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ISSN: 2056-9890

2,3-Di­hydro-1H-pyrrolizin-1-one

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[Skvortsov, I. M. & Astakhova, L. N. (1992). Chem. Heterocycl. Compd, 28, 117-134.]). For the preparation, see: Braunholtz et al. (1962[Braunholtz, J. T., Mallion, K. B. & Frederick, G. M. (1962). J. Chem. Soc. pp. 4346-4353.]); Clemo & Ramage (1931[Clemo, G. R. & Ramage, G. R. (1931). J. Chem. Soc. 7, 49-55.]). For natural sources, see: Meinwald & Meinwald (1965[Meinwald, J. & Meinwald, Y. C. (1965). J. Am. Chem. Soc. 88, 1305-1310.]).

[Scheme 1]

Experimental

Crystal data
  • C7H7NO

  • Mr = 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[Rigaku (2009). CrystalClear-SM Expert. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.989, Tmax = 0.996

  • 10183 measured reflections

  • 2284 independent reflections

  • 2003 reflections with I > 2σ(I)

  • Rint = 0.051

Refinement
  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 0.118

  • S = 1.16

  • 2284 reflections

  • 163 parameters

  • H-atom parameters constrained

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.30 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2009). CrystalClear-SM Expert. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H = 0.95 and 0.99Å for aromatic and methylene respectively. Uiso(H) values were taken to be equal to 1.2 Ueq(C) for all hydrogen atoms.

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
[Figure 1] Fig. 1. Displacement ellipsoid plot (80% probability level) showing atom numbering scheme.
[Figure 2] Fig. 2. The packing showing the zigzg chains. Dashed lines indicate hydrogen bonds
2,3-Dihydro-1H-pyrrolizin-1-one top
Crystal data top
C7H7NOF(000) = 512
Mr = 121.14Dx = 1.381 Mg m3
Monoclinic, P21/cMelting point: 327(1) K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71075 Å
a = 11.301 (1) ÅCell parameters from 3403 reflections
b = 7.1730 (7) Åθ = 1.8–28.1°
c = 14.3760 (16) ŵ = 0.09 mm1
β = 90.989 (5)°T = 113 K
V = 1165.2 (2) Å3Prism, colorless
Z = 80.12 × 0.06 × 0.04 mm
Data collection top
Rigaku Saturn724 CCD camera
diffractometer
2284 independent reflections
Radiation source: rotating anode2003 reflections with I > 2σ(I)
Multilayer monochromatorRint = 0.051
ω scansθmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2009)
h = 1313
Tmin = 0.989, Tmax = 0.996k = 88
10183 measured reflectionsl = 1715
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.043P)2 + 0.3505P]
where P = (Fo2 + 2Fc2)/3
2284 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.30 e Å3
Crystal data top
C7H7NOV = 1165.2 (2) Å3
Mr = 121.14Z = 8
Monoclinic, P21/cMo Kα radiation
a = 11.301 (1) ŵ = 0.09 mm1
b = 7.1730 (7) ÅT = 113 K
c = 14.3760 (16) Å0.12 × 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)
Tmin = 0.989, Tmax = 0.996Rint = 0.051
10183 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 1.16Δρmax = 0.19 e Å3
2284 reflectionsΔρmin = 0.30 e Å3
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
xyzUiso*/Ueq
O10.84120 (12)0.0832 (2)0.57308 (9)0.0293 (4)
O20.49964 (11)0.0828 (2)0.17318 (10)0.0329 (4)
N10.72173 (13)0.1521 (2)0.35032 (11)0.0181 (4)
N20.20229 (13)0.1557 (2)0.11650 (11)0.0190 (4)
C10.78107 (17)0.0987 (3)0.50200 (13)0.0214 (4)
C20.64640 (16)0.0776 (3)0.49734 (13)0.0229 (5)
H2A0.60860.16460.54130.027*
H2B0.62330.05130.51360.027*
C30.60795 (16)0.1231 (3)0.39650 (13)0.0222 (4)
H3A0.56340.01830.36800.027*
H3B0.55860.23710.39380.027*
C40.81910 (16)0.1386 (3)0.40853 (13)0.0186 (4)
C50.91883 (17)0.1737 (3)0.35603 (13)0.0226 (4)
H50.99880.17280.37750.027*
C60.87834 (16)0.2109 (3)0.26502 (13)0.0218 (4)
H60.92650.24050.21360.026*
C70.75535 (16)0.1968 (3)0.26317 (13)0.0209 (4)
H70.70460.21520.21060.025*
C80.39292 (16)0.1181 (3)0.16955 (14)0.0219 (4)
C90.32016 (16)0.1840 (3)0.25181 (13)0.0223 (4)
H9A0.34900.30650.27430.027*
H9B0.32600.09340.30360.027*
C100.19132 (16)0.1993 (3)0.21584 (13)0.0208 (4)
H10A0.13950.10840.24720.025*
H10B0.15960.32650.22500.025*
C110.31432 (15)0.1065 (3)0.09001 (13)0.0186 (4)
C120.30999 (17)0.0643 (3)0.00456 (14)0.0223 (4)
H120.37410.02580.04190.027*
C130.19207 (17)0.0901 (3)0.03344 (14)0.0239 (5)
H130.16150.07210.09480.029*
C140.12721 (17)0.1468 (3)0.04322 (14)0.0238 (5)
H140.04500.17410.04350.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0349 (8)0.0343 (9)0.0185 (8)0.0044 (6)0.0039 (6)0.0005 (6)
O20.0195 (7)0.0467 (10)0.0324 (9)0.0055 (6)0.0011 (6)0.0079 (7)
N10.0169 (7)0.0209 (8)0.0165 (8)0.0002 (6)0.0003 (6)0.0004 (7)
N20.0187 (8)0.0195 (9)0.0188 (9)0.0013 (6)0.0020 (7)0.0012 (7)
C10.0263 (10)0.0175 (10)0.0203 (11)0.0021 (8)0.0006 (8)0.0020 (8)
C20.0280 (10)0.0213 (10)0.0196 (10)0.0017 (8)0.0044 (8)0.0000 (8)
C30.0179 (9)0.0247 (10)0.0241 (11)0.0019 (8)0.0032 (8)0.0006 (8)
C40.0198 (9)0.0198 (10)0.0160 (10)0.0012 (7)0.0031 (8)0.0022 (8)
C50.0189 (9)0.0254 (10)0.0233 (11)0.0002 (8)0.0016 (8)0.0033 (9)
C60.0224 (10)0.0237 (10)0.0193 (10)0.0013 (8)0.0032 (8)0.0003 (8)
C70.0238 (10)0.0227 (10)0.0161 (10)0.0015 (8)0.0015 (8)0.0016 (8)
C80.0207 (9)0.0200 (10)0.0249 (11)0.0004 (8)0.0007 (8)0.0004 (8)
C90.0230 (10)0.0251 (10)0.0187 (10)0.0004 (8)0.0007 (8)0.0008 (8)
C100.0222 (10)0.0228 (10)0.0177 (10)0.0015 (8)0.0043 (8)0.0020 (8)
C110.0190 (9)0.0183 (10)0.0184 (10)0.0016 (7)0.0030 (8)0.0000 (8)
C120.0267 (10)0.0199 (10)0.0204 (10)0.0004 (8)0.0039 (8)0.0003 (8)
C130.0307 (11)0.0233 (11)0.0176 (10)0.0011 (8)0.0024 (8)0.0005 (8)
C140.0222 (10)0.0244 (11)0.0246 (11)0.0008 (8)0.0044 (8)0.0001 (9)
Geometric parameters (Å, º) top
O1—C11.222 (2)C5—H50.9500
O2—C81.232 (2)C6—C71.393 (2)
N1—C71.354 (2)C6—H60.9500
N1—C41.374 (2)C7—H70.9500
N1—C31.472 (2)C8—C111.438 (3)
N2—C141.343 (2)C8—C91.527 (3)
N2—C111.374 (2)C9—C101.541 (3)
N2—C101.469 (2)C9—H9A0.9900
C1—C41.446 (3)C9—H9B0.9900
C1—C21.530 (3)C10—H10A0.9900
C2—C31.541 (3)C10—H10B0.9900
C2—H2A0.9900C11—C121.393 (3)
C2—H2B0.9900C12—C131.401 (3)
C3—H3A0.9900C12—H120.9500
C3—H3B0.9900C13—C141.395 (3)
C4—C51.390 (3)C13—H130.9500
C5—C61.404 (3)C14—H140.9500
C7—N1—C4110.21 (16)N1—C7—C6107.17 (17)
C7—N1—C3135.39 (16)N1—C7—H7126.4
C4—N1—C3114.33 (15)C6—C7—H7126.4
C14—N2—C11110.07 (16)O2—C8—C11127.76 (18)
C14—N2—C10135.23 (16)O2—C8—C9124.78 (18)
C11—N2—C10114.68 (15)C11—C8—C9107.47 (15)
O1—C1—C4128.66 (18)C8—C9—C10106.29 (15)
O1—C1—C2124.46 (18)C8—C9—H9A110.5
C4—C1—C2106.88 (16)C10—C9—H9A110.5
C1—C2—C3106.52 (15)C8—C9—H9B110.5
C1—C2—H2A110.4C10—C9—H9B110.5
C3—C2—H2A110.4H9A—C9—H9B108.7
C1—C2—H2B110.4N2—C10—C9102.47 (14)
C3—C2—H2B110.4N2—C10—H10A111.3
H2A—C2—H2B108.6C9—C10—H10A111.3
N1—C3—C2102.70 (14)N2—C10—H10B111.3
N1—C3—H3A111.2C9—C10—H10B111.3
C2—C3—H3A111.2H10A—C10—H10B109.2
N1—C3—H3B111.2N2—C11—C12108.01 (16)
C2—C3—H3B111.2N2—C11—C8108.92 (16)
H3A—C3—H3B109.1C12—C11—C8143.08 (18)
N1—C4—C5107.75 (16)C11—C12—C13106.13 (17)
N1—C4—C1109.38 (16)C11—C12—H12126.9
C5—C4—C1142.83 (17)C13—C12—H12126.9
C4—C5—C6106.62 (16)C14—C13—C12108.33 (17)
C4—C5—H5126.7C14—C13—H13125.8
C6—C5—H5126.7C12—C13—H13125.8
C7—C6—C5108.24 (17)N2—C14—C13107.47 (17)
C7—C6—H6125.9N2—C14—H14126.3
C5—C6—H6125.9C13—C14—H14126.3
O1—C1—C2—C3175.74 (18)O2—C8—C9—C10176.94 (19)
C4—C1—C2—C34.4 (2)C11—C8—C9—C103.2 (2)
C7—N1—C3—C2179.46 (19)C14—N2—C10—C9178.40 (19)
C4—N1—C3—C22.6 (2)C11—N2—C10—C93.8 (2)
C1—C2—C3—N14.14 (19)C8—C9—C10—N24.05 (19)
C7—N1—C4—C50.8 (2)C14—N2—C11—C120.0 (2)
C3—N1—C4—C5178.45 (15)C10—N2—C11—C12178.29 (15)
C7—N1—C4—C1177.53 (15)C14—N2—C11—C8179.72 (15)
C3—N1—C4—C10.1 (2)C10—N2—C11—C82.0 (2)
O1—C1—C4—N1177.28 (18)O2—C8—C11—N2179.24 (19)
C2—C1—C4—N12.8 (2)C9—C8—C11—N20.9 (2)
O1—C1—C4—C50.1 (4)O2—C8—C11—C121.2 (4)
C2—C1—C4—C5179.7 (2)C9—C8—C11—C12178.7 (2)
N1—C4—C5—C60.7 (2)N2—C11—C12—C130.1 (2)
C1—C4—C5—C6176.7 (2)C8—C11—C12—C13179.6 (2)
C4—C5—C6—C70.4 (2)C11—C12—C13—C140.1 (2)
C4—N1—C7—C60.6 (2)C11—N2—C14—C130.0 (2)
C3—N1—C7—C6177.51 (19)C10—N2—C14—C13177.84 (19)
C5—C6—C7—N10.1 (2)C12—C13—C14—N20.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O1i0.952.553.151 (2)121
C7—H7···O20.952.553.250 (2)130
C12—H12···O2ii0.952.513.435 (2)165
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC7H7NO
Mr121.14
Crystal system, space groupMonoclinic, P21/c
Temperature (K)113
a, b, c (Å)11.301 (1), 7.1730 (7), 14.3760 (16)
β (°) 90.989 (5)
V3)1165.2 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.12 × 0.06 × 0.04
Data collection
DiffractometerRigaku Saturn724 CCD camera
diffractometer
Absorption correctionMulti-scan
(CrystalClear-SM Expert; Rigaku, 2009)
Tmin, Tmax0.989, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
10183, 2284, 2003
Rint0.051
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.118, 1.16
No. of reflections2284
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C6—H6···O1i0.952.553.151 (2)121
C7—H7···O20.952.553.250 (2)130
C12—H12···O2ii0.952.513.435 (2)165
Symmetry codes: (i) x, y+1/2, z1/2; (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

First citationBraunholtz, J. T., Mallion, K. B. & Frederick, G. M. (1962). J. Chem. Soc. pp. 4346–4353.  CrossRef Web of Science Google Scholar
First citationClemo, G. R. & Ramage, G. R. (1931). J. Chem. Soc. 7, 49–55.  CrossRef Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationMeinwald, J. & Meinwald, Y. C. (1965). J. Am. Chem. Soc. 88, 1305–1310.  CrossRef Web of Science Google Scholar
First citationRigaku (2009). CrystalClear-SM Expert. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSkvortsov, I. M. & Astakhova, L. N. (1992). Chem. Heterocycl. Compd, 28, 117–134.  CrossRef Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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