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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1224.
Published online 2008 June 7. doi:  10.1107/S1600536808015006
PMCID: PMC2961666

(3,6-Dichloro­pyridin-2-yl)(3,5-dimethyl-1H-pyrazol-1-yl)methanone

Abstract

In the crystal structure of the title compound, C11H9Cl2N3O, mol­ecules are held together by short inter­molecular Cl(...)Cl contacts [3.319 (1) Å] and C—H(...)N hydrogen bonds, forming two-dimensional networks parallel to (01An external file that holds a picture, illustration, etc.
Object name is e-64-o1224-efi1.jpg).

Related literature

For related literature, see: Mann et al. (1992 [triangle]); Perevalov et al. (2001 [triangle]).

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Object name is e-64-o1224-scheme1.jpg

Experimental

Crystal data

  • C11H9Cl2N3O
  • M r = 270.11
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1224-efi2.jpg
  • a = 7.3440 (10) Å
  • b = 8.7981 (12) Å
  • c = 9.6490 (14) Å
  • α = 75.554 (2)°
  • β = 89.627 (3)°
  • γ = 86.819 (2)°
  • V = 602.79 (15) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.52 mm−1
  • T = 298 (2) K
  • 0.50 × 0.49 × 0.48 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.780, T max = 0.787
  • 3145 measured reflections
  • 2102 independent reflections
  • 1543 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.126
  • S = 1.04
  • 2101 reflections
  • 154 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); 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/S1600536808015006/bg2182sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015006/bg2182Isup2.hkl

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

Acknowledgments

The authors thank the National Natural Science Foundation of China (20761002). This research was sponsored by the Fund of the Talent Highland Research Program of Guangxi University (205121), the Science Foundation of the State Ethnic Affairs Commission (07GX05), the Development Foundation of Guangxi Research Institute of Chemical Industry and the Science Foundation of Guangxi University for Nationalities (0409032, 0409012, 0509ZD047).

supplementary crystallographic information

Comment

The chemical and pharmacological properties of pyrazoles have been investigated extensively, owing to their chelating ability with metal ions and their potentially beneficial chemical and biological activities (Mann et al., 1992, Perevalov et al., 2001). As part of our studies on the synthesis and characterization of these compounds, we report here the synthesis and crystal structure of (3,6-dichloropyridin-2-yl)(3,5-dimethyl-1H-pyrazol-1-yl)methanone.

The crystal structure of the monomeric title compound is built up by C11H9Cl2N3O molecules (Fig.1), linked by intermolecular C—H···N hydrogen bonds along [100] (Table 1) and by Cl···Cl short contacts along the [011] direction (Cl1···Cl1ii: 3.319 (1)Å, (ii): 2-x, 1-y, 1-z) , forming a two-dimensional network parallel to (011).

The short C=O bond length (1.199 (3)Å) indicates that the molecule is in a keto form (Fig.1). The two rings are nearly perpendicular to each other (dihedral angle: 82.319 (84) °), and this fact helps in minimizing steric effects between them. Finally, there is an intermolecular π—π contact between pyridine groups with and intercentroid distance of 3.40 (1) Å, which contributes to the stability of the crystal packing.

Experimental

A solution of 3,6-dichloropicolinoyl chloride (10 mmol) in 50 ml toluene was added to a solution of 3,5-dimethyl-1H-pyrazole (10 mmol) in 10 ml toluene. The reaction mixture was refluxed for 1 h with stirring then the resulting white precipitate was obtained by filtration, washed several times with ethanol and dried in vacuo (yield 90%). Elemental analysis calculate: Elemental analysis: found: C, 48.89; H, 3.33; N, 15.56; calc. for C11H9Cl2N3O: C, 48.99; H, 3.23; N, 15.46.

Refinement

Data collection: 2102 independent reflections but 2101 in Refinement. H atoms on C atoms were positoned geometrically and refined using a riding model with C—H = 0.96Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The structure of the title compound (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
Crystal packing of (I) showing the short contacts interactions as dashed lines.

Crystal data

C11H9Cl2N3OZ = 2
Mr = 270.11F000 = 276
Triclinic, P1Dx = 1.488 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.3440 (10) ÅCell parameters from 1363 reflections
b = 8.7981 (12) Åθ = 2.2–27.4º
c = 9.6490 (14) ŵ = 0.52 mm1
α = 75.554 (2)ºT = 298 (2) K
β = 89.627 (3)ºBlock, colourless
γ = 86.819 (2)º0.50 × 0.49 × 0.48 mm
V = 602.79 (15) Å3

Data collection

Bruker SMART CCD area-detector diffractometer2102 independent reflections
Radiation source: fine-focus sealed tube1543 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.038
T = 298(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −8→8
Tmin = 0.780, Tmax = 0.787k = −9→10
3145 measured reflectionsl = −9→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.126  w = 1/[σ2(Fo2) + (0.0468P)2 + 0.2168P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2101 reflectionsΔρmax = 0.22 e Å3
154 parametersΔρmin = −0.27 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
Cl10.60627 (11)0.85128 (9)0.94981 (8)0.0634 (3)
Cl20.90422 (12)0.19393 (9)0.92556 (10)0.0712 (3)
N10.8160 (3)0.4899 (3)0.8173 (2)0.0434 (5)
N20.6305 (3)0.7559 (2)0.5846 (2)0.0415 (5)
N30.4844 (3)0.6627 (2)0.6266 (2)0.0421 (5)
O10.8838 (3)0.8463 (3)0.6636 (2)0.0712 (7)
C10.7630 (4)0.7572 (3)0.6853 (3)0.0440 (6)
C20.7517 (3)0.6330 (3)0.8231 (2)0.0368 (6)
C30.6925 (3)0.6653 (3)0.9493 (3)0.0407 (6)
C40.6996 (4)0.5468 (3)1.0739 (3)0.0469 (7)
H40.65960.56621.15980.056*
C50.7666 (4)0.4004 (3)1.0686 (3)0.0488 (7)
H50.77460.31811.15080.059*
C60.8220 (4)0.3782 (3)0.9384 (3)0.0445 (7)
C70.7566 (5)0.9440 (4)0.3653 (3)0.0670 (9)
H7A0.75931.03320.40560.101*
H7B0.72590.97890.26540.101*
H7C0.87430.88900.37640.101*
C80.6167 (4)0.8362 (3)0.4409 (3)0.0483 (7)
C90.4615 (4)0.7924 (3)0.3939 (3)0.0548 (8)
H90.41450.82540.30130.066*
C100.3819 (4)0.6865 (3)0.5110 (3)0.0444 (6)
C110.2080 (4)0.6066 (4)0.5140 (3)0.0622 (8)
H11A0.10740.67820.52230.093*
H11B0.20910.51660.59440.093*
H11C0.19530.57330.42720.093*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0743 (6)0.0459 (4)0.0697 (5)0.0120 (4)0.0039 (4)−0.0172 (4)
Cl20.0775 (6)0.0408 (4)0.0948 (7)0.0118 (4)−0.0144 (5)−0.0188 (4)
N10.0444 (13)0.0417 (13)0.0441 (13)0.0003 (10)−0.0022 (10)−0.0110 (10)
N20.0448 (13)0.0369 (12)0.0379 (12)−0.0010 (10)0.0017 (10)−0.0006 (9)
N30.0440 (13)0.0414 (12)0.0388 (12)−0.0010 (10)0.0006 (10)−0.0062 (9)
O10.0706 (15)0.0756 (16)0.0611 (14)−0.0326 (13)−0.0013 (11)0.0012 (11)
C10.0466 (16)0.0413 (15)0.0422 (15)−0.0033 (13)0.0020 (12)−0.0066 (12)
C20.0338 (13)0.0387 (14)0.0360 (13)−0.0027 (11)−0.0032 (10)−0.0058 (11)
C30.0382 (14)0.0390 (14)0.0438 (15)0.0000 (12)−0.0031 (11)−0.0084 (12)
C40.0507 (17)0.0510 (17)0.0380 (15)−0.0034 (13)−0.0011 (12)−0.0088 (12)
C50.0527 (18)0.0462 (17)0.0406 (15)−0.0082 (13)−0.0079 (13)0.0036 (12)
C60.0415 (15)0.0343 (14)0.0559 (17)0.0001 (11)−0.0102 (12)−0.0083 (12)
C70.079 (2)0.062 (2)0.0488 (18)−0.0075 (18)0.0099 (16)0.0091 (15)
C80.0604 (19)0.0408 (15)0.0373 (15)0.0049 (13)0.0037 (13)0.0009 (12)
C90.064 (2)0.0595 (19)0.0359 (15)0.0079 (16)−0.0081 (14)−0.0047 (13)
C100.0488 (16)0.0445 (15)0.0382 (14)0.0057 (12)−0.0024 (12)−0.0090 (12)
C110.0570 (19)0.076 (2)0.0561 (19)−0.0005 (17)−0.0078 (15)−0.0219 (16)

Geometric parameters (Å, °)

Cl1—C31.722 (3)C5—C61.375 (4)
Cl2—C61.732 (3)C5—H50.9300
N1—C61.325 (3)C7—C81.496 (4)
N1—C21.334 (3)C7—H7A0.9600
N2—C11.382 (3)C7—H7B0.9600
N2—N31.383 (3)C7—H7C0.9600
N2—C81.392 (3)C8—C91.340 (4)
N3—C101.316 (3)C9—C101.419 (4)
O1—C11.199 (3)C9—H90.9300
C1—C21.502 (3)C10—C111.488 (4)
C2—C31.380 (3)C11—H11A0.9600
C3—C41.380 (4)C11—H11B0.9600
C4—C51.366 (4)C11—H11C0.9600
C4—H40.9300
C6—N1—C2117.4 (2)C5—C6—Cl2119.8 (2)
C1—N2—N3118.3 (2)C8—C7—H7A109.5
C1—N2—C8130.2 (2)C8—C7—H7B109.5
N3—N2—C8111.5 (2)H7A—C7—H7B109.5
C10—N3—N2104.7 (2)C8—C7—H7C109.5
O1—C1—N2123.1 (2)H7A—C7—H7C109.5
O1—C1—C2121.5 (2)H7B—C7—H7C109.5
N2—C1—C2115.3 (2)C9—C8—N2105.3 (2)
N1—C2—C3122.1 (2)C9—C8—C7131.3 (3)
N1—C2—C1114.8 (2)N2—C8—C7123.4 (3)
C3—C2—C1123.0 (2)C8—C9—C10107.6 (2)
C4—C3—C2119.4 (3)C8—C9—H9126.2
C4—C3—Cl1120.5 (2)C10—C9—H9126.2
C2—C3—Cl1120.03 (19)N3—C10—C9110.9 (2)
C5—C4—C3118.7 (3)N3—C10—C11120.8 (2)
C5—C4—H4120.6C9—C10—C11128.3 (2)
C3—C4—H4120.6C10—C11—H11A109.5
C4—C5—C6118.1 (2)C10—C11—H11B109.5
C4—C5—H5121.0H11A—C11—H11B109.5
C6—C5—H5121.0C10—C11—H11C109.5
N1—C6—C5124.3 (3)H11A—C11—H11C109.5
N1—C6—Cl2115.9 (2)H11B—C11—H11C109.5
C1—N2—N3—C10179.3 (2)Cl1—C3—C4—C5179.1 (2)
C8—N2—N3—C10−0.6 (3)C3—C4—C5—C6−0.7 (4)
N3—N2—C1—O1−171.8 (3)C2—N1—C6—C50.0 (4)
C8—N2—C1—O18.1 (5)C2—N1—C6—Cl2179.37 (18)
N3—N2—C1—C211.2 (3)C4—C5—C6—N10.5 (4)
C8—N2—C1—C2−169.0 (2)C4—C5—C6—Cl2−178.9 (2)
C6—N1—C2—C3−0.2 (4)C1—N2—C8—C9−179.9 (3)
C6—N1—C2—C1175.1 (2)N3—N2—C8—C90.0 (3)
O1—C1—C2—N1−98.9 (3)C1—N2—C8—C71.1 (5)
N2—C1—C2—N178.2 (3)N3—N2—C8—C7−179.1 (3)
O1—C1—C2—C376.4 (4)N2—C8—C9—C100.5 (3)
N2—C1—C2—C3−106.5 (3)C7—C8—C9—C10179.5 (3)
N1—C2—C3—C40.0 (4)N2—N3—C10—C90.9 (3)
C1—C2—C3—C4−174.9 (2)N2—N3—C10—C11−179.3 (2)
N1—C2—C3—Cl1−178.62 (19)C8—C9—C10—N3−0.9 (3)
C1—C2—C3—Cl16.4 (3)C8—C9—C10—C11179.3 (3)
C2—C3—C4—C50.4 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C11—H11C···N1i0.962.563.514 (4)174

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2182).

References

  • Mann, F., Chiment, F., Balasco, A., Cenicola, M. L., Amico, M. D., Parrilo, C., Rossi, F. & Marmo, E. (1992). Eur. J. Med. Chem.27, 633–639.
  • Perevalov, S. G., Burgart, Y. V., Saloutin, V. I. & Chupakhin, O. N. (2001). Russ. Chem. Rev.70, 921–925.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography