C141.381 (3)
C3—C61.466 (2)C9—C101.396 (2)
C4—O11.194 (2)C10—C111.394 (3)
C4—O21.332 (2)C10—C151.440 (3)
C5—O21.441 (2)C11—C121.367 (3)
C5—H5A0.9600C11—H110.9300
C5—H5B0.9600C12—C131.372 (3)
C5—H5C0.9600C12—H120.9300
C6—O31.202 (2)C13—C141.385 (3)
C6—O41.324 (2)C13—H130.9300
C7—O41.446 (2)C14—H140.9300
C7—H7A0.9600C15—N31.141 (3)
C7—H7B0.9600N1—N21.3376 (18)
N2—C1—C2111.35 (14)C9—C8—H8A109.1
N2—C1—C4119.02 (14)N1—C8—H8B109.1
C2—C1—C4129.63 (15)C9—C8—H8B109.1
C3—C2—C1105.13 (14)H8A—C8—H8B107.8
C3—C2—H2127.4C14—C9—C10117.76 (16)
C1—C2—H2127.4C14—C9—C8121.46 (15)
N1—C3—C2106.57 (13)C10—C9—C8120.69 (16)
N1—C3—C6122.89 (14)C11—C10—C9121.04 (18)
C2—C3—C6130.53 (15)C11—C10—C15117.53 (17)
O1—C4—O2124.53 (16)C9—C10—C15121.42 (16)
O1—C4—C1125.21 (16)C12—C11—C10119.74 (18)
O2—C4—C1110.25 (14)C12—C11—H11120.1
O2—C5—H5A109.5C10—C11—H11120.1
O2—C5—H5B109.5C11—C12—C13119.98 (18)
H5A—C5—H5B109.5C11—C12—H12120.0
O2—C5—H5C109.5C13—C12—H12120.0
H5A—C5—H5C109.5C12—C13—C14120.5 (2)
H5B—C5—H5C109.5C12—C13—H13119.7
O3—C6—O4124.65 (16)C14—C13—H13119.7
O3—C6—C3125.05 (16)C9—C14—C13120.93 (18)
O4—C6—C3110.30 (14)C9—C14—H14119.5
O4—C7—H7A109.5C13—C14—H14119.5
O4—C7—H7B109.5N3—C15—C10177.0 (2)
H7A—C7—H7B109.5N2—N1—C3111.90 (13)
O4—C7—H7C109.5N2—N1—C8118.35 (13)
H7A—C7—H7C109.5C3—N1—C8129.75 (14)
H7B—C7—H7C109.5N1—N2—C1105.04 (12)
N1—C8—C9112.67 (14)C4—O2—C5116.21 (14)
N1—C8—H8A109.1C6—O4—C7116.47 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8A···O30.972.412.917 (2)112

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2312).

References

  • Dvorak, C.-A., Rudolph, D. A., Ma, S. & Carruthers, N. I. (2005). J. Org. Chem.70, 4188–4190. [PubMed]
  • Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206.
  • Radl, S., Hezky, P., Konvicka, P. & Krejci, J. (2000). Collect. Czech. Chem. Commun.65, 1093–1108.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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