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

Abstract

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,

• a = 4.919 (3) Å

• b = 9.995 (7) Å

• c = 10.382 (7) Å

• β = 99.05 (3)°

• V = 504.1 (6) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681103786X/dn2719Isup3.cml

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—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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic); C—H = 0.97 Å (methylene), and C—H = 0.98 Å (methine), and with U_iso(H) = 1.2U_eq(C), while N-bound H atoms were found from difference Fourier and were refined using restraints [ N—H = 0.90 (1)Å].

Figures

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.

Crystal data

C11H12N2O2	F(000) = 216
Mr = 204.23	Dx = 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

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

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.082	w = 1/[σ2(Fo2) + (0.0429P)2 + 0.035P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2184 reflections	Δρmax = 0.17 e Å−3
145 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.