(S)-5-Oxo-N-phenyl­pyrrolidine-2-carboxamide

Qin, W.-Y.; Liu, B.; Ma, J.; Wang, H.-J.

doi:10.1107/S160053681103786X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2763

https://doi.org/10.1107/S160053681103786X

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(S)-5-Oxo-N-phenylpyrrolidine-2-carboxamide

Wei-Yan Qin,^a Bo Liu,^a ^* Jing Ma ^a and Hui-Juan Wang ^a

^aKey Laboratory of Green Chemical Technology, College of Heilongjiang Province, School of Chemistry and Environmental Engineering, Harbin University of Science and Technology, Harbin 150040, People's Republic of China
^*Correspondence e-mail: liubo@hrbust.edu.cn

(Received 24 August 2011; accepted 16 September 2011; online 30 September 2011)

The title compound, C₁₁H₁₂N₂O₂, shows an S configuration, in which the pyrrolidinone ring is twisted with respect to the phenyl plane, making a dihedral angle of 70.73 (7)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, building up a layer parallel to (001).

Related literature

For the synthesis of the title compound, see Feng et al. (2010 ). For its chemical properties, including assignment of absolute structure, see: Brunel et al. (1999 ).

Experimental

Crystal data

C₁₁H₁₂N₂O₂
M_r = 204.23
Monoclinic, P 2₁
a = 4.919 (3) Å
b = 9.995 (7) Å
c = 10.382 (7) Å
β = 99.05 (3)°
V = 504.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.23 × 0.18 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan ABSCOR (Higashi, 1995 ) T_min = 0.979, T_max = 0.985
3688 measured reflections
2184 independent reflections
1997 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.082
S = 1.05
2184 reflections
145 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O2ⁱ	0.89 (1)	1.98 (1)	2.869 (2)	172 (2)
N2—H12⋯O1ⁱⁱ	0.89 (1)	2.19 (1)	3.038 (2)	158 (2)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (ii) x+1, y, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681103786X/dn2719sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681103786X/dn2719Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681103786X/dn2719Isup3.cml

checkCIF report

Comment top

The title compound is an intermediate in the synthesis of highly potent and selective insecticide (Feng et al., 2010). Herein, we report its synthesis and crystal structure.

The pyrrolidinone ring is twisted with respect to phenyl plane with a dihedral angle of 70.73 (7) ° (Fig. 1).

Themolecules are linked by N—H···O hydrogen bonds into planar structure parallel to the (0 0 1) plane (Fig. 2, Table 1).

Related literature top

For the synthesis of the title compound, see Feng et al. (2010). For its chemical properties, see: Brunel et al. (1999).

Experimental top

The title compound was synthesized as the reference method (Feng et al., 2010; Brunel et al., 1999): a mixture of L-glutamic acid (3 g) and aniline (18 mL) was stirred at 195-200 °C. After 30 min, the mixture became clear, and the water formed was removed by azeotropic distillation. Stirring was maintained for 4 h. Excess of aniline was then recovered at 60-70 °C under reduced pressure distillation. The hot oily residue was swirled with acetone (25 mL) to lead to the formation of a brown solid, which was collected by filtration and dissolved in hot methanol (40 mL). The solution was slowly cooled to room temperature to afford crystalline optically pure (S)-N-phenylpyrrolidine-2-carboxamide as white crystals in 85% with the specific rotation about [α]²⁰_D + 18.0 (c 1.0, MeOH, 24 °C).

Structure description top

The title compound is an intermediate in the synthesis of highly potent and selective insecticide (Feng et al., 2010). Herein, we report its synthesis and crystal structure.

The pyrrolidinone ring is twisted with respect to phenyl plane with a dihedral angle of 70.73 (7) ° (Fig. 1).

Themolecules are linked by N—H···O hydrogen bonds into planar structure parallel to the (0 0 1) plane (Fig. 2, Table 1).

For the synthesis of the title compound, see Feng et al. (2010). For its chemical properties, see: Brunel et al. (1999).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular view of the title compound. Ellipsoids are drawn at the 50% probability level for non-H atoms.
	Fig. 2. A partial packing view, showing hydrogen-bonding layer structure parallel to the (0 0 1) plane.

(S)-5-Oxo-N-phenylpyrrolidine-2-carboxamide top

Crystal data top

C₁₁H₁₂N₂O₂	F(000) = 216
M_r = 204.23	D_x = 1.345 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1906 reflections
a = 4.919 (3) Å	θ = 2.9–28.3°
b = 9.995 (7) Å	µ = 0.09 mm⁻¹
c = 10.382 (7) Å	T = 296 K
β = 99.05 (3)°	Block, yellow
V = 504.1 (6) Å³	0.23 × 0.18 × 0.16 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	2184 independent reflections
Radiation source: fine-focus sealed tube	1997 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
ω scans	θ_max = 28.4°, θ_min = 2.0°
Absorption correction: multi-scan ABSCOR (Higashi, 1995)	h = −4→6
T_min = 0.979, T_max = 0.985	k = −12→13
3688 measured reflections	l = −13→11

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0429P)² + 0.035P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2184 reflections	Δρ_max = 0.17 e Å⁻³
145 parameters	Δρ_min = −0.11 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (6)

Crystal data top

C₁₁H₁₂N₂O₂	V = 504.1 (6) Å³
M_r = 204.23	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.919 (3) Å	µ = 0.09 mm⁻¹
b = 9.995 (7) Å	T = 296 K
c = 10.382 (7) Å	0.23 × 0.18 × 0.16 mm
β = 99.05 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2184 independent reflections
Absorption correction: multi-scan ABSCOR (Higashi, 1995)	1997 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.985	R_int = 0.014
3688 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	3 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.17 e Å⁻³
2184 reflections	Δρ_min = −0.11 e Å⁻³
145 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.5338 (3)	0.92196 (15)	0.78902 (13)	0.0367 (3)
C2	0.4415 (4)	1.02616 (18)	0.85717 (15)	0.0487 (4)
H2	0.4934	1.1134	0.8416	0.058*
C3	0.2721 (4)	1.0014 (2)	0.94858 (18)	0.0615 (5)
H3	0.2118	1.0721	0.9951	0.074*
C4	0.1922 (4)	0.8728 (2)	0.97111 (16)	0.0602 (5)
H4	0.0767	0.8561	1.0321	0.072*
C5	0.2838 (4)	0.7705 (2)	0.90327 (17)	0.0586 (5)
H5	0.2297	0.6835	0.9185	0.070*
C6	0.4553 (4)	0.79267 (18)	0.81216 (16)	0.0483 (4)
H6	0.5171	0.7214	0.7670	0.058*
C7	0.7855 (2)	0.87730 (14)	0.60470 (12)	0.0337 (3)
C8	0.9689 (3)	0.94686 (15)	0.51984 (13)	0.0360 (3)
H8	1.0871	1.0137	0.5700	0.043*
C9	0.7915 (3)	1.01089 (16)	0.40036 (14)	0.0413 (3)
H9A	0.6115	1.0355	0.4197	0.050*
H9B	0.8801	1.0898	0.3719	0.050*
C10	0.7685 (3)	0.90159 (17)	0.29767 (14)	0.0449 (4)
H10A	0.6000	0.8508	0.2960	0.054*
H10B	0.7722	0.9391	0.2118	0.054*
C11	1.0170 (3)	0.81512 (14)	0.33982 (14)	0.0373 (3)
N1	0.7110 (2)	0.95458 (13)	0.69845 (11)	0.0385 (3)
N2	1.1299 (2)	0.85149 (13)	0.46021 (11)	0.0388 (3)
O1	0.7047 (2)	0.76321 (11)	0.58091 (10)	0.0443 (3)
O2	1.1033 (3)	0.72678 (12)	0.27523 (12)	0.0538 (3)
H11	0.784 (3)	1.0363 (11)	0.7055 (16)	0.041 (4)*
H12	1.273 (3)	0.8084 (17)	0.5056 (15)	0.050 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0352 (6)	0.0417 (8)	0.0334 (6)	−0.0014 (6)	0.0056 (5)	0.0025 (5)
C2	0.0548 (9)	0.0447 (9)	0.0494 (8)	0.0007 (7)	0.0166 (7)	−0.0014 (7)
C3	0.0635 (10)	0.0709 (13)	0.0555 (10)	0.0069 (10)	0.0262 (8)	−0.0052 (9)
C4	0.0541 (9)	0.0852 (15)	0.0446 (8)	−0.0073 (10)	0.0178 (7)	0.0076 (10)
C5	0.0620 (10)	0.0636 (12)	0.0523 (9)	−0.0153 (9)	0.0157 (8)	0.0113 (8)
C6	0.0559 (9)	0.0435 (9)	0.0477 (8)	−0.0071 (7)	0.0146 (7)	0.0024 (7)
C7	0.0301 (5)	0.0332 (7)	0.0371 (6)	0.0013 (5)	0.0034 (5)	0.0012 (5)
C8	0.0322 (6)	0.0332 (7)	0.0437 (7)	−0.0036 (5)	0.0091 (5)	−0.0042 (6)
C9	0.0433 (7)	0.0323 (7)	0.0505 (8)	0.0080 (6)	0.0147 (6)	0.0060 (6)
C10	0.0453 (7)	0.0479 (9)	0.0415 (7)	0.0079 (7)	0.0067 (6)	0.0015 (6)
C11	0.0379 (7)	0.0317 (7)	0.0452 (7)	0.0000 (5)	0.0151 (6)	0.0031 (6)
N1	0.0439 (6)	0.0332 (7)	0.0403 (6)	−0.0069 (5)	0.0127 (5)	−0.0030 (5)
N2	0.0295 (5)	0.0416 (7)	0.0461 (6)	0.0063 (5)	0.0086 (4)	0.0022 (5)
O1	0.0458 (5)	0.0333 (5)	0.0561 (6)	−0.0059 (4)	0.0152 (5)	−0.0061 (4)
O2	0.0670 (7)	0.0397 (7)	0.0591 (7)	0.0090 (5)	0.0236 (6)	−0.0055 (5)

Geometric parameters (Å, º) top

C1—C2	1.376 (2)	C7—C8	1.524 (2)
C1—C6	1.381 (2)	C8—N2	1.4400 (19)
C1—N1	1.4170 (19)	C8—C9	1.539 (2)
C2—C3	1.380 (3)	C8—H8	0.9800
C2—H2	0.9300	C9—C10	1.518 (2)
C3—C4	1.375 (3)	C9—H9A	0.9700
C3—H3	0.9300	C9—H9B	0.9700
C4—C5	1.358 (3)	C10—C11	1.505 (2)
C4—H4	0.9300	C10—H10A	0.9700
C5—C6	1.381 (2)	C10—H10B	0.9700
C5—H5	0.9300	C11—O2	1.2244 (18)
C6—H6	0.9300	C11—N2	1.336 (2)
C7—O1	1.2201 (19)	N1—H11	0.891 (9)
C7—N1	1.3380 (19)	N2—H12	0.893 (9)

C2—C1—C6	119.69 (14)	N2—C8—H8	111.0
C2—C1—N1	117.01 (14)	C7—C8—H8	111.0
C6—C1—N1	123.30 (13)	C9—C8—H8	111.0
C1—C2—C3	120.12 (18)	C10—C9—C8	103.69 (13)
C1—C2—H2	119.9	C10—C9—H9A	111.0
C3—C2—H2	119.9	C8—C9—H9A	111.0
C4—C3—C2	120.27 (18)	C10—C9—H9B	111.0
C4—C3—H3	119.9	C8—C9—H9B	111.0
C2—C3—H3	119.9	H9A—C9—H9B	109.0
C5—C4—C3	119.24 (16)	C11—C10—C9	104.00 (13)
C5—C4—H4	120.4	C11—C10—H10A	111.0
C3—C4—H4	120.4	C9—C10—H10A	111.0
C4—C5—C6	121.53 (19)	C11—C10—H10B	111.0
C4—C5—H5	119.2	C9—C10—H10B	111.0
C6—C5—H5	119.2	H10A—C10—H10B	109.0
C1—C6—C5	119.15 (17)	O2—C11—N2	125.43 (14)
C1—C6—H6	120.4	O2—C11—C10	126.21 (14)
C5—C6—H6	120.4	N2—C11—C10	108.36 (13)
O1—C7—N1	124.68 (13)	C7—N1—C1	128.11 (13)
O1—C7—C8	120.86 (13)	C7—N1—H11	115.8 (12)
N1—C7—C8	114.32 (12)	C1—N1—H11	116.1 (11)
N2—C8—C7	111.24 (12)	C11—N2—C8	113.99 (11)
N2—C8—C9	102.08 (12)	C11—N2—H12	122.6 (12)
C7—C8—C9	110.08 (12)	C8—N2—H12	122.2 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2ⁱ	0.89 (1)	1.98 (1)	2.869 (2)	172 (2)
N2—H12···O1ⁱⁱ	0.89 (1)	2.19 (1)	3.038 (2)	158 (2)

Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂O₂
M_r	204.23
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	4.919 (3), 9.995 (7), 10.382 (7)
β (°)	99.05 (3)
V (Å³)	504.1 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan ABSCOR (Higashi, 1995)
T_min, T_max	0.979, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	3688, 2184, 1997
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.082, 1.05
No. of reflections	2184
No. of parameters	145
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.11

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), 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—H11···O2ⁱ	0.891 (9)	1.984 (10)	2.869 (2)	172.2 (16)
N2—H12···O1ⁱⁱ	0.893 (9)	2.192 (11)	3.038 (2)	157.7 (16)

Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) x+1, y, z.

Acknowledgements

The authors thank the National Natural Science Foundation of China (No. 20272011) and Harbin University of Science and Technology for supporting this work.

References

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