organic compounds
Ethyl 2-(3-chloro-2-pyridyl)-5-oxopyrazolidine-3-carboxylate
aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and bJiangsu Pesticide Research Institute Co Ltd, Nanjing 210036, People's Republic of China
*Correspondence e-mail: zhuhj@njut.edu.cn
In the molecule of the title compound, C11H12ClN3O3, the five membered ring adopts an In the intermolecular N—H⋯O hydrogen bonds link the molecules into centrosymmetric dimers.
Related literature
For the synthetic procedure, see: Lahm et al. (2007). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809020789/hk2697sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809020789/hk2697Isup2.hkl
The title compound was synthesized according to a literature method (Lahm et al., 2007). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.
H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93, 0.98, 0.97 and 0.96 Å for aromatic, methine, methylene and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.
Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell
CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C11H12ClN3O3 | F(000) = 1120 |
Mr = 269.69 | Dx = 1.422 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 15.488 (3) Å | θ = 0.9–1.0° |
b = 10.009 (2) Å | µ = 0.31 mm−1 |
c = 16.249 (3) Å | T = 298 K |
V = 2518.9 (8) Å3 | Block, colorless |
Z = 8 | 0.30 × 0.20 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 1635 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 25.3°, θmin = 2.5° |
ω/2θ scans | h = 0→18 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
Tmin = 0.913, Tmax = 0.970 | l = −19→19 |
4453 measured reflections | 3 standard reflections every 120 min |
2273 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0473P)2 + 0.824P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2273 reflections | Δρmax = 0.29 e Å−3 |
164 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0065 (7) |
C11H12ClN3O3 | V = 2518.9 (8) Å3 |
Mr = 269.69 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 15.488 (3) Å | µ = 0.31 mm−1 |
b = 10.009 (2) Å | T = 298 K |
c = 16.249 (3) Å | 0.30 × 0.20 × 0.10 mm |
Enraf–Nonius CAD-4 diffractometer | 1635 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.029 |
Tmin = 0.913, Tmax = 0.970 | 3 standard reflections every 120 min |
4453 measured reflections | intensity decay: none |
2273 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.29 e Å−3 |
2273 reflections | Δρmin = −0.23 e Å−3 |
164 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl | 0.45523 (4) | 0.14184 (7) | 0.43566 (5) | 0.0629 (3) | |
O1 | 0.30427 (10) | 0.43898 (19) | 0.31272 (11) | 0.0561 (5) | |
O2 | 0.34478 (11) | 0.4578 (2) | 0.44373 (11) | 0.0597 (5) | |
O3 | 0.55616 (12) | 0.7407 (2) | 0.33051 (13) | 0.0667 (6) | |
N1 | 0.54947 (12) | 0.55100 (18) | 0.40815 (12) | 0.0372 (5) | |
H1A | 0.5776 | 0.5814 | 0.4497 | 0.045* | |
N2 | 0.51613 (11) | 0.41865 (17) | 0.40548 (11) | 0.0328 (4) | |
N3 | 0.66149 (12) | 0.3566 (2) | 0.37919 (13) | 0.0456 (5) | |
C1 | 0.1756 (2) | 0.3232 (4) | 0.3592 (2) | 0.0876 (11) | |
H1B | 0.1163 | 0.3358 | 0.3745 | 0.131* | |
H1C | 0.2069 | 0.2863 | 0.4049 | 0.131* | |
H1D | 0.1789 | 0.2631 | 0.3133 | 0.131* | |
C2 | 0.21401 (15) | 0.4539 (3) | 0.3359 (2) | 0.0666 (9) | |
H2A | 0.1820 | 0.4915 | 0.2902 | 0.080* | |
H2B | 0.2096 | 0.5152 | 0.3820 | 0.080* | |
C3 | 0.36204 (14) | 0.4419 (2) | 0.37295 (15) | 0.0389 (6) | |
C4 | 0.45184 (14) | 0.4216 (2) | 0.33772 (13) | 0.0363 (5) | |
H4A | 0.4542 | 0.3381 | 0.3063 | 0.044* | |
C5 | 0.48079 (15) | 0.5388 (3) | 0.28374 (15) | 0.0471 (6) | |
H5A | 0.5154 | 0.5078 | 0.2378 | 0.056* | |
H5B | 0.4315 | 0.5878 | 0.2627 | 0.056* | |
C6 | 0.53378 (15) | 0.6246 (3) | 0.34130 (15) | 0.0434 (6) | |
C7 | 0.58184 (14) | 0.3194 (2) | 0.39697 (13) | 0.0332 (5) | |
C8 | 0.72260 (16) | 0.2612 (3) | 0.37550 (18) | 0.0565 (8) | |
H8A | 0.7790 | 0.2872 | 0.3639 | 0.068* | |
C9 | 0.70658 (18) | 0.1279 (3) | 0.38781 (17) | 0.0548 (7) | |
H9A | 0.7509 | 0.0655 | 0.3842 | 0.066* | |
C10 | 0.62367 (17) | 0.0884 (3) | 0.40552 (16) | 0.0490 (6) | |
H10A | 0.6104 | −0.0013 | 0.4134 | 0.059* | |
C11 | 0.56048 (14) | 0.1858 (2) | 0.41127 (15) | 0.0389 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0487 (4) | 0.0514 (4) | 0.0885 (6) | −0.0128 (3) | 0.0079 (4) | 0.0135 (4) |
O1 | 0.0322 (9) | 0.0815 (14) | 0.0546 (11) | 0.0039 (9) | −0.0095 (8) | −0.0041 (10) |
O2 | 0.0367 (10) | 0.0944 (16) | 0.0479 (11) | 0.0071 (10) | 0.0002 (8) | −0.0127 (11) |
O3 | 0.0629 (12) | 0.0508 (12) | 0.0864 (16) | −0.0110 (10) | −0.0068 (10) | 0.0283 (11) |
N1 | 0.0399 (10) | 0.0307 (10) | 0.0411 (11) | −0.0008 (8) | −0.0056 (9) | −0.0020 (9) |
N2 | 0.0301 (9) | 0.0308 (10) | 0.0374 (10) | 0.0009 (8) | −0.0036 (8) | −0.0011 (8) |
N3 | 0.0314 (10) | 0.0402 (12) | 0.0650 (14) | 0.0003 (9) | 0.0035 (10) | −0.0027 (10) |
C1 | 0.0537 (19) | 0.097 (3) | 0.112 (3) | −0.0200 (19) | 0.0081 (19) | −0.017 (2) |
C2 | 0.0295 (13) | 0.087 (2) | 0.084 (2) | 0.0059 (14) | −0.0081 (14) | −0.0055 (18) |
C3 | 0.0339 (12) | 0.0399 (14) | 0.0429 (14) | 0.0027 (10) | −0.0047 (11) | −0.0039 (11) |
C4 | 0.0342 (11) | 0.0409 (13) | 0.0339 (12) | 0.0046 (10) | −0.0039 (9) | −0.0051 (10) |
C5 | 0.0389 (13) | 0.0647 (17) | 0.0377 (13) | 0.0061 (12) | −0.0017 (10) | 0.0091 (12) |
C6 | 0.0364 (13) | 0.0465 (16) | 0.0474 (15) | 0.0045 (11) | 0.0034 (11) | 0.0107 (12) |
C7 | 0.0318 (11) | 0.0340 (12) | 0.0337 (12) | 0.0022 (10) | −0.0027 (10) | −0.0002 (10) |
C8 | 0.0323 (12) | 0.0542 (18) | 0.083 (2) | 0.0046 (12) | 0.0019 (13) | −0.0045 (15) |
C9 | 0.0498 (16) | 0.0481 (16) | 0.0666 (19) | 0.0201 (13) | −0.0077 (14) | −0.0037 (13) |
C10 | 0.0581 (16) | 0.0342 (13) | 0.0548 (15) | 0.0072 (13) | −0.0068 (13) | 0.0069 (12) |
C11 | 0.0379 (13) | 0.0351 (13) | 0.0439 (14) | −0.0019 (10) | −0.0037 (10) | 0.0032 (11) |
Cl—C11 | 1.735 (2) | C2—H2A | 0.9700 |
O1—C2 | 1.456 (3) | C2—H2B | 0.9700 |
O1—C3 | 1.326 (3) | C3—C4 | 1.518 (3) |
O2—C3 | 1.191 (3) | C4—C5 | 1.531 (3) |
O3—C6 | 1.226 (3) | C4—H4A | 0.9800 |
N1—N2 | 1.422 (2) | C5—C6 | 1.512 (4) |
N1—C6 | 1.335 (3) | C5—H5A | 0.9700 |
N1—H1A | 0.8600 | C5—H5B | 0.9700 |
N2—C4 | 1.485 (3) | C7—C11 | 1.396 (3) |
N2—C7 | 1.429 (3) | C8—C9 | 1.372 (4) |
N3—C7 | 1.321 (3) | C8—H8A | 0.9300 |
N3—C8 | 1.346 (3) | C9—C10 | 1.374 (4) |
C1—C2 | 1.485 (4) | C9—H9A | 0.9300 |
C1—H1B | 0.9600 | C10—C11 | 1.385 (3) |
C1—H1C | 0.9600 | C10—H10A | 0.9300 |
C1—H1D | 0.9600 | ||
C3—O1—C2 | 117.0 (2) | C3—C4—H4A | 110.1 |
N2—N1—H1A | 122.5 | C5—C4—H4A | 110.1 |
C6—N1—N2 | 115.02 (19) | C6—C5—C4 | 103.85 (18) |
C6—N1—H1A | 122.5 | C6—C5—H5A | 111.0 |
N1—N2—C7 | 113.08 (17) | C4—C5—H5A | 111.0 |
N1—N2—C4 | 104.33 (16) | C6—C5—H5B | 111.0 |
C7—N2—C4 | 114.82 (17) | C4—C5—H5B | 111.0 |
C7—N3—C8 | 117.8 (2) | H5A—C5—H5B | 109.0 |
C2—C1—H1B | 109.5 | O3—C6—N1 | 126.0 (2) |
C2—C1—H1C | 109.5 | O3—C6—C5 | 127.1 (2) |
H1B—C1—H1C | 109.5 | N1—C6—C5 | 106.8 (2) |
C2—C1—H1D | 109.5 | N3—C7—C11 | 121.9 (2) |
H1B—C1—H1D | 109.5 | N3—C7—N2 | 119.3 (2) |
H1C—C1—H1D | 109.5 | C11—C7—N2 | 118.7 (2) |
O1—C2—C1 | 111.1 (2) | N3—C8—C9 | 123.8 (2) |
O1—C2—H2A | 109.4 | N3—C8—H8A | 118.1 |
C1—C2—H2A | 109.4 | C9—C8—H8A | 118.1 |
O1—C2—H2B | 109.4 | C8—C9—C10 | 118.6 (2) |
C1—C2—H2B | 109.4 | C8—C9—H9A | 120.7 |
H2A—C2—H2B | 108.0 | C10—C9—H9A | 120.7 |
O2—C3—O1 | 124.3 (2) | C9—C10—C11 | 118.2 (2) |
O2—C3—C4 | 126.0 (2) | C9—C10—H10A | 120.9 |
O1—C3—C4 | 109.70 (19) | C11—C10—H10A | 120.9 |
N2—C4—C3 | 109.73 (17) | C10—C11—C7 | 119.7 (2) |
N2—C4—C5 | 104.11 (18) | C10—C11—Cl | 120.06 (19) |
C3—C4—C5 | 112.46 (19) | C7—C11—Cl | 120.25 (17) |
N2—C4—H4A | 110.1 | ||
C6—N1—N2—C7 | 108.8 (2) | C4—C5—C6—O3 | −164.6 (2) |
C6—N1—N2—C4 | −16.6 (2) | C4—C5—C6—N1 | 13.3 (2) |
C3—O1—C2—C1 | −85.7 (3) | C8—N3—C7—C11 | −0.3 (3) |
C2—O1—C3—O2 | −1.2 (4) | C8—N3—C7—N2 | 176.9 (2) |
C2—O1—C3—C4 | 178.6 (2) | N1—N2—C7—N3 | −10.9 (3) |
N1—N2—C4—C3 | −97.1 (2) | C4—N2—C7—N3 | 108.6 (2) |
C7—N2—C4—C3 | 138.54 (19) | N1—N2—C7—C11 | 166.3 (2) |
N1—N2—C4—C5 | 23.4 (2) | C4—N2—C7—C11 | −74.1 (3) |
C7—N2—C4—C5 | −100.9 (2) | C7—N3—C8—C9 | 1.1 (4) |
O2—C3—C4—N2 | 2.4 (3) | N3—C8—C9—C10 | −0.5 (4) |
O1—C3—C4—N2 | −177.44 (18) | C8—C9—C10—C11 | −0.9 (4) |
O2—C3—C4—C5 | −113.0 (3) | C9—C10—C11—C7 | 1.7 (4) |
O1—C3—C4—C5 | 67.2 (2) | C9—C10—C11—Cl | −178.6 (2) |
N2—C4—C5—C6 | −22.5 (2) | N3—C7—C11—C10 | −1.1 (4) |
C3—C4—C5—C6 | 96.2 (2) | N2—C7—C11—C10 | −178.3 (2) |
N2—N1—C6—O3 | 179.8 (2) | N3—C7—C11—Cl | 179.22 (18) |
N2—N1—C6—C5 | 1.8 (3) | N2—C7—C11—Cl | 2.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.14 | 2.910 (3) | 149 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H12ClN3O3 |
Mr | 269.69 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 15.488 (3), 10.009 (2), 16.249 (3) |
V (Å3) | 2518.9 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.913, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4453, 2273, 1635 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.110, 1.03 |
No. of reflections | 2273 |
No. of parameters | 164 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.23 |
Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.14 | 2.910 (3) | 149 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
The authors thank Dr Shan Liu and Dr Rui Liu of the College of Science, Nanjing University of Technology, for useful discussions and the Center of Testing and Analysis, Nanjing University, for support.
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. CrossRef Web of Science Google Scholar
Enraf–Nonius (1985). CAD-4 Software. Enraf–Nonius, Delft. The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Lahm, G. P., Stevenson, T. M., Selby, T. P., Freudenberger, J. H., Cordova, D., Flexner, L., Bellin, C. A., Dubas, C. M., Smith, B. K., Hughes, K. A., Hollingshaus, J. G., Clark, C. E. & Benner, E. A. (2007). Bioorg. Med. Chem. Lett. 17, 6274–6279. Web of Science CrossRef PubMed CAS Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound is one of the most important intermediates used for the synthesis of Rynaxypyre, a new insecticidal anthranilic diamide as a potent and selective ryanodine receptor activator (Lahm et al., 2007). We report herein the crystal structure of the title compound.
In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring B (N3/C7-C11) is, of course, planar. Ring A (N1/N2/C4-C6) adopts envelope conformation with atom C4 displaced by -0.375 (3) Å from the plane of the other ring atoms.
In the crystal structure, intermolecular N-H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure.