Ethyl 5-bromo-1-benzofuran-2-carboxyl­ate

Abdel-Aziz, H.A.; Bari, A.; Ng, S.W.

doi:10.1107/S1600536811005897

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o696

doi:10.1107/S1600536811005897

Open

access

Ethyl 5-bromo-1-benzofuran-2-carboxylate

Hatem A. Abdel-Aziz,^a Ahmed Bari ^a and Seik Weng Ng ^b ^*

^aDepartment of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 14 February 2011; accepted 16 February 2011; online 23 February 2011)

In the title compound, C₁₁H₉BrO₃, the benzofuran fused-ring system is almost planar, with a maximum atomic deviation of 0.024 (5) Å; the carboxyl –CO₂ fragment is aligned at 4.8 (7)° with respect to the fused-ring plane. Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure. π–π stacking is also observed between parallel molecules, the centroid–centroid distance between benzene and furan rings of adjacent molecules being 3.662 (3) Å.

Related literature

For our previous reports of the pharmacological properties of benzofurans, see: Abdel-Aziz & Mekawey (2009 ); Abdel-Aziz et al. (2009 ). For a related structure, see: Kossakowski et al. (2005 ).

Experimental

Crystal data

C₁₁H₉BrO₃
M_r = 269.09
Monoclinic, P 2₁ /n
a = 3.8869 (3) Å
b = 23.780 (2) Å
c = 11.0820 (7) Å
β = 96.905 (8)°
V = 1016.89 (13) Å³
Z = 4
Mo Kα radiation
μ = 4.02 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.378, T_max = 0.689
6060 measured reflections
2250 independent reflections
1843 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.109
S = 1.18
2250 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2ⁱ	0.95	2.57	3.400 (6)	146
C11—H11A⋯O2ⁱⁱ	0.98	2.53	3.472 (6)	160
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005897/xu5164sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005897/xu5164Isup2.hkl

checkCIF report

Comment top

Ethyl 5-bromobenzofuran-2-carboxylate (Scheme I) is a commercially available chemical that has been evaluated for its pharmacological properties. We have reported the pharmacological properties of related compounds (Abdel-Aziz & Mekawey, 2009; Abdel-Aziz et al., 2009). The title compound is an approximately planar molecule; the carboxyl –CO₂ fragment is aligned at 4.8 (7)° with respect to the benzofuran fused-ring (Fig. 1). Bond dimensions are similar to those found in methyl 7-methoxybenzofuran-2-carboxylate (Kossakowski et al., 2005).

Related literature top

For our previous reports of the pharmacological properties of benzofurans, see: Abdel-Aziz & Mekawey (2009); Abdel-Aziz et al. (2009). For a related structure, see: Kossakowski et al. (2005).

Experimental top

5-Bromosalicyladehyde (2.01 g, 10 mm l), diethyl bromomalonate (2.63 g 11 mmol) and potassium carbonate (2.28 g, 20 mmol) were heated in 2-butanone (20 ml) for 14 h. The solvent was evaporated and water was added to the residue. The organic compound was extracted by ether. The ether phase was washed with 5% sodium hydroxide. The ether was then evaporated and the product recrystallized from ethanol to give the title ester, m.p. 333–335 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₁H₉BrO₃ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Ethyl 5-bromo-1-benzofuran-2-carboxylate top

Crystal data top

C₁₁H₉BrO₃	F(000) = 536
M_r = 269.09	D_x = 1.758 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2599 reflections
a = 3.8869 (3) Å	θ = 2.5–29.3°
b = 23.780 (2) Å	µ = 4.02 mm⁻¹
c = 11.0820 (7) Å	T = 100 K
β = 96.905 (8)°	Prism, colorless
V = 1016.89 (13) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2250 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1843 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.045
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.5°
ω scans	h = −3→5
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −30→30
T_min = 0.378, T_max = 0.689	l = −13→14
6060 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.18	w = 1/[σ²(F_o²) + (0.0086P)² + 5.1797P] where P = (F_o² + 2F_c²)/3
2250 reflections	(Δ/σ)_max = 0.001
136 parameters	Δρ_max = 0.97 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

C₁₁H₉BrO₃	V = 1016.89 (13) Å³
M_r = 269.09	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.8869 (3) Å	µ = 4.02 mm⁻¹
b = 23.780 (2) Å	T = 100 K
c = 11.0820 (7) Å	0.30 × 0.20 × 0.10 mm
β = 96.905 (8)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	2250 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1843 reflections with I > 2σ(I)
T_min = 0.378, T_max = 0.689	R_int = 0.045
6060 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.18	Δρ_max = 0.97 e Å⁻³
2250 reflections	Δρ_min = −0.71 e Å⁻³
136 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.84947 (14)	0.52531 (2)	0.18162 (5)	0.02119 (16)
O1	0.2581 (9)	0.32380 (14)	0.4040 (3)	0.0157 (7)
O2	0.0007 (10)	0.25870 (14)	0.5783 (3)	0.0228 (9)
O3	0.1752 (9)	0.32488 (14)	0.7194 (3)	0.0165 (8)
C1	0.3994 (13)	0.3662 (2)	0.3427 (4)	0.0146 (10)
C2	0.4194 (14)	0.3670 (2)	0.2183 (4)	0.0189 (11)
H2	0.3416	0.3363	0.1672	0.023*
C3	0.5588 (15)	0.4150 (2)	0.1733 (4)	0.0216 (12)
H3	0.5746	0.4181	0.0886	0.026*
C4	0.6767 (13)	0.4590 (2)	0.2510 (4)	0.0163 (11)
C5	0.6666 (13)	0.4576 (2)	0.3740 (4)	0.0151 (10)
H5	0.7541	0.4878	0.4248	0.018*
C6	0.5205 (12)	0.4095 (2)	0.4220 (4)	0.0135 (10)
C7	0.4517 (13)	0.3916 (2)	0.5397 (4)	0.0153 (10)
H7	0.5060	0.4113	0.6141	0.018*
C8	0.2932 (14)	0.3408 (2)	0.5243 (4)	0.0161 (11)
C9	0.1403 (13)	0.3029 (2)	0.6073 (4)	0.0157 (10)
C10	0.0273 (14)	0.2924 (2)	0.8131 (4)	0.0202 (11)
H10A	0.1957	0.2639	0.8488	0.024*
H10B	−0.1857	0.2728	0.7775	0.024*
C11	−0.0555 (14)	0.3333 (2)	0.9091 (4)	0.0202 (11)
H11A	−0.1540	0.3130	0.9738	0.030*
H11B	−0.2234	0.3611	0.8728	0.030*
H11C	0.1571	0.3526	0.9433	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0225 (3)	0.0210 (3)	0.0205 (3)	−0.0006 (2)	0.0046 (2)	0.0051 (2)
O1	0.020 (2)	0.0151 (17)	0.0107 (15)	−0.0015 (15)	−0.0019 (14)	−0.0010 (14)
O2	0.032 (2)	0.0169 (19)	0.0191 (18)	−0.0038 (17)	0.0022 (17)	−0.0014 (15)
O3	0.019 (2)	0.0196 (18)	0.0108 (15)	−0.0032 (15)	0.0007 (14)	0.0015 (14)
C1	0.015 (3)	0.016 (2)	0.013 (2)	0.003 (2)	−0.0009 (19)	0.0018 (19)
C2	0.021 (3)	0.022 (3)	0.013 (2)	0.002 (2)	−0.001 (2)	−0.002 (2)
C3	0.032 (3)	0.021 (3)	0.013 (2)	0.004 (2)	0.006 (2)	0.002 (2)
C4	0.013 (3)	0.018 (2)	0.019 (2)	0.002 (2)	0.005 (2)	0.007 (2)
C5	0.013 (3)	0.014 (2)	0.018 (2)	0.000 (2)	0.001 (2)	−0.003 (2)
C6	0.008 (2)	0.018 (2)	0.012 (2)	0.001 (2)	−0.0063 (19)	−0.0007 (19)
C7	0.016 (3)	0.016 (2)	0.013 (2)	0.004 (2)	−0.001 (2)	−0.0006 (19)
C8	0.021 (3)	0.016 (2)	0.010 (2)	0.007 (2)	0.000 (2)	0.0000 (19)
C9	0.014 (3)	0.019 (3)	0.013 (2)	0.005 (2)	−0.003 (2)	0.001 (2)
C10	0.023 (3)	0.022 (3)	0.016 (2)	−0.003 (2)	0.004 (2)	0.006 (2)
C11	0.020 (3)	0.027 (3)	0.014 (2)	−0.007 (2)	0.001 (2)	0.003 (2)

Geometric parameters (Å, º) top

Br1—C4	1.912 (5)	C5—C6	1.410 (7)
O1—C1	1.367 (6)	C5—H5	0.9500
O1—C8	1.384 (5)	C6—C7	1.428 (6)
O2—C9	1.208 (6)	C7—C8	1.357 (7)
O3—C9	1.340 (5)	C7—H7	0.9500
O3—C10	1.465 (6)	C8—C9	1.464 (7)
C1—C2	1.390 (6)	C10—C11	1.505 (7)
C1—C6	1.398 (7)	C10—H10A	0.9900
C2—C3	1.382 (7)	C10—H10B	0.9900
C2—H2	0.9500	C11—H11A	0.9800
C3—C4	1.397 (7)	C11—H11B	0.9800
C3—H3	0.9500	C11—H11C	0.9800
C4—C5	1.369 (6)

C1—O1—C8	105.3 (4)	C8—C7—H7	126.8
C9—O3—C10	116.5 (4)	C6—C7—H7	126.8
O1—C1—C2	125.2 (4)	C7—C8—O1	111.9 (4)
O1—C1—C6	110.8 (4)	C7—C8—C9	133.0 (4)
C2—C1—C6	124.0 (5)	O1—C8—C9	115.1 (4)
C3—C2—C1	116.1 (5)	O2—C9—O3	125.3 (5)
C3—C2—H2	121.9	O2—C9—C8	124.9 (4)
C1—C2—H2	121.9	O3—C9—C8	109.8 (4)
C2—C3—C4	120.6 (4)	O3—C10—C11	107.2 (4)
C2—C3—H3	119.7	O3—C10—H10A	110.3
C4—C3—H3	119.7	C11—C10—H10A	110.3
C5—C4—C3	123.4 (5)	O3—C10—H10B	110.3
C5—C4—Br1	118.2 (4)	C11—C10—H10B	110.3
C3—C4—Br1	118.4 (4)	H10A—C10—H10B	108.5
C4—C5—C6	117.1 (4)	C10—C11—H11A	109.5
C4—C5—H5	121.5	C10—C11—H11B	109.5
C6—C5—H5	121.5	H11A—C11—H11B	109.5
C1—C6—C5	118.8 (4)	C10—C11—H11C	109.5
C1—C6—C7	105.6 (4)	H11A—C11—H11C	109.5
C5—C6—C7	135.6 (5)	H11B—C11—H11C	109.5
C8—C7—C6	106.4 (4)

C8—O1—C1—C2	−179.8 (5)	C4—C5—C6—C7	−178.1 (5)
C8—O1—C1—C6	−0.3 (5)	C1—C6—C7—C8	−1.0 (6)
O1—C1—C2—C3	177.3 (5)	C5—C6—C7—C8	177.8 (6)
C6—C1—C2—C3	−2.1 (8)	C6—C7—C8—O1	0.9 (6)
C1—C2—C3—C4	1.2 (8)	C6—C7—C8—C9	−175.5 (5)
C2—C3—C4—C5	0.7 (8)	C1—O1—C8—C7	−0.4 (6)
C2—C3—C4—Br1	−177.6 (4)	C1—O1—C8—C9	176.7 (4)
C3—C4—C5—C6	−1.6 (7)	C10—O3—C9—O2	−0.7 (7)
Br1—C4—C5—C6	176.6 (4)	C10—O3—C9—C8	178.6 (4)
O1—C1—C6—C5	−178.3 (4)	C7—C8—C9—O2	178.6 (6)
C2—C1—C6—C5	1.2 (8)	O1—C8—C9—O2	2.3 (7)
O1—C1—C6—C7	0.8 (5)	C7—C8—C9—O3	−0.7 (8)
C2—C1—C6—C7	−179.7 (5)	O1—C8—C9—O3	−177.1 (4)
C4—C5—C6—C1	0.7 (7)	C9—O3—C10—C11	−154.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.95	2.57	3.400 (6)	146
C11—H11A···O2ⁱⁱ	0.98	2.53	3.472 (6)	160

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

Experimental details

Crystal data
Chemical formula	C₁₁H₉BrO₃
M_r	269.09
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	3.8869 (3), 23.780 (2), 11.0820 (7)
β (°)	96.905 (8)
V (Å³)	1016.89 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.02
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.378, 0.689
No. of measured, independent and observed [I > 2σ(I)] reflections	6060, 2250, 1843
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.109, 1.18
No. of reflections	2250
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.97, −0.71

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2ⁱ	0.95	2.57	3.400 (6)	146
C11—H11A···O2ⁱⁱ	0.98	2.53	3.472 (6)	160

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

Acknowledgements

We thank King Saud University and the University of Malaya for supporting this study.

References

Abdel-Aziz, H. A. & Mekawey, A. A. I. (2009). Eur. J. Med. Chem. 44, 3985–3997. Google Scholar
Abdel-Aziz, H. A., Mekawey, A. A. I. & Dawood, K. M. (2009). Eur. J. Med. Chem. 44, 3637–3644. Web of Science PubMed CAS Google Scholar
Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Kossakowski, J., Ostrowska, K., Hejchman, E. & Wolska, I. (2005). Farmaco, 60, 519–527. CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar