PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1578.
Published online 2010 June 5. doi:  10.1107/S1600536810017939
PMCID: PMC3006878

(E)-2-(2-Furylmethyl­idene)-2,3-dihydro-1H-pyrrolizin-1-one

Abstract

The title compound, C12H9NO2, was prepared by an Aldol reaction of furfuraldehyde with 2,3-dihydro-1H-pyrrolizin-1-one. The mol­ecule is almost planar, with an r.m.s. deviation of 0.045 Å, excluding the methyl­ene H atoms. In the crystal structure, mol­ecules are linked via weak inter­molecular C—H(...)O hydrogen bonding and aromatic π–π stacking [centroid–centroid distance = 3.6151 (9) Å].

Related literature

For general background to synthetic dihydro­pyrrolizines and for the biological activity of related structures, see: Meinwald & Meinwald (1965 [triangle]); Skvortsov & Astakhova (1992 [triangle]). For the preparation of the starting material, see: Clemo & Ramage (1931 [triangle]); Braunholtz et al. (1962 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1578-scheme1.jpg

Experimental

Crystal data

  • C12H9NO2
  • M r = 199.20
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1578-efi1.jpg
  • a = 11.8170 (16) Å
  • b = 6.1242 (6) Å
  • c = 14.432 (2) Å
  • β = 113.157 (3)°
  • V = 960.3 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 113 K
  • 0.22 × 0.18 × 0.12 mm

Data collection

  • Rigaku Saturn724 CCD camera diffractometer
  • 9348 measured reflections
  • 2271 independent reflections
  • 1796 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.100
  • S = 1.07
  • 2271 reflections
  • 136 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.23 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017939/xu2760sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017939/xu2760Isup2.hkl

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

Acknowledgments

YA is grateful to the Pakistan Council of Scientific & Industrial Research, Ministry of Science & Technology, Government of Pakistan, for financial support.

supplementary crystallographic information

Comment

Derivatives of 2,3-dihydropyrrolizine became known through studies of their synthesis (Clemo & Ramage, 1931; Braunholtz et al., 1962) and isolation from natural source (Meinwald & Meinwald, 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 & Astakhova, 1992).

Numbering scheme for the title compound is shown in an ORTEP (Farrugia, 1997) plot of the molecule, see Fig. 1. The three rings are essentially planar, rms deviation = 0.045 Å, with two metnylene H atoms above and below the plane (Fig. 2). Weak intermolecular C–H···O hydrogen bonding (Table 1) and aromatic π-π stacking between O2-containg ring and N1-containg ring [the centroids distance 3.6151 (9) Å] are present in the crystal structure (Fig. 3). Double bond connecting two ring systems have an E configuration.

Experimental

Title compound was prepared by an Aldol reaction of furfuraldehyde with 2,3-dihydro-1H-pyrrolizin-1-one (Fig. 4). Purification was carried out by Flash Column Chromatography, Petroleum Ether : Ethyl Acetate = 3:1, followed by recrystalization from Petroleum Ether.

Refinement

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

Figures

Fig. 1.
View of the single molecule showing atom numbering scheme. Displacement ellipsoids are drawn at 80% probability level.
Fig. 2.
View of molecule from top, showing two H atoms of methylene group, one above and one below the rings.
Fig. 3.
Packing diagram of cell unit showing straight chains not parallel to each other.
Fig. 4.
The preparation of the title compound.

Crystal data

C12H9NO2F(000) = 416
Mr = 199.20Dx = 1.378 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybcCell parameters from 2971 reflections
a = 11.8170 (16) Åθ = 1.5–28.0°
b = 6.1242 (6) ŵ = 0.10 mm1
c = 14.432 (2) ÅT = 113 K
β = 113.157 (3)°Prism, colourless
V = 960.3 (2) Å30.22 × 0.18 × 0.12 mm
Z = 4

Data collection

Rigaku Saturn724 CCD camera diffractometer1796 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.025
multilayerθmax = 27.9°, θmin = 1.9°
ω scansh = −14→15
9348 measured reflectionsk = −7→7
2271 independent reflectionsl = −18→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0572P)2 + 0.0917P] where P = (Fo2 + 2Fc2)/3
2271 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

Experimental. Single crystals suitable for X-ray crystallography were grown by slow evaporatin from ethyl acetate solution and of by slow cooling of a hot saturated solution of Petroleum Ether. Crystals obtained from later were found more suitable for X ray analysis.
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 > 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)

xyzUiso*/Ueq
O10.81898 (7)0.03138 (13)0.87581 (6)0.0268 (2)
O21.15722 (7)0.60788 (13)0.91369 (6)0.0239 (2)
N10.76145 (8)0.52826 (15)0.74753 (7)0.0190 (2)
C10.82061 (10)0.21177 (18)0.83928 (8)0.0190 (2)
C20.71886 (10)0.33225 (17)0.76750 (8)0.0187 (2)
C30.59277 (10)0.32408 (19)0.71216 (8)0.0219 (3)
H30.53870.20830.71100.026*
C40.56100 (11)0.52063 (19)0.65837 (9)0.0254 (3)
H40.48060.56180.61330.030*
C50.66732 (10)0.64550 (18)0.68219 (8)0.0229 (3)
H50.67250.78690.65710.027*
C60.89436 (10)0.56200 (19)0.80194 (8)0.0209 (2)
H6A0.91190.69130.84660.025*
H6B0.93630.57840.75500.025*
C70.93162 (10)0.35275 (17)0.86190 (8)0.0182 (2)
C81.04282 (10)0.29109 (18)0.92790 (8)0.0194 (2)
H81.04680.15250.95860.023*
C91.15627 (10)0.40818 (18)0.95782 (8)0.0197 (2)
C101.27159 (10)0.35966 (18)1.02555 (8)0.0221 (3)
H101.29590.23231.06620.026*
C111.34842 (10)0.5362 (2)1.02364 (8)0.0238 (3)
H111.43420.54991.06260.029*
C121.27594 (10)0.6803 (2)0.95590 (8)0.0247 (3)
H121.30370.81480.93960.030*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0259 (4)0.0196 (4)0.0298 (4)−0.0021 (3)0.0056 (4)0.0068 (3)
O20.0229 (4)0.0244 (4)0.0219 (4)−0.0043 (3)0.0061 (3)0.0043 (3)
N10.0198 (5)0.0185 (5)0.0183 (4)0.0014 (4)0.0070 (4)0.0023 (4)
C10.0218 (6)0.0175 (5)0.0178 (5)−0.0001 (4)0.0079 (4)−0.0011 (4)
C20.0212 (6)0.0179 (5)0.0180 (5)0.0000 (4)0.0087 (4)0.0000 (4)
C30.0206 (6)0.0244 (6)0.0208 (5)0.0000 (4)0.0082 (4)−0.0007 (4)
C40.0216 (6)0.0292 (7)0.0236 (5)0.0067 (5)0.0070 (5)0.0015 (5)
C50.0256 (6)0.0204 (6)0.0218 (5)0.0066 (5)0.0084 (5)0.0044 (4)
C60.0202 (6)0.0203 (6)0.0212 (5)−0.0011 (4)0.0072 (4)0.0029 (4)
C70.0203 (6)0.0177 (5)0.0174 (5)−0.0001 (4)0.0083 (4)0.0002 (4)
C80.0219 (5)0.0187 (5)0.0182 (5)0.0002 (4)0.0085 (4)0.0006 (4)
C90.0227 (6)0.0192 (5)0.0186 (5)−0.0001 (4)0.0095 (4)0.0002 (4)
C100.0211 (6)0.0237 (6)0.0207 (5)−0.0003 (4)0.0075 (4)−0.0009 (4)
C110.0198 (6)0.0297 (6)0.0217 (5)−0.0037 (5)0.0078 (4)−0.0036 (5)
C120.0236 (6)0.0286 (6)0.0222 (5)−0.0090 (5)0.0094 (5)−0.0020 (5)

Geometric parameters (Å, °)

O1—C11.2274 (13)C5—H50.9500
O2—C121.3652 (14)C6—C71.5117 (14)
O2—C91.3810 (13)C6—H6A0.9900
N1—C51.3480 (14)C6—H6B0.9900
N1—C21.3754 (14)C7—C81.3388 (14)
N1—C61.4683 (14)C8—C91.4292 (15)
C1—C21.4435 (14)C8—H80.9500
C1—C71.4953 (15)C9—C101.3613 (15)
C2—C31.3873 (15)C10—C111.4191 (16)
C3—C41.4011 (15)C10—H100.9500
C3—H30.9500C11—C121.3451 (17)
C4—C51.3935 (17)C11—H110.9500
C4—H40.9500C12—H120.9500
C12—O2—C9105.97 (9)N1—C6—H6B111.5
C5—N1—C2110.01 (9)C7—C6—H6B111.5
C5—N1—C6135.57 (10)H6A—C6—H6B109.3
C2—N1—C6114.42 (9)C8—C7—C1121.59 (10)
O1—C1—C2128.24 (10)C8—C7—C6129.04 (10)
O1—C1—C7125.91 (10)C1—C7—C6109.36 (9)
C2—C1—C7105.85 (9)C7—C8—C9127.96 (11)
N1—C2—C3108.03 (9)C7—C8—H8116.0
N1—C2—C1109.05 (9)C9—C8—H8116.0
C3—C2—C1142.91 (10)C10—C9—O2109.70 (10)
C2—C3—C4106.33 (10)C10—C9—C8131.50 (11)
C2—C3—H3126.8O2—C9—C8118.80 (9)
C4—C3—H3126.8C9—C10—C11106.69 (10)
C5—C4—C3108.40 (10)C9—C10—H10126.7
C5—C4—H4125.8C11—C10—H10126.7
C3—C4—H4125.8C12—C11—C10106.53 (10)
N1—C5—C4107.23 (10)C12—C11—H11126.7
N1—C5—H5126.4C10—C11—H11126.7
C4—C5—H5126.4C11—C12—O2111.11 (10)
N1—C6—C7101.32 (8)C11—C12—H12124.4
N1—C6—H6A111.5O2—C12—H12124.4
C7—C6—H6A111.5
C5—N1—C2—C30.38 (12)C2—C1—C7—C8178.79 (10)
C6—N1—C2—C3179.39 (9)O1—C1—C7—C6−179.66 (11)
C5—N1—C2—C1−178.70 (9)C2—C1—C7—C60.05 (12)
C6—N1—C2—C10.31 (12)N1—C6—C7—C8−178.51 (11)
O1—C1—C2—N1179.49 (11)N1—C6—C7—C10.11 (11)
C7—C1—C2—N1−0.21 (12)C1—C7—C8—C9−179.33 (10)
O1—C1—C2—C30.9 (2)C6—C7—C8—C9−0.85 (19)
C7—C1—C2—C3−178.76 (14)C12—O2—C9—C100.11 (12)
N1—C2—C3—C40.06 (12)C12—O2—C9—C8−179.84 (10)
C1—C2—C3—C4178.62 (14)C7—C8—C9—C10178.22 (11)
C2—C3—C4—C5−0.46 (12)C7—C8—C9—O2−1.85 (17)
C2—N1—C5—C4−0.67 (13)O2—C9—C10—C11−0.21 (12)
C6—N1—C5—C4−179.37 (11)C8—C9—C10—C11179.73 (11)
C3—C4—C5—N10.69 (13)C9—C10—C11—C120.23 (13)
C5—N1—C6—C7178.40 (12)C10—C11—C12—O2−0.17 (13)
C2—N1—C6—C7−0.26 (11)C9—O2—C12—C110.04 (12)
O1—C1—C7—C8−0.91 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6A···O1i0.992.473.3076 (15)142
C8—H8···O1ii0.952.553.3096 (14)137
C10—H10···O1ii0.952.463.1789 (15)133

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2760).

References

  • Braunholtz, J. T., Mallion, K. B. & Frederick, G. M. (1962). J. Chem. Soc pp. 4346–4353.
  • Clemo, G. R. & Ramage, G. R. (1931). J. Chem. Soc.7, 49–55.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Meinwald, J. & Meinwald, Y. C. (1965). J. Am. Chem. Soc. 88, 1305–1310.
  • Rigaku (2009). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Skvortsov, I. M. & Astakhova, L. N. (1992). Chem. Heterocycl. Compd, 28, 117–134.
  • Westrip, S. P. (2010). J. Appl. Cryst.43 Submitted.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography