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

Abstract

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,

• a = 15.488 (3) Å

• b = 10.009 (2) Å

• c = 16.249 (3) Å

• V = 2518.9 (8) ų

• 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[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

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 U_iso(H) = xU_eq(C,N), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

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.

Crystal data

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

Data collection

Enraf–Nonius CAD-4 diffractometer	1635 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
graphite	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

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)

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	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, °)

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, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2i	0.86	2.14	2.910 (3)	149

Symmetry codes: (i) −x+1, −y+1, −z+1.