Ethyl 3-amino-5-bromo-1-benzo­furan-2-carboxyl­ate

Yamuna, A.J.; Karunakar, P.; Girija, C.R.; Vaidya, V.P.; Krishnamurthy, V.

doi:10.1107/S1600536813010209

organic compounds

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Volume 69| Part 5| May 2013| Page o775

https://doi.org/10.1107/S1600536813010209

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Ethyl 3-amino-5-bromo-1-benzofuran-2-carboxylate

A. J. Yamuna,^a P. Karunakar,^b C. R. Girija,^c ^* V. P. Vaidya ^a and V. Krishnamurthy ^b

^aDepartment of Chemistry, Kuvempu University, Jnana Sahyadri, Shankaraghatta 577 451, India, ^bDepartment of Biotechnology, PES Institute of Technology, BSK III Stg, Bangalore 560 085, India, and ^cDepartment of Chemistry, SSMRV College, 4th T Block, Jayanagar, Bangalore 560 041, India
^*Correspondence e-mail: girija.shivakumar@rediffmail.com

(Received 1 April 2013; accepted 14 April 2013; online 20 April 2013)

The title compound, C₁₁H₁₀BrNO₃, is close to planar with the benzofuran unit and the ester group subtending a dihedral angle of 5.25 (2)°. The molecular structure features an intramolecular N—H⋯O interaction. In the crystal, N—H⋯O hydrogen bonds involving carboxyl O-atom acceptors generate a chain extending along [201].

Related literature

For the biological activity of benzofuran derivatives, see: Oter et al. (2007 ); Habermann et al. (1999 ). For a similar structure, see: Karunakar et al. (2013 ).

Experimental

Crystal data

C₁₁H₁₀BrNO₃
M_r = 284.11
Monoclinic, P 2₁ /c
a = 5.775 (5) Å
b = 25.550 (2) Å
c = 7.640 (1) Å
β = 98.292 (1)°
V = 1115.5 (10) Å³
Z = 4
Mo Kα radiation
μ = 3.68 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.591, T_max = 0.732
10542 measured reflections
1957 independent reflections
1658 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.076
S = 1.08
1957 reflections
154 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.82 (2)	2.17 (2)	2.977 (4)	171 (3)
N1—H1B⋯O3	0.82 (2)	2.31 (3)	2.835 (4)	123 (3)
Symmetry code: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813010209/zs2255sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813010209/zs2255Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813010209/zs2255Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S1600536813010209/zs2255Isup4.cml

checkCIF report

Comment top

Substituted benzofurans find their applications in different fields such as fluorescent sensors (Oter et al., 2007), antioxidants, brightening agents and as drugs and agricultural chemicals (Habermann et al., 1999). In the title compound, C₁₁H₁₀BrNO₃, the ester group is close to coplanar with the benzofuran plane [dihedral angle = 5.25 (2)°] which compares with 7.84 (2)° in the previously reported analogous compound ethyl 5-bromo-3-ethoxycarbonylamino-1-benzofuran-2-carboxylate (Karunakar et al., 2013). The structure is stabilized by an intramolecular amine N1—H1B···O3 interaction (Table 1) while an intermolecular N1—HA···O2ⁱ hydrogen-bond to a carboxyl O-atom acceptor generates a one-dimensional chain structure extending along [201] (Fig. 2).

Related literature top

For the biological activity of benzofuran derivatives, see: Oter et al. (2007); Habermann et al. (1999). For a similar structure, see: Karunakar et al. (2013).

Experimental top

The mixture of 5-bromo-2-hydroxybenzonitrile (1.98 g, 0.01 mol), ethyl chloroacetate (1 ml, 0.01 mol) and potassium carbonate (2.76 g, 0.02 mol) in 5 ml of DMF was refluxed for 90 min. The potassium carbonate was removed by filtration and crushed ice was added to the filtrate, with constant stirring. The solid separated was filtered, dried and recrystallized from ethanol. Yeild: 87% (0.247 g); m.p. 154–156 °C.

Structure description top

For the biological activity of benzofuran derivatives, see: Oter et al. (2007); Habermann et al. (1999). For a similar structure, see: Karunakar et al. (2013).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular conformation and atom numbering scheme for the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing in the unit cell viewed down a. Hydrogen bonds are drawn as dashed lines. For symmetry code (i), see Table 1.

Ethyl 3-amino-5-bromo-1-benzofuran-2-carboxylate top

Crystal data top

C₁₁H₁₀BrNO₃	F(000) = 568
M_r = 284.11	D_x = 1.692 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 427–429 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 5.775 (5) Å	Cell parameters from 4034 reflections
b = 25.550 (2) Å	θ = 3.1–25.0°
c = 7.640 (1) Å	µ = 3.68 mm⁻¹
β = 98.292 (1)°	T = 293 K
V = 1115.5 (10) Å³	Block, yellow
Z = 4	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1957 independent reflections
Radiation source: fine-focus sealed tube	1658 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and φ scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
T_min = 0.591, T_max = 0.732	k = −30→30
10542 measured reflections	l = −9→9

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0258P)² + 1.2998P] where P = (F_o² + 2F_c²)/3
1957 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.42 e Å⁻³
1 restraint	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₁H₁₀BrNO₃	V = 1115.5 (10) Å³
M_r = 284.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.775 (5) Å	µ = 3.68 mm⁻¹
b = 25.550 (2) Å	T = 293 K
c = 7.640 (1) Å	0.20 × 0.15 × 0.10 mm
β = 98.292 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1957 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1658 reflections with I > 2σ(I)
T_min = 0.591, T_max = 0.732	R_int = 0.025
10542 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	1 restraint
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.42 e Å⁻³
1957 reflections	Δρ_min = −0.34 e Å⁻³
154 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
C1	0.7527 (5)	0.13047 (11)	0.2409 (4)	0.0367 (6)
H1	0.9027	0.1351	0.3018	0.044*
C2	0.6640 (5)	0.08164 (12)	0.1981 (4)	0.0400 (7)
C3	0.4395 (5)	0.07344 (12)	0.1094 (4)	0.0449 (8)
H3	0.3859	0.0395	0.0855	0.054*
C4	0.2971 (5)	0.11501 (13)	0.0572 (4)	0.0457 (8)
H4	0.1464	0.1102	−0.0023	0.055*
C5	0.3869 (5)	0.16441 (12)	0.0968 (4)	0.0373 (7)
C6	0.6077 (5)	0.17270 (11)	0.1889 (4)	0.0339 (6)
C7	0.6341 (5)	0.22874 (11)	0.2061 (4)	0.0345 (6)
C8	0.4298 (5)	0.24944 (12)	0.1214 (4)	0.0385 (7)
C9	0.3548 (5)	0.30198 (12)	0.0857 (4)	0.0402 (7)
C10	0.4688 (6)	0.39058 (12)	0.1228 (4)	0.0464 (8)
H10A	0.3386	0.4018	0.1810	0.056*
H10B	0.4292	0.3967	−0.0032	0.056*
C11	0.6871 (6)	0.41993 (14)	0.1950 (5)	0.0613 (10)
H11A	0.7188	0.4152	0.3208	0.092*
H11B	0.6657	0.4565	0.1686	0.092*
H11C	0.8163	0.4069	0.1416	0.092*
N1	0.8245 (5)	0.25350 (11)	0.2871 (4)	0.0472 (7)
O1	0.2739 (3)	0.21006 (8)	0.0521 (3)	0.0446 (5)
O2	0.1709 (4)	0.31544 (9)	0.0025 (3)	0.0579 (6)
O3	0.5187 (4)	0.33597 (8)	0.1573 (3)	0.0463 (5)
Br1	0.85639 (7)	0.022292 (13)	0.26302 (6)	0.06241 (16)
H1A	0.930 (5)	0.2374 (11)	0.347 (4)	0.045 (9)*
H1B	0.821 (6)	0.2852 (9)	0.299 (5)	0.058 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0319 (14)	0.0367 (16)	0.0390 (16)	−0.0032 (13)	−0.0029 (12)	0.0002 (13)
C2	0.0411 (17)	0.0360 (16)	0.0422 (18)	0.0023 (13)	0.0036 (13)	0.0003 (13)
C3	0.0427 (17)	0.0379 (17)	0.0527 (19)	−0.0096 (14)	0.0020 (14)	−0.0093 (15)
C4	0.0344 (16)	0.0486 (19)	0.0508 (19)	−0.0091 (14)	−0.0053 (14)	−0.0077 (15)
C5	0.0314 (15)	0.0382 (16)	0.0406 (16)	0.0011 (13)	−0.0005 (12)	−0.0001 (13)
C6	0.0321 (15)	0.0359 (16)	0.0322 (15)	−0.0034 (12)	−0.0002 (12)	0.0002 (12)
C7	0.0295 (15)	0.0373 (16)	0.0347 (16)	−0.0027 (12)	−0.0024 (12)	0.0003 (12)
C8	0.0309 (15)	0.0376 (16)	0.0434 (17)	−0.0012 (13)	−0.0067 (13)	−0.0009 (13)
C9	0.0313 (16)	0.0427 (17)	0.0438 (17)	−0.0016 (13)	−0.0036 (13)	0.0037 (14)
C10	0.0490 (19)	0.0368 (17)	0.0522 (19)	0.0022 (14)	0.0034 (15)	0.0026 (15)
C11	0.061 (2)	0.050 (2)	0.072 (3)	−0.0128 (17)	0.0062 (19)	−0.0075 (18)
N1	0.0345 (14)	0.0365 (16)	0.0635 (19)	−0.0002 (13)	−0.0171 (13)	0.0010 (14)
O1	0.0316 (11)	0.0415 (12)	0.0556 (13)	−0.0025 (9)	−0.0107 (9)	−0.0014 (10)
O2	0.0409 (13)	0.0439 (13)	0.0798 (17)	0.0019 (10)	−0.0221 (12)	0.0092 (12)
O3	0.0402 (12)	0.0369 (12)	0.0568 (13)	0.0004 (9)	−0.0097 (10)	0.0023 (10)
Br1	0.0607 (2)	0.0360 (2)	0.0857 (3)	0.00615 (17)	−0.00581 (18)	−0.00165 (18)

Geometric parameters (Å, º) top

C1—C2	1.370 (4)	C8—O1	1.402 (3)
C1—C6	1.388 (4)	C8—C9	1.425 (4)
C1—H1	0.9300	C9—O2	1.207 (3)
C2—C3	1.389 (4)	C9—O3	1.342 (3)
C2—Br1	1.903 (3)	C10—O3	1.441 (4)
C3—C4	1.367 (4)	C10—C11	1.501 (5)
C3—H3	0.9300	C10—H10A	0.9700
C4—C5	1.381 (4)	C10—H10B	0.9700
C4—H4	0.9300	C11—H11A	0.9600
C5—O1	1.356 (3)	C11—H11B	0.9600
C5—C6	1.381 (4)	C11—H11C	0.9600
C6—C7	1.444 (4)	N1—H1A	0.82 (2)
C7—N1	1.340 (4)	N1—H1B	0.82 (2)
C7—C8	1.368 (4)

C2—C1—C6	116.7 (3)	C7—C8—C9	132.3 (3)
C2—C1—H1	121.6	O1—C8—C9	116.3 (2)
C6—C1—H1	121.6	O2—C9—O3	123.1 (3)
C1—C2—C3	123.0 (3)	O2—C9—C8	126.1 (3)
C1—C2—Br1	118.6 (2)	O3—C9—C8	110.8 (2)
C3—C2—Br1	118.4 (2)	O3—C10—C11	106.3 (3)
C4—C3—C2	120.3 (3)	O3—C10—H10A	110.5
C4—C3—H3	119.8	C11—C10—H10A	110.5
C2—C3—H3	119.8	O3—C10—H10B	110.5
C3—C4—C5	117.1 (3)	C11—C10—H10B	110.5
C3—C4—H4	121.5	H10A—C10—H10B	108.7
C5—C4—H4	121.5	C10—C11—H11A	109.5
O1—C5—C6	111.8 (2)	C10—C11—H11B	109.5
O1—C5—C4	125.4 (3)	H11A—C11—H11B	109.5
C6—C5—C4	122.8 (3)	C10—C11—H11C	109.5
C5—C6—C1	120.1 (3)	H11A—C11—H11C	109.5
C5—C6—C7	106.0 (2)	H11B—C11—H11C	109.5
C1—C6—C7	133.9 (3)	C7—N1—H1A	121 (2)
N1—C7—C8	129.1 (3)	C7—N1—H1B	119 (3)
N1—C7—C6	125.4 (3)	H1A—N1—H1B	118 (3)
C8—C7—C6	105.5 (2)	C5—O1—C8	105.2 (2)
C7—C8—O1	111.4 (3)	C9—O3—C10	116.2 (2)

C6—C1—C2—C3	−0.9 (5)	C1—C6—C7—C8	177.9 (3)
C6—C1—C2—Br1	179.1 (2)	N1—C7—C8—O1	179.3 (3)
C1—C2—C3—C4	1.3 (5)	C6—C7—C8—O1	0.4 (3)
Br1—C2—C3—C4	−178.7 (2)	N1—C7—C8—C9	2.5 (6)
C2—C3—C4—C5	0.0 (5)	C6—C7—C8—C9	−176.4 (3)
C3—C4—C5—O1	178.4 (3)	C7—C8—C9—O2	176.9 (3)
C3—C4—C5—C6	−1.7 (5)	O1—C8—C9—O2	0.2 (5)
O1—C5—C6—C1	−177.9 (3)	C7—C8—C9—O3	−2.8 (5)
C4—C5—C6—C1	2.1 (5)	O1—C8—C9—O3	−179.5 (2)
O1—C5—C6—C7	1.1 (3)	C6—C5—O1—C8	−0.8 (3)
C4—C5—C6—C7	−178.9 (3)	C4—C5—O1—C8	179.2 (3)
C2—C1—C6—C5	−0.7 (4)	C7—C8—O1—C5	0.3 (3)
C2—C1—C6—C7	−179.4 (3)	C9—C8—O1—C5	177.6 (3)
C5—C6—C7—N1	−179.8 (3)	O2—C9—O3—C10	−2.8 (4)
C1—C6—C7—N1	−1.1 (5)	C8—C9—O3—C10	176.9 (3)
C5—C6—C7—C8	−0.8 (3)	C11—C10—O3—C9	−172.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.82 (2)	2.17 (2)	2.977 (4)	171 (3)
N1—H1B···O3	0.82 (2)	2.31 (3)	2.835 (4)	123 (3)

Symmetry code: (i) x+1, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀BrNO₃
M_r	284.11
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	5.775 (5), 25.550 (2), 7.640 (1)
β (°)	98.292 (1)
V (Å³)	1115.5 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.68
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.591, 0.732
No. of measured, independent and observed [I > 2σ(I)] reflections	10542, 1957, 1658
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.076, 1.08
No. of reflections	1957
No. of parameters	154
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.34

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.82 (2)	2.17 (2)	2.977 (4)	171 (3)
N1—H1B···O3	0.82 (2)	2.31 (3)	2.835 (4)	123 (3)

Symmetry code: (i) x+1, −y+1/2, z+1/2.

Acknowledgements

The authors thank Sophisticated Analytical Instrument Facility (SAIF), Indian Institute of Technology (IIT), Chennai, India, for the data collection. They also thank Dr K. M. Mahadevan, Department of Chemistry, and Dr V. Krishna, Department of Biotechnology of Kuvempu University, Jnana Sahyadri, Shankaraghatta, for their support.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Bruker (2004). APEX2, SAINT-Plus and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2008). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Habermann, J., Ley, S. V., Scicinski, J. J., Scott, J. S., Smits, R. & Thomas, A. W. (1999). J. Chem. Soc. Perkin Trans. 1, pp. 2425–2427. Web of Science CrossRef Google Scholar
Karunakar, P., Krishnamurthy, V., Girija, C. R., Krishna, V., Vaidya, V. P. & Yamuna, A. J. (2013). Acta Cryst. E69, o342. CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Oter, O., Ertekin, K., Kirilmis, C., Koca, M. & Ahmedzade, M. (2007). Sens. Actuators B, 122, 450–456. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar