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Acta Crystallogr Sect E Struct Rep Online. 2010 June 1; 66(Pt 6): o1310.
Published online 2010 May 12. doi:  10.1107/S1600536810016193
PMCID: PMC2979556

Ethyl 4-(2-fur­yl)-2-oxochroman-3-carboxyl­ate

Abstract

The title compound, C16H14O5, was prepared from the reaction of 3-carbethoxy­coumarin with furan in the presence of AlCl3 as catalyst. In the crystal, inter­molecular C—H(...)O hydrogen-bonding inter­actions between four mol­ecules lead to a tetra­mer in the unit cell. The furan ring is anti­periplanar [C—C—C—O = 167.9 (13)°] and the ethoxy­carbonyl group is (−)anti­clinal [C—C—C—O = −128.6 (14)°] to the lactone ring.

Related literature

For the medicinal and biological activity of coumarins and their derivatives, see: Borges et al. (2005 [triangle]); Kontogiorgis & Hadjipavlou-Litina (2005 [triangle]); Gursoy & Karali (2003 [triangle]); Prabhakar et al. (2010 [triangle]). For the assignment of conformations and the orientation of the substituents, see: Nardelli (1983 [triangle], 1995 [triangle]); Klyne & Prelog (1960 [triangle]).

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Object name is e-66-o1310-scheme1.jpg

Experimental

Crystal data

  • C16H14O5
  • M r = 286.27
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1310-efi1.jpg
  • a = 10.393 (3) Å
  • b = 8.459 (3) Å
  • c = 15.819 (5) Å
  • β = 95.464 (5)°
  • V = 1384.5 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 298 K
  • 0.34 × 0.24 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2003 [triangle]) T min = 0.966, T max = 0.980
  • 13767 measured reflections
  • 2711 independent reflections
  • 2099 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.111
  • S = 1.04
  • 2711 reflections
  • 227 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 2003 [triangle]); cell refinement: SAINT (Bruker, 2003 [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 I, global. DOI: 10.1107/S1600536810016193/ds2028sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016193/ds2028Isup2.hkl

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

Acknowledgments

We thank the Director, Institute of Life Sciences, for support and also the Dean, School of Chemistry, University of Hyderabad, for the X-ray crystallographic data.

supplementary crystallographic information

Comment

We have synthesized and reported our serendipitous observations on the Diels-Alder reaction of 3-carbethoxy coumarin with furan, followed by a ring opening to yield Michael product, 3-carbethoxy-4-(2-furyl)-chroman-2-one in good yields.

Experimental

3-Carbethoxy coumarin (3 m mol) was taken into 30 mmol of furan and 10 mol% of AlCl3 catalyst was added. The reaction mixture was stirred at room temperature for 24 hours. After completion of the reaction, the excess of the furan was distilled off and extracted thrice with water/dichloromethane. The product was separated from flash column chromatography and recrystallized from dichloromethane.

Refinement

All H atoms were found on difference maps, with C—H=0.93 Å and included in the final cycles of refinement using a riding model, with Uiso(H)=1.2Ueq(C)

Figures

Fig. 1.
Chemical diagram of the title compound.
Fig. 2.
ORTEP diagram of the 3-carbethoxy-4-(2-furyl)-chroman-2-one. (Thermal ellipsoids are at 50% probability level).
Fig. 3.
Crystal packing of (I) showing the formation of tetramer. The C—H•••O contacts are shown as dashed lines. Symmetry code: (i) 1-x,-1/2+y, 1/2-z (ii) x, -1/2-y, -1/2+z
Fig. 4.
The formation of the title compound.

Crystal data

C16H14O5F(000) = 600
Mr = 286.27Dx = 1.373 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5174 reflections
a = 10.393 (3) Åθ = 2.5–25.8°
b = 8.459 (3) ŵ = 0.10 mm1
c = 15.819 (5) ÅT = 298 K
β = 95.464 (5)°Block, colourless
V = 1384.5 (8) Å30.34 × 0.24 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2711 independent reflections
Radiation source: fine-focus sealed tube2099 reflections with I > 2σ(I)
graphiteRint = 0.035
phi and ω scansθmax = 25.9°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)h = −12→12
Tmin = 0.966, Tmax = 0.980k = −10→10
13767 measured reflectionsl = −19→19

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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.058P)2 + 0.1619P] where P = (Fo2 + 2Fc2)/3
2711 reflections(Δ/σ)max < 0.001
227 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = −0.15 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
H20.5893 (16)0.9788 (19)0.7769 (10)0.045 (4)*
H130.648 (2)1.325 (3)1.0884 (14)0.084 (7)*
H110.598 (2)1.251 (2)0.8313 (14)0.076 (6)*
H120.598 (2)1.472 (3)0.9435 (13)0.081 (6)*
H71.082 (2)0.672 (3)1.0318 (14)0.085 (7)*
H60.8933 (19)0.630 (2)1.0962 (13)0.073 (6)*
H81.077 (2)0.828 (2)0.9093 (13)0.078 (6)*
H50.6973 (18)0.7462 (19)1.0400 (11)0.048 (5)*
H30.5753 (15)0.8783 (17)0.9186 (9)0.033 (4)*
C60.8921 (2)0.6956 (2)1.04771 (12)0.0626 (5)
O30.65502 (12)1.13244 (14)1.01627 (7)0.0545 (3)
O10.88812 (11)0.98037 (14)0.83531 (7)0.0523 (3)
O50.74734 (13)0.71312 (14)0.73664 (7)0.0598 (4)
O20.78518 (13)1.08381 (15)0.72090 (7)0.0635 (4)
C30.65067 (15)0.93666 (18)0.90397 (9)0.0404 (4)
O40.57089 (13)0.66307 (15)0.80304 (8)0.0651 (4)
C40.77275 (15)0.86004 (17)0.94453 (9)0.0388 (4)
C10.77894 (17)1.00313 (19)0.78254 (10)0.0460 (4)
C90.88546 (15)0.88312 (18)0.90688 (10)0.0429 (4)
C20.65772 (16)0.92533 (19)0.80739 (10)0.0425 (4)
C140.65204 (17)0.7516 (2)0.78227 (10)0.0465 (4)
C130.63873 (19)1.2923 (2)1.02691 (14)0.0597 (5)
C81.00056 (18)0.8154 (2)0.93811 (12)0.0576 (5)
C50.77720 (19)0.7640 (2)1.01532 (10)0.0502 (4)
C100.63742 (14)1.10518 (19)0.93083 (9)0.0419 (4)
C110.61161 (18)1.2410 (2)0.89003 (12)0.0550 (5)
C120.61250 (19)1.3618 (2)0.95281 (13)0.0593 (5)
C150.7673 (2)0.5456 (2)0.71929 (12)0.0718 (6)
H15A0.80290.53390.66520.086*
H15B0.68530.49020.71620.086*
C71.0035 (2)0.7225 (2)1.00924 (13)0.0656 (5)
C160.8571 (2)0.4771 (2)0.78765 (14)0.0738 (6)
H16A0.93560.53760.79350.111*
H16B0.87630.36980.77370.111*
H16C0.81770.47950.84010.111*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C60.0812 (15)0.0569 (11)0.0475 (10)0.0109 (10)−0.0047 (10)0.0124 (9)
O30.0658 (8)0.0534 (7)0.0449 (7)0.0049 (6)0.0093 (5)−0.0084 (5)
O10.0463 (7)0.0581 (7)0.0526 (7)−0.0034 (5)0.0059 (5)0.0137 (6)
O50.0819 (9)0.0466 (7)0.0524 (7)0.0094 (6)0.0151 (7)−0.0060 (5)
O20.0824 (9)0.0614 (8)0.0474 (7)0.0061 (7)0.0110 (6)0.0171 (6)
C30.0377 (8)0.0423 (9)0.0416 (8)−0.0022 (7)0.0052 (7)−0.0030 (7)
O40.0666 (8)0.0592 (8)0.0684 (9)−0.0165 (7)0.0007 (7)−0.0116 (6)
C40.0459 (9)0.0342 (8)0.0357 (8)−0.0005 (6)0.0000 (6)−0.0043 (6)
C10.0571 (10)0.0409 (9)0.0403 (9)0.0072 (7)0.0058 (8)0.0004 (7)
C90.0453 (9)0.0417 (8)0.0410 (8)−0.0012 (7)0.0005 (7)0.0016 (7)
C20.0446 (9)0.0423 (9)0.0392 (8)0.0078 (7)−0.0041 (7)−0.0021 (7)
C140.0539 (10)0.0482 (9)0.0352 (8)0.0012 (8)−0.0077 (7)−0.0034 (7)
C130.0629 (12)0.0556 (11)0.0622 (12)−0.0001 (9)0.0144 (10)−0.0197 (10)
C80.0456 (10)0.0652 (12)0.0609 (11)0.0047 (8)−0.0008 (9)0.0030 (9)
C50.0623 (11)0.0471 (10)0.0420 (9)−0.0002 (8)0.0081 (8)0.0010 (8)
C100.0384 (8)0.0479 (9)0.0394 (8)0.0024 (7)0.0044 (6)−0.0057 (7)
C110.0628 (12)0.0512 (10)0.0508 (11)0.0106 (8)0.0039 (9)−0.0008 (9)
C120.0629 (12)0.0441 (10)0.0723 (13)0.0059 (9)0.0138 (10)−0.0066 (9)
C150.1093 (17)0.0474 (11)0.0597 (12)0.0141 (11)0.0133 (12)−0.0108 (9)
C70.0622 (13)0.0673 (13)0.0641 (12)0.0171 (10)−0.0104 (10)0.0071 (10)
C160.0813 (15)0.0552 (11)0.0863 (15)0.0111 (10)0.0158 (12)0.0064 (11)

Geometric parameters (Å, °)

C6—C71.377 (3)C2—C141.522 (2)
C6—C51.381 (3)C2—H20.937 (17)
C6—H60.94 (2)C13—C121.317 (3)
O3—C101.3663 (19)C13—H131.01 (2)
O3—C131.375 (2)C8—C71.371 (3)
O1—C11.357 (2)C8—H80.96 (2)
O1—C91.4020 (19)C5—H50.962 (18)
O5—C141.321 (2)C10—C111.333 (2)
O5—C151.462 (2)C11—C121.425 (3)
O2—C11.1969 (19)C11—H110.93 (2)
C3—C101.498 (2)C12—H120.95 (2)
C3—C41.512 (2)C15—C161.478 (3)
C3—C21.539 (2)C15—H15A0.9700
C3—H30.972 (15)C15—H15B0.9700
O4—C141.197 (2)C7—H70.95 (2)
C4—C91.378 (2)C16—H16A0.9600
C4—C51.381 (2)C16—H16B0.9600
C1—C21.506 (2)C16—H16C0.9600
C9—C81.375 (2)
C7—C6—C5120.05 (18)O3—C13—H13113.0 (13)
C7—C6—H6120.5 (13)C7—C8—C9118.97 (19)
C5—C6—H6119.4 (13)C7—C8—H8119.9 (13)
C10—O3—C13106.29 (14)C9—C8—H8121.0 (13)
C1—O1—C9120.03 (12)C6—C5—C4120.55 (18)
C14—O5—C15117.97 (15)C6—C5—H5122.2 (10)
C10—C3—C4112.56 (13)C4—C5—H5117.2 (10)
C10—C3—C2110.80 (13)C11—C10—O3109.59 (14)
C4—C3—C2106.09 (12)C11—C10—C3134.68 (15)
C10—C3—H3108.5 (8)O3—C10—C3115.73 (13)
C4—C3—H3110.1 (8)C10—C11—C12107.06 (17)
C2—C3—H3108.7 (8)C10—C11—H11124.6 (13)
C9—C4—C5118.03 (15)C12—C11—H11128.3 (13)
C9—C4—C3117.99 (13)C13—C12—C11106.68 (17)
C5—C4—C3123.94 (15)C13—C12—H12126.2 (13)
O2—C1—O1118.36 (16)C11—C12—H12127.1 (13)
O2—C1—C2124.98 (16)O5—C15—C16109.51 (16)
O1—C1—C2116.65 (13)O5—C15—H15A109.8
C8—C9—C4122.14 (15)C16—C15—H15A109.8
C8—C9—O1116.82 (15)O5—C15—H15B109.8
C4—C9—O1121.02 (13)C16—C15—H15B109.8
C1—C2—C14111.48 (13)H15A—C15—H15B108.2
C1—C2—C3110.60 (13)C8—C7—C6120.24 (18)
C14—C2—C3108.36 (13)C8—C7—H7120.9 (14)
C1—C2—H2105.5 (10)C6—C7—H7118.8 (14)
C14—C2—H2108.9 (10)C15—C16—H16A109.5
C3—C2—H2112.1 (10)C15—C16—H16B109.5
O4—C14—O5125.46 (16)H16A—C16—H16B109.5
O4—C14—C2122.91 (16)C15—C16—H16C109.5
O5—C14—C2111.62 (15)H16A—C16—H16C109.5
C12—C13—O3110.37 (17)H16B—C16—H16C109.5
C12—C13—H13136.6 (13)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C3—H3···O3i0.972 (15)2.696 (15)3.576 (2)150.8 (11)
C16—H16B···O2ii0.962.703.549 (3)148
C16—H16A···O2iii0.962.963.841 (3)153
C8—H8···O3iv0.96 (2)2.94 (2)3.611 (3)128.2 (15)
C11—H11···O4v0.93 (2)2.73 (2)3.501 (3)140.9 (17)
C13—H13···O2vi1.01 (2)2.54 (2)3.456 (3)151.0 (17)
C12—H12···O4vii0.95 (2)2.74 (2)3.478 (3)134.9 (16)

Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) x, y−1, z; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, −y+2, −z+2; (v) −x+1, y+1/2, −z+3/2; (vi) x, −y+5/2, z+1/2; (vii) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DS2028).

References

  • Borges, F., Roleira, F., Milhazes, N., Santana, L. & Uriarte, E. (2005). Curr. Med. Chem 12, 887–916. [PubMed]
  • Bruker (2003). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gursoy, A. & &Karali, N. (2003). Turk. J. Chem 27, 545–551.
  • Klyne, W. & Prelog, V. (1960). Experientia, 16, 521–568.
  • Kontogiorgis, C. A. & Hadjipavlou-Litina, D. J. (2005). J. Med. Chem 48, 6400–6408. [PubMed]
  • Nardelli, M. (1983). Acta Cryst. C39, 1141–1142.
  • Nardelli, M. (1995). J. Appl. Cryst 28, 659.
  • Prabhakar, M., Narendar Reddy, G., Srinu, G., Manjulatha, K., Venkata Prasad, J., Pramod Kumar, S., Srinivas, O., Iqbal, J. & Anil Kumar, K. (2010). Synlett, pp. 947–951.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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