Ethyl 1-aminona­phtho[2,1-b]furan-2-carboxyl­ate

Madan, K.S.; Shruthi, E.; Sagar, A.M.; Abdoh, M.M.M.; Vaidya, V.P.; Lokanath, N.K.

doi:10.1107/S1600536812025342

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2114

https://doi.org/10.1107/S1600536812025342

Open

access

Ethyl 1-aminonaphtho[2,1-b]furan-2-carboxylate

K. S. Madan,^a E. Shruthi,^b A. M. Sagar,^b M. M. M Abdoh,^c V. P. Vaidya ^b and N. K. Lokanath ^a ^*

^aDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, ^bDepartment of Chemistry, Kuvempu University, Shankaraghatta 577 451, India, and ^cDepartment of Physics, Faculty of Science, An Najah National University, Nabtus, West Bank, Palestinian Territories
^*Correspondence e-mail: lokanath@physics.uni-mysore.ac.in

(Received 24 May 2012; accepted 4 June 2012; online 16 June 2012)

In the title compound, C₁₅H₁₃NO₃, there is intramolecular N—H⋯O hydrogen bond between the amino group and the ester carbonyl O atom and the dihedral angle between the aromatic ring and the ester group is 2.05 (15)°. In the crystal, molecules are connected by N—H⋯O hydrogen bonds into chains parallel to [010]. In addition there are short C—H⋯O interactions and π–π stacking interactions with a distance of 3.555 (2) Å between the centroids of the furan and benzene rings.

Related literature

For bioactivity of naphthofuran compounds, see: Nagaraja et al. (2006 ); Mahadevan et al. (2005 ). For similar structures, see: Shruthi et al. (2012 ). For the synthesis of the title compound, see: Veena et al. (2011 )

Experimental

Crystal data

C₁₅H₁₃NO₃
M_r = 255.26
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.2217 (5) Å
b = 8.3795 (6) Å
c = 23.4692 (17) Å
V = 1223.56 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 103 K
0.28 × 0.22 × 0.22 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
18171 measured reflections
1288 independent reflections
1093 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.117
S = 1.03
1288 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O2	0.86	2.30	2.872 (4)	124
N4—H4B⋯O2ⁱ	0.86	2.29	3.027 (4)	144
C9—H9⋯O2ⁱ	0.93	2.50	3.308 (4)	146
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812025342/gk2494sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025342/gk2494Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025342/gk2494Isup3.cml

checkCIF report

Comment top

Various derivatives of naphtho[2,1-b]furan synthesized in our laboratory have been shown to possess broad spectrum of pharmacological and biological activities (Nagaraja et al., 2006).

The title compound was synthesized as an intermediate in the synthesis of aza heterocyclic derivative of naphtho[2,1-b]furan. The synthesis of the title compound was reported by Veena et al. (2011).

The ORTEP drawing of the title molecule is shown in Fig. 1. The naphthofuran system is basically planar and its geometry is similar to ethyl naphtho[2,1- b]furan-2-carboxylate (Shruthi et al., 2012). The dihedral angle between aromatic ring and the ester group is 2.05 (15)°.

The molecules are connected by N-H···O interactions into chains along the b axis (Fig. 2). There are π-π stacking interactions between molecules related by unit translation along the a axis with the distance of 3.555 (2) Å between centroids of the furan and benzene rings.

Related literature top

For bioactivity of naphthofuran compounds, see: Nagaraja et al. (2006); Mahadevan et al. (2005). For similar structures, see: Shruthi et al. (2012). For the synthesis of the title compound, see: Veena et al. (2011)

Experimental top

Ethyl 3-aminonaphtho[2,1-b]furan-2-carboxylate was synthesized as per the procedure reported in the literature (Veena et al., 2011). The final product was obtained by recrystallization using aqueous ethanol as a solvent. Slow evaporation method yielded crystals.

Structure description top

Various derivatives of naphtho[2,1-b]furan synthesized in our laboratory have been shown to possess broad spectrum of pharmacological and biological activities (Nagaraja et al., 2006).

For bioactivity of naphthofuran compounds, see: Nagaraja et al. (2006); Mahadevan et al. (2005). For similar structures, see: Shruthi et al. (2012). For the synthesis of the title compound, see: Veena et al. (2011)

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. ORTEP diagram of the title compound with 50% probability ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed along the crystallographic a axis. N—H···O hydrogen bonds are indicated by dashed lines.

Ethyl 1-aminonaphtho[2,1-b]furan-2-carboxylate top

Crystal data top

C₁₅H₁₃NO₃	F(000) = 536
M_r = 255.26	D_x = 1.386 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1288 reflections
a = 6.2217 (5) Å	θ = 1.7–25.0°
b = 8.3795 (6) Å	µ = 0.10 mm⁻¹
c = 23.4692 (17) Å	T = 103 K
V = 1223.56 (16) Å³	Block, colorless
Z = 4	0.28 × 0.22 × 0.22 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1093 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.064
Graphite monochromator	θ_max = 25.0°, θ_min = 1.7°
Detector resolution: 16.0839 pixels mm^-1	h = −7→7
ω scans	k = −9→9
18171 measured reflections	l = −27→26
1288 independent 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) = 0.117	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0749P)² + 0.4783P] where P = (F_o² + 2F_c²)/3
1288 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₅H₁₃NO₃	V = 1223.56 (16) Å³
M_r = 255.26	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.2217 (5) Å	µ = 0.10 mm⁻¹
b = 8.3795 (6) Å	T = 103 K
c = 23.4692 (17) Å	0.28 × 0.22 × 0.22 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	1093 reflections with I > 2σ(I)
18171 measured reflections	R_int = 0.064
1288 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.03	Δρ_max = 0.31 e Å⁻³
1288 reflections	Δρ_min = −0.36 e Å⁻³
173 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
O1	0.9439 (3)	0.7967 (3)	0.08591 (8)	0.0215 (7)
O2	0.7201 (4)	0.7539 (3)	0.22562 (9)	0.0245 (7)
O3	0.6156 (4)	0.6531 (3)	0.14062 (9)	0.0243 (7)
N4	1.0980 (4)	0.9507 (3)	0.22348 (11)	0.0233 (8)
C5	0.9186 (5)	0.8149 (4)	0.14469 (12)	0.0196 (9)
C6	1.0771 (5)	0.9106 (4)	0.16666 (13)	0.0200 (10)
C7	1.2157 (5)	0.9524 (4)	0.11969 (12)	0.0194 (9)
C8	1.4090 (5)	1.0413 (4)	0.11392 (13)	0.0199 (9)
C9	1.5215 (5)	1.1151 (4)	0.15900 (13)	0.0220 (9)
C10	1.7085 (5)	1.1961 (4)	0.14924 (14)	0.0258 (10)
C11	1.7922 (6)	1.2091 (4)	0.09382 (14)	0.0276 (10)
C12	1.6865 (6)	1.1397 (4)	0.04934 (14)	0.0263 (11)
C13	1.4948 (6)	1.0545 (4)	0.05737 (13)	0.0226 (9)
C14	1.3886 (6)	0.9777 (4)	0.01060 (13)	0.0252 (10)
C15	1.2054 (6)	0.8914 (4)	0.01695 (12)	0.0241 (10)
C16	1.1224 (5)	0.8797 (4)	0.07259 (13)	0.0201 (9)
C17	0.7458 (5)	0.7406 (4)	0.17366 (13)	0.0197 (10)
C18	0.4392 (5)	0.5720 (4)	0.16960 (14)	0.0249 (10)
C19	0.3046 (6)	0.4943 (4)	0.12417 (15)	0.0302 (11)
H4A	1.00740	0.91480	0.24800	0.0280*
H4B	1.20160	1.01150	0.23430	0.0280*
H9	1.46750	1.10840	0.19590	0.0260*
H10	1.78100	1.24320	0.17960	0.0310*
H11	1.91940	1.26470	0.08750	0.0330*
H12	1.74280	1.14920	0.01280	0.0320*
H14	1.44760	0.98740	−0.02560	0.0300*
H15	1.13830	0.84250	−0.01390	0.0290*
H18A	0.35390	0.64800	0.19110	0.0300*
H18B	0.49460	0.49230	0.19570	0.0300*
H19A	0.25390	0.57410	0.09810	0.0450*
H19B	0.18410	0.44170	0.14150	0.0450*
H19C	0.38990	0.41750	0.10390	0.0450*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0281 (12)	0.0267 (12)	0.0098 (10)	−0.0011 (11)	0.0003 (9)	−0.0002 (9)
O2	0.0339 (13)	0.0273 (13)	0.0122 (11)	0.0006 (12)	0.0006 (9)	0.0017 (9)
O3	0.0282 (12)	0.0274 (12)	0.0173 (11)	−0.0038 (11)	−0.0004 (9)	−0.0010 (9)
N4	0.0301 (15)	0.0319 (15)	0.0080 (12)	−0.0032 (15)	−0.0007 (11)	−0.0010 (11)
C5	0.0276 (17)	0.0217 (16)	0.0094 (13)	−0.0001 (16)	−0.0013 (13)	−0.0003 (12)
C6	0.0288 (18)	0.0185 (17)	0.0126 (15)	0.0043 (15)	0.0007 (13)	0.0009 (12)
C7	0.0282 (17)	0.0197 (16)	0.0104 (14)	0.0061 (15)	0.0012 (14)	−0.0007 (12)
C8	0.0270 (17)	0.0173 (16)	0.0153 (15)	0.0042 (16)	0.0013 (14)	0.0020 (12)
C9	0.0255 (17)	0.0211 (16)	0.0193 (16)	0.0032 (16)	−0.0019 (14)	−0.0002 (13)
C10	0.0281 (18)	0.0224 (18)	0.0268 (17)	0.0030 (17)	−0.0058 (14)	0.0010 (15)
C11	0.0261 (18)	0.0242 (18)	0.0324 (18)	0.0009 (17)	0.0018 (15)	0.0057 (15)
C12	0.0325 (19)	0.0256 (19)	0.0207 (17)	0.0016 (16)	0.0074 (15)	0.0033 (14)
C13	0.0289 (17)	0.0212 (17)	0.0177 (15)	0.0065 (16)	0.0020 (14)	0.0009 (13)
C14	0.038 (2)	0.0237 (18)	0.0138 (15)	0.0006 (18)	0.0060 (14)	−0.0007 (13)
C15	0.0369 (19)	0.0236 (18)	0.0119 (15)	0.0025 (17)	−0.0006 (14)	−0.0037 (13)
C16	0.0236 (16)	0.0209 (16)	0.0157 (15)	0.0016 (15)	0.0002 (13)	0.0022 (13)
C17	0.0237 (17)	0.0177 (17)	0.0177 (16)	0.0021 (15)	−0.0026 (13)	0.0007 (13)
C18	0.0269 (18)	0.0228 (18)	0.0249 (17)	−0.0034 (16)	−0.0020 (14)	0.0014 (14)
C19	0.033 (2)	0.0276 (19)	0.0300 (19)	−0.0028 (17)	−0.0091 (16)	−0.0003 (15)

Geometric parameters (Å, º) top

O1—C5	1.397 (3)	C11—C12	1.364 (5)
O1—C16	1.347 (4)	C12—C13	1.403 (5)
O2—C17	1.235 (4)	C13—C14	1.434 (5)
O3—C17	1.340 (4)	C14—C15	1.358 (5)
O3—C18	1.459 (4)	C15—C16	1.408 (4)
N4—C6	1.381 (4)	C18—C19	1.504 (5)
N4—H4A	0.8600	C9—H9	0.9300
N4—H4B	0.8600	C10—H10	0.9300
C5—C17	1.416 (4)	C11—H11	0.9300
C5—C6	1.372 (4)	C12—H12	0.9300
C6—C7	1.443 (4)	C14—H14	0.9300
C7—C16	1.389 (4)	C15—H15	0.9300
C7—C8	1.421 (4)	C18—H18A	0.9700
C8—C9	1.411 (4)	C18—H18B	0.9700
C8—C13	1.435 (4)	C19—H19A	0.9600
C9—C10	1.366 (4)	C19—H19B	0.9600
C10—C11	1.405 (5)	C19—H19C	0.9600

C5—O1—C16	105.4 (2)	O1—C16—C15	123.6 (3)
C17—O3—C18	116.1 (2)	O2—C17—O3	122.9 (3)
H4A—N4—H4B	120.00	O2—C17—C5	122.2 (3)
C6—N4—H4B	120.00	O3—C17—C5	114.9 (3)
C6—N4—H4A	120.00	O3—C18—C19	106.9 (3)
C6—C5—C17	128.5 (3)	C8—C9—H9	119.00
O1—C5—C17	120.8 (3)	C10—C9—H9	120.00
O1—C5—C6	110.7 (3)	C9—C10—H10	120.00
N4—C6—C5	125.0 (3)	C11—C10—H10	120.00
N4—C6—C7	128.5 (3)	C10—C11—H11	120.00
C5—C6—C7	106.5 (3)	C12—C11—H11	120.00
C8—C7—C16	120.5 (3)	C11—C12—H12	119.00
C6—C7—C8	134.9 (3)	C13—C12—H12	119.00
C6—C7—C16	104.6 (3)	C13—C14—H14	119.00
C7—C8—C9	125.3 (3)	C15—C14—H14	119.00
C7—C8—C13	116.3 (3)	C14—C15—H15	122.00
C9—C8—C13	118.4 (3)	C16—C15—H15	122.00
C8—C9—C10	121.0 (3)	O3—C18—H18A	110.00
C9—C10—C11	120.6 (3)	O3—C18—H18B	110.00
C10—C11—C12	119.8 (3)	C19—C18—H18A	110.00
C11—C12—C13	121.6 (3)	C19—C18—H18B	110.00
C8—C13—C14	120.1 (3)	H18A—C18—H18B	109.00
C8—C13—C12	118.7 (3)	C18—C19—H19A	109.00
C12—C13—C14	121.2 (3)	C18—C19—H19B	109.00
C13—C14—C15	122.8 (3)	C18—C19—H19C	109.00
C14—C15—C16	116.5 (3)	H19A—C19—H19B	109.00
C7—C16—C15	123.7 (3)	H19A—C19—H19C	109.00
O1—C16—C7	112.7 (3)	H19B—C19—H19C	109.00

C16—O1—C5—C6	1.3 (4)	C16—C7—C8—C13	1.9 (5)
C16—O1—C5—C17	−179.2 (3)	C6—C7—C16—O1	−0.8 (4)
C5—O1—C16—C7	−0.3 (4)	C6—C7—C16—C15	179.3 (3)
C5—O1—C16—C15	179.7 (3)	C8—C7—C16—O1	178.2 (3)
C18—O3—C17—O2	−0.3 (4)	C8—C7—C16—C15	−1.8 (5)
C18—O3—C17—C5	178.6 (3)	C7—C8—C9—C10	178.9 (3)
C17—O3—C18—C19	175.1 (3)	C13—C8—C9—C10	−0.5 (5)
O1—C5—C6—N4	−179.5 (3)	C7—C8—C13—C12	−179.4 (3)
O1—C5—C6—C7	−1.8 (4)	C7—C8—C13—C14	−1.2 (5)
C17—C5—C6—N4	1.1 (6)	C9—C8—C13—C12	0.1 (5)
C17—C5—C6—C7	178.8 (3)	C9—C8—C13—C14	178.3 (3)
O1—C5—C17—O2	179.6 (3)	C8—C9—C10—C11	0.6 (5)
O1—C5—C17—O3	0.7 (4)	C9—C10—C11—C12	−0.3 (5)
C6—C5—C17—O2	−1.0 (6)	C10—C11—C12—C13	−0.1 (5)
C6—C5—C17—O3	−179.9 (3)	C11—C12—C13—C8	0.2 (5)
N4—C6—C7—C8	0.4 (6)	C11—C12—C13—C14	−178.0 (3)
N4—C6—C7—C16	179.1 (3)	C8—C13—C14—C15	0.4 (5)
C5—C6—C7—C8	−177.2 (4)	C12—C13—C14—C15	178.6 (3)
C5—C6—C7—C16	1.5 (4)	C13—C14—C15—C16	−0.2 (5)
C6—C7—C8—C9	1.0 (6)	C14—C15—C16—O1	−179.1 (3)
C6—C7—C8—C13	−179.6 (4)	C14—C15—C16—C7	0.9 (5)
C16—C7—C8—C9	−177.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2	0.86	2.30	2.872 (4)	124
N4—H4B···O2ⁱ	0.86	2.29	3.027 (4)	144
C9—H9···O2ⁱ	0.93	2.50	3.308 (4)	146

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃NO₃
M_r	255.26
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	103
a, b, c (Å)	6.2217 (5), 8.3795 (6), 23.4692 (17)
V (Å³)	1223.56 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.28 × 0.22 × 0.22

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18171, 1288, 1093
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.117, 1.03
No. of reflections	1288
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.36

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2	0.86	2.30	2.872 (4)	124
N4—H4B···O2ⁱ	0.86	2.29	3.027 (4)	144
C9—H9···O2ⁱ	0.93	2.50	3.308 (4)	146

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

Acknowledgements

MKS thanks Research Cell, SBRR Mahajana First Grade College. SE, SAM and VVP are thankful to the UGC and the Department of Chemistry, Kuvempu University, Shankaraghatta, for financial assistance and laboratory facilities.

References

Mahadevan, K. M., Basavaraj, K. M., Prathima Mathias, D. A. & Vaidya, V. P. (2005). Indian J. Chem. Section B, 44, 789–793. Google Scholar
Nagaraja, G. K., Prakash, G. K., Satyanarayan, N. D., Vaidya, V. P. & Mahadevan, K. M. (2006). ARKIVOC, XV, 142–152. Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shruthi, E., Madan, K. S., Kusuma, K., Manjunath, H. R., Vaidya, V. P., Sridhar, M. A. & Lokanth, N. K. (2012). Anal. Sci. X-ray Struct. Anal. Online, 28, 23–24. CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Veena, K., Shashikaladevi, K., Shanmukha, I., Ramaiah, V. & Vaidya, V. P. (2011). Pharmacology Online, 1, 304–316. Google Scholar