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

Shet Prakash, M.; Suchetan, P.A.; Mahadevan, K.M.; Vaidya, V.P.; Velumurgan, D.; Palakshamurthy, B.S.

doi:10.1107/S160053681205204X

organic compounds

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Volume 69| Part 2| February 2013| Page o198

doi:10.1107/S160053681205204X

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

M. Shet Prakash,^a P. A. Suchetan,^a K. M. Mahadevan,^b V. P. Vaidya,^b D. Velumurgan ^c and B. S. Palakshamurthy ^d ^*

^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 π–π 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 ).

Experimental

Crystal data

C₁₅H₁₁BrO₃
M_r = 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) T_min = 0.467, T_max = 0.595
10028 measured reflections
2249 independent reflections
1699 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.127
S = 1.08
2249 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.54 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681205204X/hb7019sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681205204X/hb7019Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681205204X/hb7019Isup3.cml

checkCIF report

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 π–π 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.

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

	Fig. 1. Molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Molecular packing of the title compound. Hydrogen bonds are shown as dashed lines.
	Fig. 3. Molecular packing of the title compound through π–π interactions are shown as dashed lines.

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

Crystal data top

C₁₅H₁₁BrO₃	prism
M_r = 319.15	D_x = 1.657 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 402 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.3108 (4) Å	Cell parameters from 2249 reflections
b = 11.1545 (6) Å	θ = 2.2–25.0°
c = 15.9752 (10) Å	µ = 3.21 mm⁻¹
β = 100.921 (4)°	T = 298 K
V = 1279.16 (13) Å³	Prism, colourless
Z = 4	0.28 × 0.24 × 0.18 mm
F(000) = 640

Data collection top

Bruker APEXII CCD diffractometer	2249 independent reflections
Radiation source: fine-focus sealed tube	1699 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 0.95 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
phi and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→13
T_min = 0.467, T_max = 0.595	l = −18→18
10028 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0587P)² + 1.4776P] where P = (F_o² + 2F_c²)/3
2249 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³
0 constraints

Crystal data top

C₁₅H₁₁BrO₃	V = 1279.16 (13) Å³
M_r = 319.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3108 (4) Å	µ = 3.21 mm⁻¹
b = 11.1545 (6) Å	T = 298 K
c = 15.9752 (10) Å	0.28 × 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)
T_min = 0.467, T_max = 0.595	R_int = 0.037
10028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.08	Δρ_max = 0.59 e Å⁻³
2249 reflections	Δρ_min = −0.54 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C15	−0.1065 (7)	−0.5565 (4)	0.3863 (3)	0.0671 (13)
H15A	−0.1556	−0.6243	0.3523	0.101*
H15B	−0.1951	−0.5306	0.4198	0.101*
H15C	0.0077	−0.5787	0.4233	0.101*
O1	0.1492 (4)	−0.0566 (2)	0.36398 (17)	0.0472 (7)
C1	0.3625 (5)	0.1416 (3)	0.5778 (3)	0.0429 (10)
C2	0.4360 (6)	0.2041 (4)	0.6518 (3)	0.0584 (12)
H2	0.4792	0.2821	0.6487	0.070*
C3	0.4446 (7)	0.1483 (5)	0.7312 (4)	0.0722 (15)
H3	0.4956	0.1924	0.7794	0.087*
C4	0.3872 (6)	0.0395 (4)	0.7436 (3)	0.0581 (12)
H4	0.3924	0.0076	0.7978	0.070*
C5	0.3127 (6)	−0.0296 (4)	0.6643 (3)	0.0552 (11)
H5	0.2734	−0.1083	0.6687	0.066*
C6	0.3009 (5)	0.0217 (3)	0.5838 (3)	0.0442 (9)
C7	0.2283 (5)	−0.0402 (3)	0.5065 (3)	0.0402 (9)
C8	0.2182 (5)	0.0167 (3)	0.4302 (3)	0.0420 (9)
C9	0.2729 (6)	0.1358 (3)	0.4210 (3)	0.0497 (10)
H9	0.2609	0.1722	0.3678	0.060*
C10	0.3435 (5)	0.1938 (3)	0.4934 (3)	0.0487 (11)
C11	0.1573 (5)	−0.1595 (3)	0.4862 (3)	0.0422 (9)
H11	0.1442	−0.2204	0.5244	0.051*
C12	0.1141 (5)	−0.1642 (3)	0.4006 (3)	0.0421 (9)
C13	0.0419 (6)	−0.2605 (4)	0.3405 (3)	0.0488 (10)
C14	−0.0706 (7)	−0.4583 (4)	0.3302 (3)	0.0616 (12)
H14A	0.0183	−0.4838	0.2958	0.074*
H14B	−0.1852	−0.4355	0.2923	0.074*
O2	0.0212 (6)	−0.2527 (3)	0.2649 (2)	0.0744 (10)
O3	0.0034 (4)	−0.3571 (2)	0.38317 (19)	0.0535 (8)
Br1	0.42767 (7)	0.35357 (4)	0.48343 (4)	0.0708 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C15	0.088 (3)	0.045 (3)	0.069 (3)	−0.018 (2)	0.017 (3)	−0.009 (2)
O1	0.0569 (16)	0.0351 (15)	0.0501 (17)	−0.0048 (12)	0.0113 (13)	0.0043 (12)
C1	0.0341 (18)	0.034 (2)	0.063 (3)	0.0046 (16)	0.0143 (18)	−0.0021 (19)
C2	0.053 (3)	0.045 (3)	0.075 (3)	0.000 (2)	0.007 (2)	−0.014 (2)
C3	0.064 (3)	0.082 (4)	0.065 (4)	0.009 (3)	−0.003 (3)	−0.029 (3)
C4	0.046 (2)	0.059 (3)	0.069 (3)	0.007 (2)	0.009 (2)	0.030 (2)
C5	0.057 (2)	0.051 (3)	0.059 (3)	0.006 (2)	0.014 (2)	0.007 (2)
C6	0.0378 (19)	0.040 (2)	0.056 (3)	0.0072 (16)	0.0116 (18)	0.0010 (19)
C7	0.0356 (18)	0.033 (2)	0.052 (2)	0.0031 (15)	0.0074 (17)	−0.0044 (18)
C8	0.0411 (19)	0.034 (2)	0.053 (3)	0.0019 (16)	0.0152 (18)	0.0009 (19)
C9	0.053 (2)	0.037 (2)	0.063 (3)	0.0029 (18)	0.020 (2)	0.008 (2)
C10	0.040 (2)	0.0272 (19)	0.081 (3)	−0.0003 (16)	0.018 (2)	−0.001 (2)
C11	0.044 (2)	0.035 (2)	0.049 (3)	0.0037 (16)	0.0113 (18)	0.0072 (18)
C12	0.042 (2)	0.030 (2)	0.054 (3)	−0.0015 (16)	0.0098 (18)	0.0041 (17)
C13	0.051 (2)	0.044 (2)	0.052 (3)	−0.0052 (18)	0.010 (2)	0.000 (2)
C14	0.083 (3)	0.045 (2)	0.057 (3)	−0.015 (2)	0.014 (2)	−0.015 (2)
O2	0.114 (3)	0.063 (2)	0.046 (2)	−0.027 (2)	0.0132 (19)	−0.0010 (16)
O3	0.0742 (19)	0.0390 (16)	0.0463 (17)	−0.0151 (14)	0.0087 (15)	−0.0038 (13)
Br1	0.0814 (4)	0.0354 (3)	0.0987 (5)	−0.0111 (2)	0.0247 (3)	0.0021 (2)

Geometric parameters (Å, º) top

C15—C14	1.470 (7)	C6—C7	1.426 (6)
C15—H15A	0.9600	C7—C8	1.363 (6)
C15—H15B	0.9600	C7—C11	1.443 (5)
C15—H15C	0.9600	C8—C9	1.403 (5)
O1—C8	1.357 (5)	C9—C10	1.341 (6)
O1—C12	1.380 (4)	C9—H9	0.9300
C1—C2	1.389 (6)	C10—Br1	1.902 (4)
C1—C6	1.420 (5)	C10—Br1	1.902 (4)
C1—C10	1.451 (6)	C11—C12	1.345 (6)
C2—C3	1.404 (8)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.471 (6)
C3—C4	1.311 (7)	C13—O2	1.192 (5)
C3—H3	0.9300	C13—O3	1.333 (5)
C4—C5	1.495 (7)	C14—O3	1.452 (5)
C4—H4	0.9300	C14—H14A	0.9700
C5—C6	1.396 (6)	C14—H14B	0.9700
C5—H5	0.9300	Br1—Br1	0.0000

C14—C15—H15A	109.5	O1—C8—C9	124.0 (4)
C14—C15—H15B	109.5	C7—C8—C9	124.5 (4)
H15A—C15—H15B	109.5	C10—C9—C8	115.9 (4)
C14—C15—H15C	109.5	C10—C9—H9	122.1
H15A—C15—H15C	109.5	C8—C9—H9	122.1
H15B—C15—H15C	109.5	C9—C10—C1	124.2 (4)
C8—O1—C12	105.4 (3)	C9—C10—Br1	117.2 (3)
C2—C1—C6	119.5 (4)	C1—C10—Br1	118.5 (3)
C2—C1—C10	122.9 (4)	C9—C10—Br1	117.2 (3)
C6—C1—C10	117.6 (4)	C1—C10—Br1	118.5 (3)
C1—C2—C3	119.4 (4)	Br1—C10—Br1	0.00 (4)
C1—C2—H2	120.3	C12—C11—C7	105.7 (3)
C3—C2—H2	120.3	C12—C11—H11	127.2
C4—C3—C2	125.9 (5)	C7—C11—H11	127.2
C4—C3—H3	117.1	C11—C12—O1	111.7 (3)
C2—C3—H3	117.1	C11—C12—C13	132.7 (4)
C3—C4—C5	115.1 (5)	O1—C12—C13	115.6 (4)
C3—C4—H4	122.4	O2—C13—O3	125.4 (4)
C5—C4—H4	122.4	O2—C13—C12	124.7 (4)
C6—C5—C4	121.2 (4)	O3—C13—C12	110.0 (4)
C6—C5—H5	119.4	O3—C14—C15	108.3 (4)
C4—C5—H5	119.4	O3—C14—H14A	110.0
C5—C6—C1	118.9 (4)	C15—C14—H14A	110.0
C5—C6—C7	123.1 (4)	O3—C14—H14B	110.0
C1—C6—C7	118.0 (4)	C15—C14—H14B	110.0
C8—C7—C6	119.8 (4)	H14A—C14—H14B	108.4
C8—C7—C11	105.8 (4)	C13—O3—C14	114.9 (3)
C6—C7—C11	134.4 (4)	Br1—Br1—C10	0
O1—C8—C7	111.4 (3)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₁BrO₃
M_r	319.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.3108 (4), 11.1545 (6), 15.9752 (10)
β (°)	100.921 (4)
V (Å³)	1279.16 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.21
Crystal size (mm)	0.28 × 0.24 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.467, 0.595
No. of measured, independent and observed [I > 2σ(I)] reflections	10028, 2249, 1699
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.127, 1.08
No. of reflections	2249
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vaidya, V. P., Mahadevan, K. M., Shet Prakash, M., Sreenivas, S. & Shivananda, M. K. (2011). Res. J. Pharm. Biol. Chem. Sci. 2, 334–342. CAS Google Scholar