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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1328.
Published online 2008 June 21. doi:  10.1107/S1600536808016504
PMCID: PMC2961739

(Z)-3-[1-(4-Methoxy­anilino)ethyl­idene]-4,5-dihydro­furan-2(3H)-one

Abstract

In the title compound, C13H15NO3, the dihydro­furan­one ring is planar to within 0.012 (4) Å and it forms a dihedral angle of 42.8 (2)° with the benzene ring. The amino­ethyl­idene group is coplanar with the dihydro­furan­one ring. The meth­oxy group is slightly twisted away from the benzene ring. An intra­molecular N—H(...)O hydrogen bond, generating an S(6) ring, is observed. In the crystal structure, the mol­ecules exist as C—H(...)O hydrogen-bonded dimers.

Related literature

For general background, see: Bartoli et al. (1994 [triangle]); Cimarelli & Palmieri (1996 [triangle]); Cimarelli et al. (1994 [triangle]); Elassar & El-Khair (2003 [triangle]); Greenhill (1977 [triangle]); Lubell et al. (1991 [triangle]); Michael et al. (1999 [triangle]); Negri et al. (2004 [triangle]); Reddy et al. (2005 [triangle]); Zhang et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1328-scheme1.jpg

Experimental

Crystal data

  • C13H15NO3
  • M r = 233.26
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1328-efi1.jpg
  • a = 12.562 (9) Å
  • b = 7.568 (5) Å
  • c = 24.531 (18) Å
  • V = 2332 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 (2) K
  • 0.26 × 0.20 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.963, T max = 0.990
  • 8990 measured reflections
  • 2051 independent reflections
  • 1409 reflections with I > 2σ(I)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.140
  • S = 1.20
  • 2051 reflections
  • 156 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016504/ci2605sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016504/ci2605Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from Jiangnan University.

supplementary crystallographic information

Comment

β-Enamino esters are a highly versatile class of intermediates for the synthesis of heterocycles (Reddy et al., 2005; Negri et al., 2004) and biologically active compounds, such as β-enamino acids, γ-enamino alcohols or β-enamino esters (Lubell et al., 1991; Bartoli et al., 1994; Cimarelli et al., 1994; Cimarelli & Palmieri, 1996). Many synthetic methods have been developed for the preparation of these compounds (Greenhill, 1977; Michael et al., 1999; Elassar & El-Khair, 2003). We synthesized a class of β-enamino compounds by reacting β-dicarbonyl compounds with amines in the presence of a catalytic amount of indium tribromide (Zhang et al. 2006). We report herein the crystal structure of the title compound (Fig.1).

In the title molecule, the dihydrofuranone ring is planar to within ±0.012 (4) Å and it forms a dihedral angle of 42.8 (2)° with the benzene ring. The aminoethylidene group is coplanar with the dihydrofuranone ring. The methoxy group is slightly twisted away from the benzene ring, with a C7—O1—C4—C5 torsion angle of 5.9 (5)°. The C11—C12 bond length [1.561 (5) Å] is markedly longther than usual C—C bond length. The N1—C8 bond length [1.400 (4) Å] is slightly shorter than the N1—C1 [1.439 (4) Å] bond length, indicating a weak electron delocalization. An intramolecular N1—H1···O2 hydrogen bond generating an S(6) ring is observed.

In the crystal structure, intermolecular C6—H6···O2 hydrogen bonds create centrosymmetric hydrogen-bonded dimers (Fig.2).

Experimental

A mixture of the 2-acetylcyclobutanone (5 mmol), 4-methoxybenzenamine (5 mmol) and InBr3 (0.05 mmol) was stirred at room temperature for 1 h. After completion of the reaction, the reaction mixture was diluted with H2O (10 ml) and extracted with EtOAc (210 ml). The combined organic layers were dried, concentrated, purified by column chromatography on SiO2 with ethyl acetate-cyclohexane (1:8). Pale yellow solid was obtained with a yield of 89% (m.p. 339–341 K). IR (neat):ν 3526, 2976, 1683, 1628, 1513, 1475, 1228, 1114, 1029, 947, 822, 763 cm-1; 1H NMR(CDCl3, 300 MHz): δ 1.91 (s, 3H), 2.89 (t, 2H), 4.02 (s, 3H), 4.34 (t, 2H), 6.84 (d, 1H), 6.99 (d, 1H), 9.77 (br s, 1H, NH). 13C NMR(CDCl3, 75 MHz): δ 17.4, 26.4, 63.7, 65.2, 87.6, 114.8, 126.6, 131.8, 154.6, 156.8, 173.9. ESI-MS: 233(M+1)+. Analysis calculated for C13H15NO: C 66.94, H 6.48, N 6.00%; found: C 67.17, H 5.58, N 5.68%. Single crystals suitable for X-ray diffraction study were obtained from ethyl acetate-cyclohexane by slow evaporation at room temperature.

Refinement

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N-H = 0.86 Å, C-H = 0.93–0.97 Å, and Uiso(H) = 1.5Ueq(CH3)or 1.2Ueq(C,N). Each methyl group was allowed to rotate freely about its C—C bond.

Figures

Fig. 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids. The dashed line indicates a hydrogen bond.
Fig. 2.
The crystal packing of the title compound, showing C—H···O hydrogen-bonded dimers.

Crystal data

C13H15NO3F000 = 992
Mr = 233.26Dx = 1.329 Mg m3Dm = 1.329 Mg m3Dm measured by not measured
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2424 reflections
a = 12.562 (9) Åθ = 2.3–26.5º
b = 7.568 (5) ŵ = 0.10 mm1
c = 24.531 (18) ÅT = 293 (2) K
V = 2332 (3) Å3Block, yellow
Z = 80.26 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer2051 independent reflections
Radiation source: fine-focus sealed tube1409 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.051
T = 293(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 1.7º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −6→14
Tmin = 0.963, Tmax = 0.990k = −6→9
8990 measured reflectionsl = −29→27

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.140  w = 1/[σ2(Fo2) + (0.0345P)2 + 1.787P] where P = (Fo2 + 2Fc2)/3
S = 1.20(Δ/σ)max = 0.001
2051 reflectionsΔρmax = 0.18 e Å3
156 parametersΔρmin = −0.21 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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 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
O10.60436 (17)0.4248 (3)0.28822 (9)0.0584 (7)
O20.56144 (16)0.3225 (3)−0.03039 (9)0.0577 (7)
O30.67421 (17)0.2671 (3)−0.09776 (9)0.0588 (7)
N10.66238 (18)0.4237 (3)0.06464 (10)0.0458 (7)
H10.60530.43650.04570.055*
C10.6483 (2)0.4258 (4)0.12125 (12)0.0359 (7)
C20.7161 (2)0.3370 (4)0.15658 (12)0.0418 (7)
H20.77360.27400.14270.050*
C30.6988 (2)0.3416 (4)0.21161 (12)0.0445 (8)
H30.74540.28320.23490.053*
C40.6133 (2)0.4313 (4)0.23285 (12)0.0397 (7)
C50.5438 (2)0.5155 (4)0.19836 (12)0.0408 (7)
H50.48450.57390.21220.049*
C60.5626 (2)0.5127 (4)0.14287 (12)0.0402 (7)
H60.51590.57120.11960.048*
C70.5122 (3)0.4963 (5)0.31207 (14)0.0639 (10)
H7A0.51030.62140.30580.096*
H7B0.51290.47380.35060.096*
H7C0.45040.44240.29610.096*
C80.7527 (2)0.4043 (4)0.03547 (11)0.0379 (7)
C90.8577 (2)0.4487 (4)0.06065 (13)0.0474 (8)
H9A0.89600.34170.06830.071*
H9B0.84640.51280.09390.071*
H9C0.89830.52010.03580.071*
C100.7493 (2)0.3554 (4)−0.01772 (11)0.0398 (7)
C110.8409 (2)0.3275 (5)−0.05534 (12)0.0511 (8)
H11A0.88770.2350−0.04210.061*
H11B0.88160.4353−0.06010.061*
C120.7864 (3)0.2733 (5)−0.10790 (14)0.0625 (10)
H12A0.80190.3582−0.13650.075*
H12B0.81180.1582−0.11950.075*
C130.6529 (3)0.3163 (4)−0.04569 (12)0.0450 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0501 (14)0.0825 (18)0.0428 (14)0.0102 (13)0.0055 (11)0.0044 (12)
O20.0335 (12)0.0875 (18)0.0520 (14)−0.0095 (12)−0.0071 (10)−0.0009 (12)
O30.0559 (14)0.0769 (17)0.0435 (13)−0.0083 (13)−0.0030 (11)−0.0100 (11)
N10.0240 (13)0.0681 (18)0.0452 (16)0.0017 (12)−0.0050 (11)−0.0001 (13)
C10.0293 (15)0.0367 (16)0.0416 (17)−0.0034 (13)−0.0038 (13)−0.0004 (13)
C20.0341 (16)0.0391 (17)0.0522 (19)0.0082 (14)0.0008 (14)−0.0047 (14)
C30.0389 (18)0.0450 (19)0.050 (2)0.0052 (15)−0.0065 (14)0.0042 (15)
C40.0347 (16)0.0399 (17)0.0444 (19)−0.0048 (14)0.0002 (13)0.0017 (13)
C50.0265 (15)0.0430 (18)0.0528 (19)0.0057 (13)0.0053 (14)0.0017 (14)
C60.0262 (15)0.0436 (18)0.0510 (19)0.0019 (13)−0.0058 (13)0.0071 (14)
C70.054 (2)0.085 (3)0.053 (2)0.000 (2)0.0131 (17)−0.0049 (19)
C80.0307 (15)0.0367 (16)0.0463 (18)0.0035 (13)−0.0058 (14)0.0018 (13)
C90.0352 (17)0.055 (2)0.052 (2)−0.0022 (15)−0.0074 (14)−0.0030 (15)
C100.0354 (16)0.0401 (17)0.0438 (18)−0.0025 (14)0.0001 (14)0.0017 (14)
C110.0454 (19)0.054 (2)0.054 (2)0.0036 (16)0.0042 (16)−0.0014 (16)
C120.061 (2)0.072 (3)0.055 (2)0.001 (2)0.0083 (18)−0.0076 (18)
C130.045 (2)0.0480 (19)0.0417 (19)−0.0052 (16)−0.0050 (15)0.0015 (14)

Geometric parameters (Å, °)

O1—C41.364 (4)C6—H60.93
O1—C71.406 (4)C7—H7A0.96
O2—C131.209 (4)C7—H7B0.96
O3—C131.357 (4)C7—H7C0.96
O3—C121.432 (4)C8—C101.357 (4)
N1—C81.349 (4)C8—C91.495 (4)
N1—C11.400 (4)C9—H9A0.96
N1—H10.86C9—H9B0.96
C1—C61.368 (4)C9—H9C0.96
C1—C21.389 (4)C10—C131.424 (4)
C2—C31.368 (4)C10—C111.490 (4)
C2—H20.93C11—C121.516 (4)
C3—C41.374 (4)C11—H11A0.97
C3—H30.93C11—H11B0.97
C4—C51.372 (4)C12—H12A0.97
C5—C61.382 (4)C12—H12B0.97
C5—H50.93
C4—O1—C7117.9 (3)H7B—C7—H7C109.5
C13—O3—C12110.4 (2)N1—C8—C10120.9 (3)
C8—N1—C1129.3 (2)N1—C8—C9119.9 (3)
C8—N1—H1115.3C10—C8—C9119.1 (3)
C1—N1—H1115.3C8—C9—H9A109.5
C6—C1—C2118.2 (3)C8—C9—H9B109.5
C6—C1—N1119.3 (3)H9A—C9—H9B109.5
C2—C1—N1122.4 (3)C8—C9—H9C109.5
C3—C2—C1120.4 (3)H9A—C9—H9C109.5
C3—C2—H2119.8H9B—C9—H9C109.5
C1—C2—H2119.8C8—C10—C13123.1 (3)
C2—C3—C4120.8 (3)C8—C10—C11127.6 (3)
C2—C3—H3119.6C13—C10—C11109.2 (3)
C4—C3—H3119.6C10—C11—C12102.5 (3)
O1—C4—C5125.3 (3)C10—C11—H11A111.3
O1—C4—C3115.1 (3)C12—C11—H11A111.3
C5—C4—C3119.5 (3)C10—C11—H11B111.3
C4—C5—C6119.4 (3)C12—C11—H11B111.3
C4—C5—H5120.3H11A—C11—H11B109.2
C6—C5—H5120.3O3—C12—C11107.8 (3)
C1—C6—C5121.6 (3)O3—C12—H12A110.1
C1—C6—H6119.2C11—C12—H12A110.1
C5—C6—H6119.2O3—C12—H12B110.1
O1—C7—H7A109.5C11—C12—H12B110.1
O1—C7—H7B109.5H12A—C12—H12B108.5
H7A—C7—H7B109.5O2—C13—O3119.4 (3)
O1—C7—H7C109.5O2—C13—C10130.6 (3)
H7A—C7—H7C109.5O3—C13—C10110.0 (3)
C8—N1—C1—C6154.5 (3)C1—N1—C8—C9−23.1 (5)
C8—N1—C1—C2−28.0 (5)N1—C8—C10—C13−2.0 (4)
C6—C1—C2—C3−2.0 (4)C9—C8—C10—C13−177.9 (3)
N1—C1—C2—C3−179.5 (3)N1—C8—C10—C11−179.7 (3)
C1—C2—C3—C41.1 (5)C9—C8—C10—C114.4 (5)
C7—O1—C4—C55.9 (5)C8—C10—C11—C12179.4 (3)
C7—O1—C4—C3−172.8 (3)C13—C10—C11—C121.4 (3)
C2—C3—C4—O1179.5 (3)C13—O3—C12—C111.9 (4)
C2—C3—C4—C50.8 (5)C10—C11—C12—O3−1.9 (4)
O1—C4—C5—C6179.6 (3)C12—O3—C13—O2178.4 (3)
C3—C4—C5—C6−1.8 (4)C12—O3—C13—C10−1.0 (4)
C2—C1—C6—C51.0 (4)C8—C10—C13—O22.3 (5)
N1—C1—C6—C5178.5 (3)C11—C10—C13—O2−179.6 (3)
C4—C5—C6—C10.9 (4)C8—C10—C13—O3−178.5 (3)
C1—N1—C8—C10161.0 (3)C11—C10—C13—O3−0.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O20.862.132.762 (4)130
C6—H6···O2i0.932.533.405 (4)158

Symmetry codes: (i) −x+1, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2605).

References

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