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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1132.
Published online 2009 April 25. doi:  10.1107/S1600536809014895
PMCID: PMC2977805

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

Abstract

In the mol­ecule of the title compound, C15H13N3O4, the dihedral angle between the pyrazole and benzene ring planes is 67.7 (1)°. The crystal structure is stabilized by an intra­molecular C—H(...)O hydrogen bond and two weak inter­molecular C—H(...)O inter­actions.

Related literature

For the biological activity of pyrazoles, see: Lee et al. (1989 [triangle]); Chambers et al. (1985 [triangle]). For the importance of nitrile derivatives in the synthesis of some heterocyclic mol­ecules, see: Radl et al. (2000 [triangle]). For related structures, see: Fu & Zhao (2007 [triangle]); Xiao & Zhao (2008a [triangle],b [triangle],c [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1132-scheme1.jpg

Experimental

Crystal data

  • C15H13N3O4
  • M r = 299.28
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1132-efi1.jpg
  • a = 8.783 (3) Å
  • b = 9.538 (4) Å
  • c = 9.999 (4) Å
  • α = 68.42 (3)°
  • β = 71.79 (4)°
  • γ = 82.13 (4)°
  • V = 739.7 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 292 K
  • 0.40 × 0.30 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.968, T max = 0.979
  • 7555 measured reflections
  • 3338 independent reflections
  • 2093 reflections with I > 2σ(I)
  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.147
  • S = 1.05
  • 3338 reflections
  • 201 parameters
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; 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/S1600536809014895/bx2204sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014895/bx2204Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

It is well known that many pyrazole-related molecules have received much attention due to their biological activities (Lee et al., 1989; Chambers et al., 1985). 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 et al., 2007; Xiao et al.,2008a, 2008b,2008c). 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 67.74 (14) °. The molecular conformation is stabilized by an intramolecular C—H···O hydrogen bond and weak intermolecular C—H···O interactions (Table 1)..

Experimental

Dimethyl 1H-Pyrazole-3,5-dicarboxylate (0.185 mg,1 mmol) and 3-(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 d. After the mixture was cooled to room temperature, the solution was filtered and the solvent removed in vacuum to afford a white precipitate of the title compound. Colourless crystals suitable for X-ray diffraction were obtained from a solution of 100 mg in 15 ml diethylether by slow evaporation after 7 d.

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 Caryl—H, Cmethylene—H, Cmethyl—H = 0.93, 097 and 0.96 Å. Uiso(Haryl)=1.2Ueq(Caryl); Uiso(Hmethylene)=1.2Ueq(Cmethylene); Uiso(Hmethyl)=1.5Ueq(Cmethyl).

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

C15H13N3O4Z = 2
Mr = 299.28F(000) = 312
Triclinic, P1Dx = 1.344 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.783 (3) ÅCell parameters from 1442 reflections
b = 9.538 (4) Åθ = 2.4–27.3°
c = 9.999 (4) ŵ = 0.10 mm1
α = 68.42 (3)°T = 292 K
β = 71.79 (4)°Block, colorless
γ = 82.13 (4)°0.40 × 0.30 × 0.20 mm
V = 739.7 (5) Å3

Data collection

Rigaku SCXmini diffractometer3338 independent reflections
Radiation source: fine-focus sealed tube2093 reflections with I > 2σ(I)
graphiteRint = 0.031
Detector resolution: 13.6612 pixels mm-1θmax = 27.4°, θmin = 2.3°
ω scansh = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −12→12
Tmin = 0.968, Tmax = 0.979l = −12→12
7555 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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0636P)2 + 0.0696P] where P = (Fo2 + 2Fc2)/3
3338 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = −0.16 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
C10.2466 (2)0.1608 (2)0.4437 (2)0.0473 (5)
C20.2324 (2)0.0151 (2)0.4487 (2)0.0485 (5)
H20.2544−0.07530.51850.058*
C30.1787 (2)0.0343 (2)0.3276 (2)0.0453 (5)
C40.2972 (2)0.2120 (3)0.5461 (2)0.0530 (5)
C50.1399 (2)−0.0794 (2)0.2763 (2)0.0516 (5)
C60.1126 (2)0.2702 (2)0.1210 (2)0.0513 (5)
H6A0.13880.21050.05610.062*
H6B0.17130.36300.06690.062*
C7−0.0655 (2)0.3076 (2)0.1568 (2)0.0441 (5)
C8−0.1362 (3)0.3905 (2)0.2511 (2)0.0548 (5)
H8−0.07350.42080.29480.066*
C9−0.2976 (3)0.4282 (3)0.2806 (3)0.0618 (6)
H9−0.34290.48180.34530.074*
C10−0.3928 (3)0.3868 (2)0.2143 (2)0.0564 (6)
H10−0.50120.41350.23270.068*
C11−0.3234 (2)0.3050 (2)0.1206 (2)0.0501 (5)
C12−0.1607 (2)0.2639 (2)0.0923 (2)0.0476 (5)
H12−0.11630.20740.03030.057*
C13−0.4218 (3)0.2621 (3)0.0498 (3)0.0625 (6)
C140.3840 (4)0.1361 (3)0.7627 (3)0.0947 (10)
H14A0.46850.20770.71280.142*
H14B0.41990.04700.83090.142*
H14C0.29220.17970.81740.142*
C150.1386 (3)−0.3432 (3)0.3310 (3)0.0756 (7)
H15A0.0277−0.33880.33430.113*
H15B0.1612−0.43580.40420.113*
H15C0.2046−0.33880.23290.113*
N10.2055 (2)0.26560 (19)0.32636 (19)0.0517 (4)
N20.16398 (19)0.18644 (18)0.25641 (17)0.0460 (4)
N3−0.4990 (3)0.2293 (3)−0.0067 (3)0.0878 (7)
O10.2979 (2)0.34090 (19)0.5354 (2)0.0816 (6)
O20.3407 (2)0.09684 (17)0.65206 (18)0.0724 (5)
O30.1723 (2)−0.21721 (16)0.36374 (17)0.0659 (5)
O40.0863 (2)−0.05489 (18)0.1728 (2)0.0769 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0473 (12)0.0513 (12)0.0480 (12)−0.0011 (9)−0.0202 (9)−0.0170 (9)
C20.0510 (12)0.0492 (12)0.0461 (12)−0.0012 (9)−0.0194 (9)−0.0126 (9)
C30.0429 (11)0.0480 (11)0.0461 (11)−0.0024 (8)−0.0145 (9)−0.0153 (9)
C40.0528 (13)0.0599 (14)0.0562 (13)0.0044 (10)−0.0243 (10)−0.0258 (11)
C50.0471 (12)0.0576 (13)0.0532 (13)−0.0022 (9)−0.0164 (10)−0.0206 (10)
C60.0494 (12)0.0601 (13)0.0435 (12)−0.0053 (9)−0.0207 (9)−0.0094 (9)
C70.0505 (12)0.0415 (11)0.0400 (11)−0.0054 (8)−0.0182 (9)−0.0078 (8)
C80.0627 (14)0.0541 (13)0.0594 (13)−0.0035 (10)−0.0279 (11)−0.0232 (10)
C90.0677 (15)0.0597 (14)0.0658 (15)0.0024 (11)−0.0194 (12)−0.0314 (12)
C100.0512 (13)0.0570 (13)0.0634 (14)0.0023 (10)−0.0194 (11)−0.0219 (11)
C110.0499 (12)0.0522 (12)0.0526 (12)−0.0029 (9)−0.0233 (10)−0.0151 (9)
C120.0529 (12)0.0511 (12)0.0459 (11)−0.0005 (9)−0.0206 (9)−0.0195 (9)
C130.0509 (13)0.0758 (16)0.0698 (16)0.0021 (11)−0.0254 (12)−0.0295 (12)
C140.140 (3)0.098 (2)0.0809 (19)0.0188 (18)−0.075 (2)−0.0427 (16)
C150.097 (2)0.0552 (15)0.0804 (18)−0.0088 (13)−0.0245 (15)−0.0280 (13)
N10.0544 (10)0.0532 (10)0.0552 (11)−0.0020 (8)−0.0259 (8)−0.0185 (8)
N20.0464 (9)0.0503 (10)0.0446 (9)−0.0034 (7)−0.0205 (7)−0.0131 (7)
N30.0656 (14)0.124 (2)0.1012 (18)0.0028 (13)−0.0437 (13)−0.0557 (16)
O10.1237 (16)0.0589 (11)0.0919 (13)0.0097 (10)−0.0644 (12)−0.0358 (9)
O20.1047 (14)0.0650 (10)0.0687 (11)0.0110 (9)−0.0542 (10)−0.0268 (8)
O30.0894 (12)0.0511 (9)0.0636 (10)−0.0076 (8)−0.0321 (9)−0.0164 (7)
O40.1025 (14)0.0705 (11)0.0837 (12)0.0033 (9)−0.0579 (11)−0.0317 (9)

Geometric parameters (Å, °)

C1—N11.345 (2)C8—H80.9300
C1—C21.393 (3)C9—C101.387 (3)
C1—C41.482 (3)C9—H90.9300
C2—C31.375 (2)C10—C111.381 (3)
C2—H20.9300C10—H100.9300
C3—N21.369 (2)C11—C121.397 (3)
C3—C51.475 (3)C11—C131.452 (3)
C4—O11.195 (2)C12—H120.9300
C4—O21.325 (2)C13—N31.143 (3)
C5—O41.201 (2)C14—O21.455 (3)
C5—O31.334 (3)C14—H14A0.9600
C6—N21.471 (2)C14—H14B0.9600
C6—C71.514 (3)C14—H14C0.9600
C6—H6A0.9700C15—O31.444 (3)
C6—H6B0.9700C15—H15A0.9600
C7—C121.385 (2)C15—H15B0.9600
C7—C81.395 (3)C15—H15C0.9600
C8—C91.380 (3)N1—N21.347 (2)
N1—C1—C2111.68 (17)C10—C9—H9119.8
N1—C1—C4118.44 (18)C11—C10—C9118.7 (2)
C2—C1—C4129.88 (18)C11—C10—H10120.6
C3—C2—C1104.90 (17)C9—C10—H10120.6
C3—C2—H2127.6C10—C11—C12121.23 (18)
C1—C2—H2127.6C10—C11—C13119.1 (2)
N2—C3—C2107.05 (17)C12—C11—C13119.63 (19)
N2—C3—C5123.21 (17)C7—C12—C11119.83 (19)
C2—C3—C5129.74 (18)C7—C12—H12120.1
O1—C4—O2124.09 (19)C11—C12—H12120.1
O1—C4—C1124.3 (2)N3—C13—C11179.5 (3)
O2—C4—C1111.57 (19)O2—C14—H14A109.5
O4—C5—O3124.0 (2)O2—C14—H14B109.5
O4—C5—C3126.4 (2)H14A—C14—H14B109.5
O3—C5—C3109.59 (18)O2—C14—H14C109.5
N2—C6—C7112.47 (16)H14A—C14—H14C109.5
N2—C6—H6A109.1H14B—C14—H14C109.5
C7—C6—H6A109.1O3—C15—H15A109.5
N2—C6—H6B109.1O3—C15—H15B109.5
C7—C6—H6B109.1H15A—C15—H15B109.5
H6A—C6—H6B107.8O3—C15—H15C109.5
C12—C7—C8118.64 (19)H15A—C15—H15C109.5
C12—C7—C6120.28 (18)H15B—C15—H15C109.5
C8—C7—C6121.05 (17)C1—N1—N2104.90 (16)
C9—C8—C7121.12 (19)N1—N2—C3111.47 (15)
C9—C8—H8119.4N1—N2—C6118.28 (16)
C7—C8—H8119.4C3—N2—C6130.24 (16)
C8—C9—C10120.4 (2)C4—O2—C14115.33 (19)
C8—C9—H9119.8C5—O3—C15117.10 (18)
N1—C1—C2—C3−0.4 (2)C9—C10—C11—C13−179.5 (2)
C4—C1—C2—C3179.1 (2)C8—C7—C12—C110.9 (3)
C1—C2—C3—N20.3 (2)C6—C7—C12—C11−177.04 (18)
C1—C2—C3—C5−179.23 (19)C10—C11—C12—C7−1.1 (3)
N1—C1—C4—O13.2 (3)C13—C11—C12—C7178.51 (18)
C2—C1—C4—O1−176.3 (2)C2—C1—N1—N20.3 (2)
N1—C1—C4—O2−177.21 (18)C4—C1—N1—N2−179.24 (16)
C2—C1—C4—O23.3 (3)C1—N1—N2—C3−0.1 (2)
N2—C3—C5—O4−3.1 (3)C1—N1—N2—C6−179.84 (16)
C2—C3—C5—O4176.4 (2)C2—C3—N2—N1−0.1 (2)
N2—C3—C5—O3177.39 (18)C5—C3—N2—N1179.45 (17)
C2—C3—C5—O3−3.1 (3)C2—C3—N2—C6179.55 (18)
N2—C6—C7—C12−124.57 (19)C5—C3—N2—C6−0.9 (3)
N2—C6—C7—C857.5 (2)C7—C6—N2—N1−87.7 (2)
C12—C7—C8—C90.2 (3)C7—C6—N2—C392.6 (2)
C6—C7—C8—C9178.21 (19)O1—C4—O2—C142.8 (4)
C7—C8—C9—C10−1.3 (3)C1—C4—O2—C14−176.8 (2)
C8—C9—C10—C111.1 (3)O4—C5—O3—C15−0.6 (3)
C9—C10—C11—C120.1 (3)C3—C5—O3—C15178.93 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C15—H15B···O1i0.962.433.363 (3)163
C9—H9···O1ii0.932.533.348 (3)147
C6—H6A···O40.972.412.979 (3)117

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2204).

References

  • Chambers, D., Denny, W. A., Buckleton, J. S. & Clark, G. R. (1985). J. Org. Chem.50, 4736–4738.
  • Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206.
  • Lee, H. H., Cain, B. F., Denny, W. A., Buckleton, J. S. & Clark, G. R. (1989). J. Org. Chem.54, 428–431.
  • 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]
  • Xiao, J. & Zhao, H. (2008a). Acta Cryst. E64, o965. [PMC free article] [PubMed]
  • Xiao, J. & Zhao, H. (2008b). Acta Cryst. E64, o986. [PMC free article] [PubMed]
  • Xiao, J. & Zhao, H. (2008c). Acta Cryst. E64, o1436. [PMC free article] [PubMed]

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