Ethyl 2-(3-chloro-2-pyridyl)-5-oxopyrazolidine-3-carboxylate

Tan, H.-J.; He, H.-B.; Xia, M.; Zhang, X.-N.; Zhu, H.-J.

doi:10.1107/S1600536809020789

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1495

doi:10.1107/S1600536809020789

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Ethyl 2-(3-chloro-2-pyridyl)-5-oxopyrazolidine-3-carboxylate

Hai-Jun Tan,^a Hai-Bing He,^a Ming Xia,^a Xiang-Ning Zhang ^b and Hong-Jun Zhu ^a ^*

^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

(Received 20 May 2009; accepted 1 June 2009; online 6 June 2009)

In the molecule of the title compound, C₁₁H₁₂ClN₃O₃, the five membered ring adopts an envelope conformation. In the crystal structure, 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

C₁₁H₁₂ClN₃O₃
M_r = 269.69
Orthorhombic, P b c a
a = 15.488 (3) Å
b = 10.009 (2) Å
c = 16.249 (3) Å
V = 2518.9 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.913, T_max = 0.970
4453 measured reflections
2273 independent reflections
1635 reflections with I > 2σ(I)
R_int = 0.029
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.110
S = 1.03
2273 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809020789/hk2697sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020789/hk2697Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

For a related structure, see: Lahm et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

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.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: 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).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids at the 50% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

Ethyl 2-(3-chloro-2-pyridyl)-5-oxopyrazolidine-3-carboxylate top

Crystal data top

C₁₁H₁₂ClN₃O₃	F(000) = 1120
M_r = 269.69	D_x = 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

Data collection top

Enraf–Nonius CAD-4 diffractometer	1635 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 25.3°, θ_min = 2.5°
ω/2θ scans	h = 0→18
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
T_min = 0.913, T_max = 0.970	l = −19→19
4453 measured reflections	3 standard reflections every 120 min
2273 independent reflections	intensity decay: none

Refinement top

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(F_o²) + (0.0473P)² + 0.824P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2273 reflections	Δρ_max = 0.29 e Å⁻³
164 parameters	Δρ_min = −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)

Crystal data top

C₁₁H₁₂ClN₃O₃	V = 2518.9 (8) Å³
M_r = 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

Data collection top

Enraf–Nonius CAD-4 diffractometer	1635 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.029
T_min = 0.913, T_max = 0.970	3 standard reflections every 120 min
4453 measured reflections	intensity decay: none
2273 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.03	Δρ_max = 0.29 e Å⁻³
2273 reflections	Δρ_min = −0.23 e Å⁻³
164 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.913, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	4453, 2273, 1635
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

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