organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Ethyl 5-bromo­naphtho­[2,1-b]furan-2-carboxyl­ate

aDepartment of Studies and Research in Chemistry, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, bDepartment of Chemistry, Kuvempu University, Shankaraghatta Shimoga, Karnataka, India, cCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and dDepartment of Studies and Research in Physics, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India
*Correspondence e-mail: palaksha.bspm@gmail.com

(Received 23 December 2012; accepted 29 December 2012; online 9 January 2013)

In the title compound, C15H11BrO3, the dihedral angle between the naphtho­furan ring system (r.m.s. deviation = 0.022 Å) and the side chain is 4.50 (2)°. In the crystal, short Br⋯Br [3.4435 (7) Å] contacts propagating along [010] in a zigzag manner and weak ππ inter­actions [shortest centroid–centroid separation = 3.573 (2) Å] directedalong [100] are observed.

Related literature

For background to the biological activity of naphtho­furan derivatives, see: Vaidya et al. (2011[Vaidya, V. P., Mahadevan, K. M., Shet Prakash, M., Sreenivas, S. & Shivananda, M. K. (2011). Res. J. Pharm. Biol. Chem. Sci. 2, 334-342.]).

[Scheme 1]

Experimental

Crystal data
  • C15H11BrO3

  • Mr = 319.15

  • Monoclinic, P 21 /c

  • a = 7.3108 (4) Å

  • b = 11.1545 (6) Å

  • c = 15.9752 (10) Å

  • β = 100.921 (4)°

  • V = 1279.16 (13) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.21 mm−1

  • T = 298 K

  • 0.28 × 0.24 × 0.18 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996)[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.] Tmin = 0.467, Tmax = 0.595

  • 10028 measured reflections

  • 2249 independent reflections

  • 1699 reflections with I > 2σ(I)

  • Rint = 0.037

Refinement
  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.127

  • S = 1.08

  • 2249 reflections

  • 172 parameters

  • H-atom parameters constrained

  • Δρmax = 0.59 e Å−3

  • Δρmin = −0.54 e Å−3

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2004[Bruker (2004). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; 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 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

As part of our ongoing studies of naphthofuran derivatives with possible biological activities (Vaidya et al., 2011), we now describe the structure of the title compound.

The title compound crystallizes in monoclinic crystal system with P21/c space group. The molecule is essentially planar with the dihedral angle between the mean planes defined by the naphthofuran moiety and the side chain is 4.50 (2)°, and the torsion angle of 179.81 (2)o for C15—C14—O3—C13 shows that the ethyl group is in planar orientation with the naphthofuran ring. In contrast to this, an antiperiplanar orientation is observed between the ethyl group and the naphthofuran ring in ethylnaphtho[2,1-b]furan-2-carboxylate. In the crystal, weak Br···Br and ππ interaction between the rings C1—C6 and O1—C12 occur.

Related literature top

For background to the biological activity of naphthofuran derivatives, see: Vaidya et al. (2011).

Experimental top

To a solution of ethyl naphtho[2,1-b]furan- 2-carboxylate (0.1 mol) in glacial acetic acid (20 ml) was added a solution of bromine (0.1 mol) in acetic acid (20 ml) with stirring during 1 h at 10–20°C and the stirring was continued for 3 h. The reaction mixture was poured into ice-cold water and the solid obtained was filtered out. It was washed with water, dried and the product was recrystallized from ethanol solution as colourless prisms.

Refinement top

The H atoms were positioned with idealized geometry using a riding model with C—H = 0.93 - 0.97 Å. The isotropic displacement parameters for all H atoms were set to 1.2 times of the Ueq of the parent atom (1.5 times of the Ueq of the parent atom for CH3).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Molecular packing of the title compound. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. Molecular packing of the title compound through ππ interactions are shown as dashed lines.
Ethyl 5-bromonaphtho[2,1-b]furan-2-carboxylate top
Crystal data top
C15H11BrO3prism
Mr = 319.15Dx = 1.657 Mg m3
Monoclinic, P21/cMelting point: 402 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.3108 (4) ÅCell parameters from 2249 reflections
b = 11.1545 (6) Åθ = 2.2–25.0°
c = 15.9752 (10) ŵ = 3.21 mm1
β = 100.921 (4)°T = 298 K
V = 1279.16 (13) Å3Prism, colourless
Z = 40.28 × 0.24 × 0.18 mm
F(000) = 640
Data collection top
Bruker APEXII CCD
diffractometer
2249 independent reflections
Radiation source: fine-focus sealed tube1699 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 0.95 pixels mm-1θmax = 25.0°, θmin = 2.2°
phi and ω scansh = 88
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1213
Tmin = 0.467, Tmax = 0.595l = 1818
10028 measured reflections
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0587P)2 + 1.4776P]
where P = (Fo2 + 2Fc2)/3
2249 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 0.54 e Å3
0 constraints
Crystal data top
C15H11BrO3V = 1279.16 (13) Å3
Mr = 319.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.3108 (4) ŵ = 3.21 mm1
b = 11.1545 (6) ÅT = 298 K
c = 15.9752 (10) Å0.28 × 0.24 × 0.18 mm
β = 100.921 (4)°
Data collection top
Bruker APEXII CCD
diffractometer
2249 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1699 reflections with I > 2σ(I)
Tmin = 0.467, Tmax = 0.595Rint = 0.037
10028 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.08Δρmax = 0.59 e Å3
2249 reflectionsΔρmin = 0.54 e Å3
172 parameters
Special details top

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) top
xyzUiso*/Ueq
C150.1065 (7)0.5565 (4)0.3863 (3)0.0671 (13)
H15A0.15560.62430.35230.101*
H15B0.19510.53060.41980.101*
H15C0.00770.57870.42330.101*
O10.1492 (4)0.0566 (2)0.36398 (17)0.0472 (7)
C10.3625 (5)0.1416 (3)0.5778 (3)0.0429 (10)
C20.4360 (6)0.2041 (4)0.6518 (3)0.0584 (12)
H20.47920.28210.64870.070*
C30.4446 (7)0.1483 (5)0.7312 (4)0.0722 (15)
H30.49560.19240.77940.087*
C40.3872 (6)0.0395 (4)0.7436 (3)0.0581 (12)
H40.39240.00760.79780.070*
C50.3127 (6)0.0296 (4)0.6643 (3)0.0552 (11)
H50.27340.10830.66870.066*
C60.3009 (5)0.0217 (3)0.5838 (3)0.0442 (9)
C70.2283 (5)0.0402 (3)0.5065 (3)0.0402 (9)
C80.2182 (5)0.0167 (3)0.4302 (3)0.0420 (9)
C90.2729 (6)0.1358 (3)0.4210 (3)0.0497 (10)
H90.26090.17220.36780.060*
C100.3435 (5)0.1938 (3)0.4934 (3)0.0487 (11)
C110.1573 (5)0.1595 (3)0.4862 (3)0.0422 (9)
H110.14420.22040.52440.051*
C120.1141 (5)0.1642 (3)0.4006 (3)0.0421 (9)
C130.0419 (6)0.2605 (4)0.3405 (3)0.0488 (10)
C140.0706 (7)0.4583 (4)0.3302 (3)0.0616 (12)
H14A0.01830.48380.29580.074*
H14B0.18520.43550.29230.074*
O20.0212 (6)0.2527 (3)0.2649 (2)0.0744 (10)
O30.0034 (4)0.3571 (2)0.38317 (19)0.0535 (8)
Br10.42767 (7)0.35357 (4)0.48343 (4)0.0708 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C150.088 (3)0.045 (3)0.069 (3)0.018 (2)0.017 (3)0.009 (2)
O10.0569 (16)0.0351 (15)0.0501 (17)0.0048 (12)0.0113 (13)0.0043 (12)
C10.0341 (18)0.034 (2)0.063 (3)0.0046 (16)0.0143 (18)0.0021 (19)
C20.053 (3)0.045 (3)0.075 (3)0.000 (2)0.007 (2)0.014 (2)
C30.064 (3)0.082 (4)0.065 (4)0.009 (3)0.003 (3)0.029 (3)
C40.046 (2)0.059 (3)0.069 (3)0.007 (2)0.009 (2)0.030 (2)
C50.057 (2)0.051 (3)0.059 (3)0.006 (2)0.014 (2)0.007 (2)
C60.0378 (19)0.040 (2)0.056 (3)0.0072 (16)0.0116 (18)0.0010 (19)
C70.0356 (18)0.033 (2)0.052 (2)0.0031 (15)0.0074 (17)0.0044 (18)
C80.0411 (19)0.034 (2)0.053 (3)0.0019 (16)0.0152 (18)0.0009 (19)
C90.053 (2)0.037 (2)0.063 (3)0.0029 (18)0.020 (2)0.008 (2)
C100.040 (2)0.0272 (19)0.081 (3)0.0003 (16)0.018 (2)0.001 (2)
C110.044 (2)0.035 (2)0.049 (3)0.0037 (16)0.0113 (18)0.0072 (18)
C120.042 (2)0.030 (2)0.054 (3)0.0015 (16)0.0098 (18)0.0041 (17)
C130.051 (2)0.044 (2)0.052 (3)0.0052 (18)0.010 (2)0.000 (2)
C140.083 (3)0.045 (2)0.057 (3)0.015 (2)0.014 (2)0.015 (2)
O20.114 (3)0.063 (2)0.046 (2)0.027 (2)0.0132 (19)0.0010 (16)
O30.0742 (19)0.0390 (16)0.0463 (17)0.0151 (14)0.0087 (15)0.0038 (13)
Br10.0814 (4)0.0354 (3)0.0987 (5)0.0111 (2)0.0247 (3)0.0021 (2)
Geometric parameters (Å, º) top
C15—C141.470 (7)C6—C71.426 (6)
C15—H15A0.9600C7—C81.363 (6)
C15—H15B0.9600C7—C111.443 (5)
C15—H15C0.9600C8—C91.403 (5)
O1—C81.357 (5)C9—C101.341 (6)
O1—C121.380 (4)C9—H90.9300
C1—C21.389 (6)C10—Br11.902 (4)
C1—C61.420 (5)C10—Br11.902 (4)
C1—C101.451 (6)C11—C121.345 (6)
C2—C31.404 (8)C11—H110.9300
C2—H20.9300C12—C131.471 (6)
C3—C41.311 (7)C13—O21.192 (5)
C3—H30.9300C13—O31.333 (5)
C4—C51.495 (7)C14—O31.452 (5)
C4—H40.9300C14—H14A0.9700
C5—C61.396 (6)C14—H14B0.9700
C5—H50.9300Br1—Br10.0000
C14—C15—H15A109.5O1—C8—C9124.0 (4)
C14—C15—H15B109.5C7—C8—C9124.5 (4)
H15A—C15—H15B109.5C10—C9—C8115.9 (4)
C14—C15—H15C109.5C10—C9—H9122.1
H15A—C15—H15C109.5C8—C9—H9122.1
H15B—C15—H15C109.5C9—C10—C1124.2 (4)
C8—O1—C12105.4 (3)C9—C10—Br1117.2 (3)
C2—C1—C6119.5 (4)C1—C10—Br1118.5 (3)
C2—C1—C10122.9 (4)C9—C10—Br1117.2 (3)
C6—C1—C10117.6 (4)C1—C10—Br1118.5 (3)
C1—C2—C3119.4 (4)Br1—C10—Br10.00 (4)
C1—C2—H2120.3C12—C11—C7105.7 (3)
C3—C2—H2120.3C12—C11—H11127.2
C4—C3—C2125.9 (5)C7—C11—H11127.2
C4—C3—H3117.1C11—C12—O1111.7 (3)
C2—C3—H3117.1C11—C12—C13132.7 (4)
C3—C4—C5115.1 (5)O1—C12—C13115.6 (4)
C3—C4—H4122.4O2—C13—O3125.4 (4)
C5—C4—H4122.4O2—C13—C12124.7 (4)
C6—C5—C4121.2 (4)O3—C13—C12110.0 (4)
C6—C5—H5119.4O3—C14—C15108.3 (4)
C4—C5—H5119.4O3—C14—H14A110.0
C5—C6—C1118.9 (4)C15—C14—H14A110.0
C5—C6—C7123.1 (4)O3—C14—H14B110.0
C1—C6—C7118.0 (4)C15—C14—H14B110.0
C8—C7—C6119.8 (4)H14A—C14—H14B108.4
C8—C7—C11105.8 (4)C13—O3—C14114.9 (3)
C6—C7—C11134.4 (4)Br1—Br1—C100
O1—C8—C7111.4 (3)

Experimental details

Crystal data
Chemical formulaC15H11BrO3
Mr319.15
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.3108 (4), 11.1545 (6), 15.9752 (10)
β (°) 100.921 (4)
V3)1279.16 (13)
Z4
Radiation typeMo Kα
µ (mm1)3.21
Crystal size (mm)0.28 × 0.24 × 0.18
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.467, 0.595
No. of measured, independent and
observed [I > 2σ(I)] reflections
10028, 2249, 1699
Rint0.037
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.127, 1.08
No. of reflections2249
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.59, 0.54

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).

 

Acknowledgements

BSPM thanks Dr H. C. Devarajegowda, Department of Physics, Yuvarajas College (constituent), University of Mysore and T. Srinivasan, Centre of Advanced Study in Crystallography and Biophysics, University of Madras Guindy Campus, Chennai for their support.

References

First citationBruker (2004). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationVaidya, V. P., Mahadevan, K. M., Shet Prakash, M., Sreenivas, S. & Shivananda, M. K. (2011). Res. J. Pharm. Biol. Chem. Sci. 2, 334–342.  CAS

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ISSN: 2056-9890
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