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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3267.
Published online 2009 November 28. doi:  10.1107/S1600536809050673
PMCID: PMC2972119

Ethyl 3-bromo-1-(3-chloro-2-pyrid­yl)-4,5-dihydro-1H-pyrazole-5-carboxyl­ate

Abstract

The title compound, C11H11BrClN3O2, contains two mol­ecules in the asymmetric unit in which the dihedral angles between the pyrazole and pyridine rings are 30.0 (2) and 22.3 (2)°.

Related literature

For background to the use of anthranilamide compounds containing N-pyridyl pyrazole groups as potential insecticides, see: Lahm et al. (2003 [triangle]). For the synthesis, see: Lahm et al. (2005 [triangle]).

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Object name is e-65-o3267-scheme1.jpg

Experimental

Crystal data

  • C11H11BrClN3O2
  • M r = 332.59
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3267-efi1.jpg
  • a = 11.9977 (18) Å
  • b = 10.8520 (17) Å
  • c = 20.762 (3) Å
  • β = 93.388 (3)°
  • V = 2698.4 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 3.24 mm−1
  • T = 296 K
  • 0.38 × 0.32 × 0.30 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.356, T max = 1.000
  • 13418 measured reflections
  • 4760 independent reflections
  • 2823 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.126
  • S = 1.02
  • 4760 reflections
  • 327 parameters
  • H-atom parameters constrained
  • Δρmax = 0.64 e Å−3
  • Δρmin = −0.49 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050673/hb5251sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050673/hb5251Isup2.hkl

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

supplementary crystallographic information

Experimental

According to the reported procedure of Lahm et al., (2005), the title compound was synthesized by ethyl 2-(3-chloro-2-Pyridinyl)-5-oxo-3-pyrazolidinecarboxylate with phosphorus oxybromide under basic condition in acetonitrile. The crude products were purified by silica-gel column chromatography and then grown from acetone to afford colorless single crystals suitable for X-ray diffraction.To a solution of ethyl 2-(3-chloro-2-Pyridinyl)-5-oxo-3-pyrazolidinecarboxylate (2.70 g, 10.0 mmol) in acetonitrile (30 ml) was added the solution of phosphorusoxybromide (2.01 g, 7.0 mmol) in acetonitrile (30 ml) at 333 K.The reaction mixturewas heated to reflux at 369 K over period of 1 h. Then neutralize concentrated reaction mixture with sodium bicarbonate until the PH=8.Then the mixture was extracted with ethyl acetate; the organic extracts were dried overmagnesium sulfate and concentrated. Afford the title product compound as a white solid (2.5 g, 75%). Anal. Calcd for C11H11N3O2: C, 39.72; H, 3.33; N, 12.63. Found: C, 39.91; H, 3.27; N, 12.50. 1H NMR (DMSO): 1.15(t, 3H, CH3), 3.29 (dd, 1H, pyrazole-H), 3.60 (dd, 1H, pyrazole-H),4.11(q,2H,CH2),5.20 (dd, 1H, pyrazole-H), 6.99 (dd, 1H, pyridine-H), 7.84 (d, 1H, pyridine-H), 8.12 (d, 1H, pyridine-H).

Refinement

All H atoms were visible in difference maps: they were placed in geometrically calculated positions, with C—H = 0.93–0.98 Å, and refined as riding with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I), with 30% probability displacement ellipsoids.

Crystal data

C11H11BrClN3O2F(000) = 1328
Mr = 332.59Dx = 1.637 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2849 reflections
a = 11.9977 (18) Åθ = 2.5–23.4°
b = 10.8520 (17) ŵ = 3.24 mm1
c = 20.762 (3) ÅT = 296 K
β = 93.388 (3)°Block, colourless
V = 2698.4 (7) Å30.38 × 0.32 × 0.30 mm
Z = 8

Data collection

Bruker SMART CCD diffractometer4760 independent reflections
Radiation source: fine-focus sealed tube2823 reflections with I > 2σ(I)
graphiteRint = 0.029
ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −14→14
Tmin = 0.356, Tmax = 1.000k = −12→8
13418 measured reflectionsl = −20→24

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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0609P)2 + 0.7833P] where P = (Fo2 + 2Fc2)/3
4760 reflections(Δ/σ)max = 0.001
327 parametersΔρmax = 0.64 e Å3
0 restraintsΔρmin = −0.49 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
Br10.61938 (4)0.12589 (5)0.11537 (3)0.0919 (2)
Br20.12166 (4)1.34462 (4)0.11712 (3)0.0871 (2)
Cl10.84050 (8)0.53502 (11)0.12056 (6)0.0843 (4)
Cl20.33983 (8)0.94532 (12)0.10673 (7)0.0940 (4)
O10.4918 (3)0.6080 (3)0.20858 (15)0.0867 (10)
O20.3214 (2)0.5466 (3)0.17635 (13)0.0802 (9)
O30.0011 (3)0.8736 (3)0.20050 (14)0.0864 (10)
O4−0.1747 (2)0.9229 (3)0.17066 (12)0.0680 (8)
N10.5454 (2)0.6660 (3)0.05716 (14)0.0553 (8)
N20.5862 (2)0.4848 (3)0.11040 (15)0.0610 (9)
N30.6393 (3)0.3738 (3)0.10056 (16)0.0601 (9)
N40.0445 (2)0.8001 (3)0.05316 (15)0.0577 (8)
N50.0807 (2)0.9898 (3)0.09552 (19)0.0750 (10)
N60.1371 (2)1.0989 (3)0.09295 (15)0.0579 (8)
C10.5772 (3)0.7712 (4)0.03040 (18)0.0640 (11)
H10.52180.82570.01530.077*
C20.6850 (3)0.8036 (4)0.02391 (19)0.0700 (12)
H20.70310.87520.00230.084*
C30.7664 (3)0.7272 (4)0.05023 (19)0.0619 (11)
H30.84130.74750.04750.074*
C40.7373 (3)0.6211 (4)0.08063 (18)0.0548 (10)
C50.6239 (3)0.5907 (3)0.08114 (16)0.0477 (9)
C60.5731 (3)0.2893 (4)0.11589 (18)0.0595 (10)
C70.4634 (3)0.3298 (4)0.13789 (19)0.0610 (10)
H7A0.45830.31750.18390.073*
H7B0.40190.28780.11470.073*
C80.4669 (3)0.4674 (3)0.12040 (17)0.0528 (9)
H80.42190.48330.08030.063*
C90.4312 (3)0.5498 (4)0.17334 (18)0.0592 (10)
C100.2759 (5)0.6186 (6)0.2280 (3)0.119 (2)
H10A0.30450.58720.26950.143*
H10B0.29900.70390.22460.143*
C110.1599 (6)0.6115 (7)0.2238 (3)0.159 (3)
H11A0.13190.64070.18230.238*
H11B0.13030.66140.25690.238*
H11C0.13730.52740.22920.238*
C120.0767 (3)0.6904 (4)0.03225 (19)0.0664 (11)
H120.02180.63350.01970.080*
C130.1851 (3)0.6570 (4)0.0282 (2)0.0708 (12)
H130.20420.58070.01170.085*
C140.2656 (3)0.7401 (4)0.0494 (2)0.0658 (11)
H140.34070.72030.04740.079*
C150.2355 (3)0.8510 (4)0.07329 (19)0.0556 (10)
C160.1219 (3)0.8812 (3)0.07301 (17)0.0490 (9)
C170.0712 (3)1.1825 (4)0.10999 (18)0.0561 (10)
C18−0.0415 (3)1.1433 (4)0.1270 (2)0.0679 (12)
H18A−0.09971.18610.10130.081*
H18B−0.05241.15570.17240.081*
C19−0.0372 (3)1.0054 (3)0.10966 (17)0.0534 (9)
H19−0.08630.98730.07150.064*
C20−0.0653 (3)0.9256 (4)0.16513 (18)0.0551 (10)
C21−0.2137 (5)0.8554 (5)0.2256 (2)0.0970 (17)
H21A−0.18500.77190.22560.116*
H21B−0.18700.89500.26540.116*
C22−0.3344 (5)0.8532 (6)0.2213 (3)0.133 (3)
H22A−0.36230.93610.22030.199*
H22B−0.36060.81090.25810.199*
H22C−0.36030.81110.18260.199*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0860 (4)0.0580 (3)0.1307 (5)0.0064 (2)−0.0007 (3)0.0112 (3)
Br20.0843 (4)0.0538 (3)0.1226 (4)−0.0033 (2)0.0012 (3)−0.0117 (3)
Cl10.0455 (6)0.0807 (8)0.1243 (10)0.0010 (5)−0.0147 (6)0.0073 (7)
Cl20.0447 (6)0.0696 (8)0.1656 (12)−0.0029 (5)−0.0116 (7)−0.0069 (8)
O10.086 (2)0.093 (2)0.080 (2)−0.0312 (19)0.0031 (17)−0.0221 (18)
O20.0583 (18)0.104 (3)0.0802 (19)−0.0035 (16)0.0172 (14)−0.0382 (18)
O30.086 (2)0.096 (3)0.077 (2)0.0324 (18)−0.0057 (17)0.0147 (17)
O40.0564 (17)0.084 (2)0.0646 (17)−0.0057 (14)0.0118 (13)0.0251 (15)
N10.0409 (17)0.063 (2)0.061 (2)−0.0002 (16)0.0015 (14)0.0043 (17)
N20.0402 (17)0.056 (2)0.088 (2)−0.0019 (15)0.0116 (15)0.0054 (18)
N30.0498 (19)0.057 (2)0.073 (2)0.0037 (16)−0.0023 (16)0.0003 (17)
N40.0416 (17)0.062 (2)0.070 (2)0.0016 (16)0.0021 (15)−0.0019 (17)
N50.0445 (19)0.051 (2)0.132 (3)0.0018 (16)0.0298 (19)−0.002 (2)
N60.0467 (18)0.050 (2)0.077 (2)−0.0038 (16)0.0032 (15)0.0022 (17)
C10.055 (2)0.071 (3)0.065 (3)0.005 (2)0.0026 (19)0.010 (2)
C20.060 (3)0.077 (3)0.074 (3)−0.010 (2)0.016 (2)0.015 (2)
C30.048 (2)0.065 (3)0.074 (3)−0.009 (2)0.0169 (19)−0.007 (2)
C40.040 (2)0.061 (3)0.064 (2)0.0042 (18)0.0026 (17)−0.007 (2)
C50.039 (2)0.052 (2)0.053 (2)−0.0038 (17)0.0079 (16)−0.0054 (18)
C60.054 (2)0.056 (3)0.067 (3)−0.003 (2)−0.0088 (19)0.002 (2)
C70.059 (2)0.060 (3)0.065 (3)−0.012 (2)0.0060 (19)−0.009 (2)
C80.043 (2)0.059 (3)0.056 (2)−0.0105 (17)0.0055 (16)−0.0042 (19)
C90.055 (2)0.062 (3)0.060 (2)−0.016 (2)0.004 (2)−0.002 (2)
C100.086 (4)0.155 (6)0.120 (5)0.000 (4)0.034 (3)−0.070 (4)
C110.172 (7)0.171 (7)0.137 (6)0.073 (6)0.047 (5)−0.040 (5)
C120.055 (2)0.071 (3)0.073 (3)−0.006 (2)−0.001 (2)−0.015 (2)
C130.060 (3)0.067 (3)0.087 (3)0.009 (2)0.018 (2)−0.015 (2)
C140.046 (2)0.064 (3)0.089 (3)0.009 (2)0.021 (2)0.000 (2)
C150.039 (2)0.053 (2)0.075 (3)−0.0008 (17)0.0065 (18)0.007 (2)
C160.040 (2)0.050 (2)0.057 (2)0.0047 (17)0.0104 (17)0.0067 (18)
C170.055 (2)0.049 (2)0.064 (3)0.0074 (19)0.0002 (18)0.003 (2)
C180.060 (3)0.057 (3)0.089 (3)0.013 (2)0.021 (2)0.014 (2)
C190.043 (2)0.052 (2)0.066 (2)0.0070 (17)0.0114 (17)0.0065 (19)
C200.051 (2)0.050 (2)0.064 (3)0.0070 (19)0.001 (2)−0.002 (2)
C210.111 (4)0.106 (4)0.077 (3)−0.013 (3)0.030 (3)0.032 (3)
C220.138 (6)0.166 (7)0.100 (4)−0.078 (5)0.042 (4)0.012 (4)

Geometric parameters (Å, °)

Br1—C61.858 (4)C7—C81.538 (5)
Br2—C171.863 (4)C7—H7A0.9700
Cl1—C41.724 (4)C7—H7B0.9700
Cl2—C151.731 (4)C8—C91.499 (5)
O1—C91.184 (4)C8—H80.9800
O2—C91.323 (4)C10—C111.392 (9)
O2—C101.459 (5)C10—H10A0.9700
O3—C201.192 (4)C10—H10B0.9700
O4—C201.325 (4)C11—H11A0.9600
O4—C211.455 (5)C11—H11B0.9600
N1—C51.321 (4)C11—H11C0.9600
N1—C11.335 (5)C12—C131.357 (5)
N2—N31.383 (4)C12—H120.9300
N2—C51.388 (5)C13—C141.374 (6)
N2—C81.471 (4)C13—H130.9300
N3—C61.266 (5)C14—C151.358 (5)
N4—C161.327 (5)C14—H140.9300
N4—C121.332 (5)C15—C161.401 (5)
N5—N61.366 (4)C17—C181.480 (5)
N5—C161.371 (5)C18—C191.541 (5)
N5—C191.470 (4)C18—H18A0.9700
N6—C171.267 (5)C18—H18B0.9700
C1—C21.355 (5)C19—C201.495 (5)
C1—H10.9300C19—H190.9800
C2—C31.370 (5)C21—C221.445 (8)
C2—H20.9300C21—H21A0.9700
C3—C41.368 (5)C21—H21B0.9700
C3—H30.9300C22—H22A0.9600
C4—C51.401 (5)C22—H22B0.9600
C6—C71.486 (5)C22—H22C0.9600
C9—O2—C10115.9 (3)C10—C11—H11A109.5
C20—O4—C21116.4 (3)C10—C11—H11B109.5
C5—N1—C1118.1 (3)H11A—C11—H11B109.5
N3—N2—C5119.5 (3)C10—C11—H11C109.5
N3—N2—C8111.7 (3)H11A—C11—H11C109.5
C5—N2—C8120.8 (3)H11B—C11—H11C109.5
C6—N3—N2107.0 (3)N4—C12—C13123.8 (4)
C16—N4—C12118.8 (3)N4—C12—H12118.1
N6—N5—C16122.8 (3)C13—C12—H12118.1
N6—N5—C19113.2 (3)C12—C13—C14117.5 (4)
C16—N5—C19122.5 (3)C12—C13—H13121.2
C17—N6—N5106.9 (3)C14—C13—H13121.2
N1—C1—C2124.1 (4)C15—C14—C13120.1 (4)
N1—C1—H1118.0C15—C14—H14120.0
C2—C1—H1118.0C13—C14—H14120.0
C1—C2—C3117.8 (4)C14—C15—C16119.0 (4)
C1—C2—H2121.1C14—C15—Cl2118.0 (3)
C3—C2—H2121.1C16—C15—Cl2122.9 (3)
C4—C3—C2119.8 (4)N4—C16—N5114.6 (3)
C4—C3—H3120.1N4—C16—C15120.6 (3)
C2—C3—H3120.1N5—C16—C15124.8 (3)
C3—C4—C5118.5 (3)N6—C17—C18117.0 (4)
C3—C4—Cl1118.8 (3)N6—C17—Br2119.6 (3)
C5—C4—Cl1122.6 (3)C18—C17—Br2123.3 (3)
N1—C5—N2115.7 (3)C17—C18—C19100.3 (3)
N1—C5—C4121.4 (3)C17—C18—H18A111.7
N2—C5—C4122.7 (3)C19—C18—H18A111.7
N3—C6—C7116.3 (4)C17—C18—H18B111.7
N3—C6—Br1119.9 (3)C19—C18—H18B111.7
C7—C6—Br1123.7 (3)H18A—C18—H18B109.5
C6—C7—C8100.2 (3)N5—C19—C20110.5 (3)
C6—C7—H7A111.7N5—C19—C18101.8 (3)
C8—C7—H7A111.7C20—C19—C18111.7 (3)
C6—C7—H7B111.7N5—C19—H19110.8
C8—C7—H7B111.7C20—C19—H19110.8
H7A—C7—H7B109.5C18—C19—H19110.8
N2—C8—C9110.5 (3)O3—C20—O4124.4 (4)
N2—C8—C7101.4 (3)O3—C20—C19125.2 (4)
C9—C8—C7113.2 (3)O4—C20—C19110.4 (3)
N2—C8—H8110.5C22—C21—O4109.1 (4)
C9—C8—H8110.5C22—C21—H21A109.9
C7—C8—H8110.5O4—C21—H21A109.9
O1—C9—O2124.2 (4)C22—C21—H21B109.9
O1—C9—C8125.4 (4)O4—C21—H21B109.9
O2—C9—C8110.3 (3)H21A—C21—H21B108.3
C11—C10—O2109.9 (5)C21—C22—H22A109.5
C11—C10—H10A109.7C21—C22—H22B109.5
O2—C10—H10A109.7H22A—C22—H22B109.5
C11—C10—H10B109.7C21—C22—H22C109.5
O2—C10—H10B109.7H22A—C22—H22C109.5
H10A—C10—H10B108.2H22B—C22—H22C109.5
C5—N2—N3—C6−161.8 (3)C7—C8—C9—O2−75.6 (4)
C8—N2—N3—C6−12.7 (4)C9—O2—C10—C11177.3 (5)
C16—N5—N6—C17172.2 (4)C16—N4—C12—C13−1.9 (6)
C19—N5—N6—C176.1 (4)N4—C12—C13—C142.6 (7)
C5—N1—C1—C22.8 (6)C12—C13—C14—C150.0 (6)
N1—C1—C2—C3−4.5 (6)C13—C14—C15—C16−3.0 (6)
C1—C2—C3—C41.3 (6)C13—C14—C15—Cl2173.6 (3)
C2—C3—C4—C53.0 (6)C12—N4—C16—N5−178.0 (4)
C2—C3—C4—Cl1−173.3 (3)C12—N4—C16—C15−1.4 (5)
C1—N1—C5—N2177.8 (3)N6—N5—C16—N4−152.2 (4)
C1—N1—C5—C42.0 (5)C19—N5—C16—N412.6 (5)
N3—N2—C5—N1139.1 (3)N6—N5—C16—C1531.3 (6)
C8—N2—C5—N1−7.1 (5)C19—N5—C16—C15−163.9 (3)
N3—N2—C5—C4−45.1 (5)C14—C15—C16—N43.8 (6)
C8—N2—C5—C4168.6 (3)Cl2—C15—C16—N4−172.6 (3)
C3—C4—C5—N1−4.9 (5)C14—C15—C16—N5−179.9 (4)
Cl1—C4—C5—N1171.4 (3)Cl2—C15—C16—N53.7 (6)
C3—C4—C5—N2179.7 (3)N5—N6—C17—C180.0 (5)
Cl1—C4—C5—N2−4.1 (5)N5—N6—C17—Br2176.5 (3)
N2—N3—C6—C70.8 (5)N6—C17—C18—C19−5.4 (5)
N2—N3—C6—Br1−175.1 (2)Br2—C17—C18—C19178.2 (3)
N3—C6—C7—C810.3 (4)N6—N5—C19—C20−127.9 (4)
Br1—C6—C7—C8−173.9 (3)C16—N5—C19—C2066.0 (5)
N3—N2—C8—C9138.6 (3)N6—N5—C19—C18−9.0 (4)
C5—N2—C8—C9−72.8 (4)C16—N5—C19—C18−175.2 (4)
N3—N2—C8—C718.3 (4)C17—C18—C19—N57.8 (4)
C5—N2—C8—C7166.9 (3)C17—C18—C19—C20125.8 (3)
C6—C7—C8—N2−15.7 (3)C21—O4—C20—O32.7 (6)
C6—C7—C8—C9−134.1 (3)C21—O4—C20—C19−175.9 (4)
C10—O2—C9—O1−1.4 (7)N5—C19—C20—O312.4 (5)
C10—O2—C9—C8177.2 (4)C18—C19—C20—O3−100.1 (5)
N2—C8—C9—O1−9.9 (6)N5—C19—C20—O4−169.0 (3)
C7—C8—C9—O1103.0 (5)C18—C19—C20—O478.4 (4)
N2—C8—C9—O2171.5 (3)C20—O4—C21—C22−175.3 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5251).

References

  • Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lahm, G. P., Selby, T. P. & Freudenberger, J. H. (2005). Bioorg. Med. Chem. Lett. 15, 4898–4906. [PubMed]
  • Lahm, G. P., Selby, T. P. & Stevenson, T. M. (2003). World Patent No. WO 03/015519.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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