2,3-Dihydro-1H-pyrrolizin-1-one

Ali, Y.; Peng, Y.; Hua, E.; Anwar, M.A.; Kalhoro, M.A.

doi:10.1107/S1600536810034902

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2612

doi:10.1107/S1600536810034902

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2,3-Dihydro-1H-pyrrolizin-1-one

Yousaf Ali,^a ^* Yu Peng,^b Erbing Hua,^b Mohammad Aijaz Anwar ^a and Mehboob Ali Kalhoro ^a

^aPharmaceutical Research Center, PCSIR Laboratories Complex, Karachi 75280, Pakistan, and ^bDepartment of Pharmaceutical Engineering, Biotechnology College, Tianjin University of Science and Technology, Tianjin 300457, People's Republic of China
^*Correspondence e-mail: usfle8pcsir@yahoo.com

(Received 6 May 2010; accepted 30 August 2010; online 25 September 2010)

There are two nearly identical molecules in the asymmetric unit of the title compound, C₇H₇NO. The molecules are nearly planar (r.m.s. deviations of 0.025 and 0.017 Å) and oriented at a dihedral angle of 28.98 (3)°. The two molecules are linked by a C—H⋯O hydrogen bond. In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the molecules into zigzag chains along the c axis.

Related literature

For general background to 2,3-dihydropyrrolizine derivatives and their biological activity, see: Skvortsov & Astakhova (1992 ). For the preparation, see: Braunholtz et al. (1962 ); Clemo & Ramage (1931 ). For natural sources, see: Meinwald & Meinwald (1965 ).

Experimental

Crystal data

C₇H₇NO
M_r = 121.14
Monoclinic, P 2₁ /c
a = 11.301 (1) Å
b = 7.1730 (7) Å
c = 14.3760 (16) Å
β = 90.989 (5)°
V = 1165.2 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 113 K
0.12 × 0.06 × 0.04 mm

Data collection

Rigaku Saturn724 CCD camera diffractometer
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2009 ) T_min = 0.989, T_max = 0.996
10183 measured reflections
2284 independent reflections
2003 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.118
S = 1.16
2284 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	0.95	2.55	3.151 (2)	121
C7—H7⋯O2	0.95	2.55	3.250 (2)	130
C12—H12⋯O2ⁱⁱ	0.95	2.51	3.435 (2)	165
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z.

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810034902/bq2209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810034902/bq2209Isup2.hkl

checkCIF report

Comment top

Derivatives of 2,3-dihydropyrrolizine became known through studies of their synthesis (Clemo et al., 1931) and isolation from natural source (Meinwald et al., 1965). Synthetic dihydropyrrolizines that are of interest as pharmaceuticals have been reported. The most important of these, Ketorolac, is a non steroid analgesic. Depending on their structure, derivatives of 2,3-dihydropyrrolizine have shown merit as analgesics, anti-inflammatory agents, myorelaxants, inhibitors of thrombocyte aggregation, fibrinolytics, temperature-lowering substances and drugs for the treatment of glaucoma and conjunctivitis (Skvortsov et al., 1992).

The ORTEP (Farrugia, 1997) drawing of the molecule is shown in Fig. 1. The sums of the three angles at N1 and C4 are 359.93 and 359.96 respectively, indicating that two rings are almost planer with an r.m.s. deviation of 0.05 Å. Molecules are held together in crystal packing by weak C—H···O hydrogen bonds (Table 1), in the form of zigzag infinite one dimensional polymeric chains (Fig. 2.).

Related literature top

For general background to 2,3-dihydropyrrolizine derivatives and their biological activity, see: Skvortsov & Astakhova (1992). For the preparation, see: Braunholtz et al. (1962); Clemo & Ramage (1931). For related literature [on hat subject?], see: Meinwald & Meinwald (1965).

Experimental top

The preparation of title compound was carried out as described in the procedure reported in literature (Braunholtz et al., 1962). Purified by Flash Column Chromatography, Petroleum Ether:Ethyl Acetate = 3:1.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert (Rigaku, 2009); data reduction: CrystalClear-SM Expert (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Displacement ellipsoid plot (80% probability level) showing atom numbering scheme.
	Fig. 2. The packing showing the zigzg chains. Dashed lines indicate hydrogen bonds

2,3-Dihydro-1H-pyrrolizin-1-one top

Crystal data top

C₇H₇NO	F(000) = 512
M_r = 121.14	D_x = 1.381 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 327(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71075 Å
a = 11.301 (1) Å	Cell parameters from 3403 reflections
b = 7.1730 (7) Å	θ = 1.8–28.1°
c = 14.3760 (16) Å	µ = 0.09 mm⁻¹
β = 90.989 (5)°	T = 113 K
V = 1165.2 (2) Å³	Prism, colorless
Z = 8	0.12 × 0.06 × 0.04 mm

Data collection top

Rigaku Saturn724 CCD camera diffractometer	2284 independent reflections
Radiation source: rotating anode	2003 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.051
ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2009)	h = −13→13
T_min = 0.989, T_max = 0.996	k = −8→8
10183 measured reflections	l = −17→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.043P)² + 0.3505P] where P = (F_o² + 2F_c²)/3
2284 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₇H₇NO	V = 1165.2 (2) Å³
M_r = 121.14	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.301 (1) Å	µ = 0.09 mm⁻¹
b = 7.1730 (7) Å	T = 113 K
c = 14.3760 (16) Å	0.12 × 0.06 × 0.04 mm
β = 90.989 (5)°

Data collection top

Rigaku Saturn724 CCD camera diffractometer	2284 independent reflections
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2009)	2003 reflections with I > 2σ(I)
T_min = 0.989, T_max = 0.996	R_int = 0.051
10183 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.16	Δρ_max = 0.19 e Å⁻³
2284 reflections	Δρ_min = −0.30 e Å⁻³
163 parameters

Special details top

Experimental. Single crystals suitable for X-ray crystallography were grown by slow cooling of a hot saturated solution of Petroleum Ether.

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 RSHELXS-97 -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
O1	0.84120 (12)	0.0832 (2)	0.57308 (9)	0.0293 (4)
O2	0.49964 (11)	0.0828 (2)	0.17318 (10)	0.0329 (4)
N1	0.72173 (13)	0.1521 (2)	0.35032 (11)	0.0181 (4)
N2	0.20229 (13)	0.1557 (2)	0.11650 (11)	0.0190 (4)
C1	0.78107 (17)	0.0987 (3)	0.50200 (13)	0.0214 (4)
C2	0.64640 (16)	0.0776 (3)	0.49734 (13)	0.0229 (5)
H2A	0.6086	0.1646	0.5413	0.027*
H2B	0.6233	−0.0513	0.5136	0.027*
C3	0.60795 (16)	0.1231 (3)	0.39650 (13)	0.0222 (4)
H3A	0.5634	0.0183	0.3680	0.027*
H3B	0.5586	0.2371	0.3938	0.027*
C4	0.81910 (16)	0.1386 (3)	0.40853 (13)	0.0186 (4)
C5	0.91883 (17)	0.1737 (3)	0.35603 (13)	0.0226 (4)
H5	0.9988	0.1728	0.3775	0.027*
C6	0.87834 (16)	0.2109 (3)	0.26502 (13)	0.0218 (4)
H6	0.9265	0.2405	0.2136	0.026*
C7	0.75535 (16)	0.1968 (3)	0.26317 (13)	0.0209 (4)
H7	0.7046	0.2152	0.2106	0.025*
C8	0.39292 (16)	0.1181 (3)	0.16955 (14)	0.0219 (4)
C9	0.32016 (16)	0.1840 (3)	0.25181 (13)	0.0223 (4)
H9A	0.3490	0.3065	0.2743	0.027*
H9B	0.3260	0.0934	0.3036	0.027*
C10	0.19132 (16)	0.1993 (3)	0.21584 (13)	0.0208 (4)
H10A	0.1395	0.1084	0.2472	0.025*
H10B	0.1596	0.3265	0.2250	0.025*
C11	0.31432 (15)	0.1065 (3)	0.09001 (13)	0.0186 (4)
C12	0.30999 (17)	0.0643 (3)	−0.00456 (14)	0.0223 (4)
H12	0.3741	0.0258	−0.0419	0.027*
C13	0.19207 (17)	0.0901 (3)	−0.03344 (14)	0.0239 (5)
H13	0.1615	0.0721	−0.0948	0.029*
C14	0.12721 (17)	0.1468 (3)	0.04322 (14)	0.0238 (5)
H14	0.0450	0.1741	0.0435	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0349 (8)	0.0343 (9)	0.0185 (8)	0.0044 (6)	−0.0039 (6)	−0.0005 (6)
O2	0.0195 (7)	0.0467 (10)	0.0324 (9)	0.0055 (6)	−0.0011 (6)	−0.0079 (7)
N1	0.0169 (7)	0.0209 (8)	0.0165 (8)	0.0002 (6)	0.0003 (6)	−0.0004 (7)
N2	0.0187 (8)	0.0195 (9)	0.0188 (9)	0.0013 (6)	0.0020 (7)	−0.0012 (7)
C1	0.0263 (10)	0.0175 (10)	0.0203 (11)	0.0021 (8)	−0.0006 (8)	−0.0020 (8)
C2	0.0280 (10)	0.0213 (10)	0.0196 (10)	−0.0017 (8)	0.0044 (8)	0.0000 (8)
C3	0.0179 (9)	0.0247 (10)	0.0241 (11)	−0.0019 (8)	0.0032 (8)	0.0006 (8)
C4	0.0198 (9)	0.0198 (10)	0.0160 (10)	0.0012 (7)	−0.0031 (8)	−0.0022 (8)
C5	0.0189 (9)	0.0254 (10)	0.0233 (11)	−0.0002 (8)	−0.0016 (8)	−0.0033 (9)
C6	0.0224 (10)	0.0237 (10)	0.0193 (10)	−0.0013 (8)	0.0032 (8)	−0.0003 (8)
C7	0.0238 (10)	0.0227 (10)	0.0161 (10)	0.0015 (8)	−0.0015 (8)	0.0016 (8)
C8	0.0207 (9)	0.0200 (10)	0.0249 (11)	−0.0004 (8)	0.0007 (8)	0.0004 (8)
C9	0.0230 (10)	0.0251 (10)	0.0187 (10)	−0.0004 (8)	0.0007 (8)	−0.0008 (8)
C10	0.0222 (10)	0.0228 (10)	0.0177 (10)	0.0015 (8)	0.0043 (8)	−0.0020 (8)
C11	0.0190 (9)	0.0183 (10)	0.0184 (10)	0.0016 (7)	0.0030 (8)	0.0000 (8)
C12	0.0267 (10)	0.0199 (10)	0.0204 (10)	0.0004 (8)	0.0039 (8)	−0.0003 (8)
C13	0.0307 (11)	0.0233 (11)	0.0176 (10)	0.0011 (8)	−0.0024 (8)	0.0005 (8)
C14	0.0222 (10)	0.0244 (11)	0.0246 (11)	0.0008 (8)	−0.0044 (8)	0.0001 (9)

Geometric parameters (Å, º) top

O1—C1	1.222 (2)	C5—H5	0.9500
O2—C8	1.232 (2)	C6—C7	1.393 (2)
N1—C7	1.354 (2)	C6—H6	0.9500
N1—C4	1.374 (2)	C7—H7	0.9500
N1—C3	1.472 (2)	C8—C11	1.438 (3)
N2—C14	1.343 (2)	C8—C9	1.527 (3)
N2—C11	1.374 (2)	C9—C10	1.541 (3)
N2—C10	1.469 (2)	C9—H9A	0.9900
C1—C4	1.446 (3)	C9—H9B	0.9900
C1—C2	1.530 (3)	C10—H10A	0.9900
C2—C3	1.541 (3)	C10—H10B	0.9900
C2—H2A	0.9900	C11—C12	1.393 (3)
C2—H2B	0.9900	C12—C13	1.401 (3)
C3—H3A	0.9900	C12—H12	0.9500
C3—H3B	0.9900	C13—C14	1.395 (3)
C4—C5	1.390 (3)	C13—H13	0.9500
C5—C6	1.404 (3)	C14—H14	0.9500

C7—N1—C4	110.21 (16)	N1—C7—C6	107.17 (17)
C7—N1—C3	135.39 (16)	N1—C7—H7	126.4
C4—N1—C3	114.33 (15)	C6—C7—H7	126.4
C14—N2—C11	110.07 (16)	O2—C8—C11	127.76 (18)
C14—N2—C10	135.23 (16)	O2—C8—C9	124.78 (18)
C11—N2—C10	114.68 (15)	C11—C8—C9	107.47 (15)
O1—C1—C4	128.66 (18)	C8—C9—C10	106.29 (15)
O1—C1—C2	124.46 (18)	C8—C9—H9A	110.5
C4—C1—C2	106.88 (16)	C10—C9—H9A	110.5
C1—C2—C3	106.52 (15)	C8—C9—H9B	110.5
C1—C2—H2A	110.4	C10—C9—H9B	110.5
C3—C2—H2A	110.4	H9A—C9—H9B	108.7
C1—C2—H2B	110.4	N2—C10—C9	102.47 (14)
C3—C2—H2B	110.4	N2—C10—H10A	111.3
H2A—C2—H2B	108.6	C9—C10—H10A	111.3
N1—C3—C2	102.70 (14)	N2—C10—H10B	111.3
N1—C3—H3A	111.2	C9—C10—H10B	111.3
C2—C3—H3A	111.2	H10A—C10—H10B	109.2
N1—C3—H3B	111.2	N2—C11—C12	108.01 (16)
C2—C3—H3B	111.2	N2—C11—C8	108.92 (16)
H3A—C3—H3B	109.1	C12—C11—C8	143.08 (18)
N1—C4—C5	107.75 (16)	C11—C12—C13	106.13 (17)
N1—C4—C1	109.38 (16)	C11—C12—H12	126.9
C5—C4—C1	142.83 (17)	C13—C12—H12	126.9
C4—C5—C6	106.62 (16)	C14—C13—C12	108.33 (17)
C4—C5—H5	126.7	C14—C13—H13	125.8
C6—C5—H5	126.7	C12—C13—H13	125.8
C7—C6—C5	108.24 (17)	N2—C14—C13	107.47 (17)
C7—C6—H6	125.9	N2—C14—H14	126.3
C5—C6—H6	125.9	C13—C14—H14	126.3

O1—C1—C2—C3	175.74 (18)	O2—C8—C9—C10	−176.94 (19)
C4—C1—C2—C3	−4.4 (2)	C11—C8—C9—C10	3.2 (2)
C7—N1—C3—C2	−179.46 (19)	C14—N2—C10—C9	−178.40 (19)
C4—N1—C3—C2	−2.6 (2)	C11—N2—C10—C9	3.8 (2)
C1—C2—C3—N1	4.14 (19)	C8—C9—C10—N2	−4.05 (19)
C7—N1—C4—C5	−0.8 (2)	C14—N2—C11—C12	0.0 (2)
C3—N1—C4—C5	−178.45 (15)	C10—N2—C11—C12	178.29 (15)
C7—N1—C4—C1	177.53 (15)	C14—N2—C11—C8	179.72 (15)
C3—N1—C4—C1	−0.1 (2)	C10—N2—C11—C8	−2.0 (2)
O1—C1—C4—N1	−177.28 (18)	O2—C8—C11—N2	179.24 (19)
C2—C1—C4—N1	2.8 (2)	C9—C8—C11—N2	−0.9 (2)
O1—C1—C4—C5	0.1 (4)	O2—C8—C11—C12	−1.2 (4)
C2—C1—C4—C5	−179.7 (2)	C9—C8—C11—C12	178.7 (2)
N1—C4—C5—C6	0.7 (2)	N2—C11—C12—C13	0.1 (2)
C1—C4—C5—C6	−176.7 (2)	C8—C11—C12—C13	−179.6 (2)
C4—C5—C6—C7	−0.4 (2)	C11—C12—C13—C14	−0.1 (2)
C4—N1—C7—C6	0.6 (2)	C11—N2—C14—C13	0.0 (2)
C3—N1—C7—C6	177.51 (19)	C10—N2—C14—C13	−177.84 (19)
C5—C6—C7—N1	−0.1 (2)	C12—C13—C14—N2	0.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.95	2.55	3.151 (2)	121
C7—H7···O2	0.95	2.55	3.250 (2)	130
C12—H12···O2ⁱⁱ	0.95	2.51	3.435 (2)	165

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

Experimental details

Crystal data
Chemical formula	C₇H₇NO
M_r	121.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	11.301 (1), 7.1730 (7), 14.3760 (16)
β (°)	90.989 (5)
V (Å³)	1165.2 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.12 × 0.06 × 0.04

Data collection
Diffractometer	Rigaku Saturn724 CCD camera diffractometer
Absorption correction	Multi-scan (CrystalClear-SM Expert; Rigaku, 2009)
T_min, T_max	0.989, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	10183, 2284, 2003
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.118, 1.16
No. of reflections	2284
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.30

Computer programs: CrystalClear-SM Expert (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.95	2.55	3.151 (2)	121
C7—H7···O2	0.95	2.55	3.250 (2)	130
C12—H12···O2ⁱⁱ	0.95	2.51	3.435 (2)	165

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

Acknowledgements

YA is grateful to the Pakistan Council of Scientific & Industrial Research, Ministry of Science & Technology, Government of Pakistan, for financial support. PY is grateful to Tianjin University of Science & Technology for research funding (research grant No. 2009 0431).

References

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