Ethyl 2-(2-hy­droxy-5-nitro­phen­yl)acetate

Guo, B.; Shi, Y.-B.; Yao, J.-H.; Guan, J.-N.

doi:10.1107/S1600536811000389

organic compounds

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Volume 67| Part 2| February 2011| Page o509

doi:10.1107/S1600536811000389

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Ethyl 2-(2-hydroxy-5-nitrophenyl)acetate

Bing Guo,^a Ya-Bin Shi,^a Jin-Hua Yao ^a and Jian-Ning Guan ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guanjn@sina.com

(Received 21 December 2010; accepted 5 January 2011; online 29 January 2011)

In the crystal structure of the title compound, C₁₀H₁₁NO₅, intermolecular O—H⋯O hydrogen bonds link the molecules into chains along the b-axis direction. Weak C—H.·O hydrogen bonds also occur.

Related literature

For the use of the title compound as a pharmaceutical intermediate and for the preparation, see: Omar et al. (2003 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₁₁NO₅
M_r = 225.20
Monoclinic, P 2₁ /c
a = 11.066 (2) Å
b = 10.860 (2) Å
c = 8.6970 (17) Å
β = 97.85 (3)°
V = 1035.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.966, T_max = 0.988
3894 measured reflections
1905 independent reflections
1382 reflections with I > 2σ(I)
R_int = 0.056
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.153
S = 1.00
1905 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱ	0.82	1.93	2.749 (2)	180
C2—H2A⋯O3ⁱⁱ	0.97	2.60	3.340 (3)	134
C4—H4A⋯O4ⁱⁱⁱ	0.97	2.54	3.431 (3)	153
C6—H6A⋯O5^iv	0.93	2.51	3.351 (3)	151
C8—H8A⋯O4^v	0.93	2.59	3.430 (3)	150
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z; (iii) -x+1, -y+1, -z; (iv) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97; software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000389/bq2266sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000389/bq2266Isup2.hkl

checkCIF report

Comment top

The compound, 5-nitrobenzofuran-2(3H)-one, which is an effective intermediate prepared dronedarone, plays an important role in the fields of natural products and medicinal chemistry. The title compound, ethyl 2-(2-hydroxy-5-nitrophenyl)acetate, (I), is a useful pharmaceutical intermediate (Omar et al., 2003).

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. In the crystal structure, intermolecular O-H···O hydrogen bonds (Table 1.) link the molecules forming a stable structure and the other weak C-H···O hydrogen bonds reinforced the packing (Fig. 2).

Related literature top

For the use of the title compound as a pharmaceutical intermediate and for the preparation, see: Omar et al. (2003). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound I was prepared by the literature method (Omar et al., 2003). To a 100 mL flask provided with Dean–Stark tramp and magnetic stirrer was added (2-hydroxy-phenyl)-acetic acid (4.4 g, 29 mmol) in 60 mL of toluene and catalytic amounts of p-TsOH. The mixture was refluxed for 4 h with removal of water and then the residual solvent was removed at reduced pressure to give 3H-benzofuran-2-one in quantitative yield (3.9 g), mp 325K. Then, a mixture of concentrated nitric acid (4 ml) and glacial acetic acid (4 ml) was added drop wise to a solution of 3H-benzofuran-2-one (3.9 g) in acetic anhydride (25 ml) while the temperature was maintained below 293 K. The mixture was stirred and refluxed for 1 hour in ethanol (30 ml). The precipitate (the desired anthranilic acid esters ethyl 2-(2-hydroxy-5-nitrophenyl) acetate) was filtered off and washed with water, yield 80%. Crystals suitable for x-ray analysis were obtained by slow evaporation of an methanol solution.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bond is shown as dashed line.

Ethyl 2-(2-hydroxy-5-nitrophenyl)acetate top

Crystal data top

C₁₀H₁₁NO₅	F(000) = 472
M_r = 225.20	D_x = 1.445 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 423 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.066 (2) Å	Cell parameters from 25 reflections
b = 10.860 (2) Å	θ = 9–12°
c = 8.6970 (17) Å	µ = 0.12 mm⁻¹
β = 97.85 (3)°	T = 293 K
V = 1035.4 (4) Å³	Block, yellow
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1382 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 25.4°, θ_min = 1.9°
ω/2θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968)	k = −13→13
T_min = 0.966, T_max = 0.988	l = −10→10
3894 measured reflections	3 standard reflections every 200 reflections
1905 independent reflections	intensity decay: 1%

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.099P)²] where P = (F_o² + 2F_c²)/3
1905 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₀H₁₁NO₅	V = 1035.4 (4) Å³
M_r = 225.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.066 (2) Å	µ = 0.12 mm⁻¹
b = 10.860 (2) Å	T = 293 K
c = 8.6970 (17) Å	0.30 × 0.20 × 0.10 mm
β = 97.85 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1382 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.056
T_min = 0.966, T_max = 0.988	3 standard reflections every 200 reflections
3894 measured reflections	intensity decay: 1%
1905 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.00	Δρ_max = 0.59 e Å⁻³
1905 reflections	Δρ_min = −0.19 e Å⁻³
145 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N	0.44757 (17)	0.77034 (17)	−0.2435 (2)	0.0459 (5)
O1	0.84749 (14)	0.35380 (12)	0.03010 (16)	0.0410 (4)
C1	0.9150 (3)	0.1519 (2)	−0.0185 (3)	0.0683 (9)
H1A	0.9544	0.1015	−0.0874	0.102*
H1B	0.8344	0.1209	−0.0133	0.102*
H1C	0.9614	0.1503	0.0832	0.102*
O2	0.86074 (14)	0.51755 (12)	−0.11869 (19)	0.0463 (4)
C2	0.9070 (2)	0.2789 (2)	−0.0764 (3)	0.0514 (6)
H2A	0.9880	0.3106	−0.0830	0.062*
H2B	0.8604	0.2813	−0.1792	0.062*
O3	0.83631 (14)	0.75835 (12)	0.23336 (18)	0.0447 (4)
H3A	0.8435	0.8252	0.2774	0.067*
C3	0.82574 (18)	0.46958 (16)	−0.0074 (2)	0.0328 (5)
O4	0.40609 (16)	0.67242 (16)	−0.2982 (2)	0.0621 (5)
C4	0.7546 (2)	0.53250 (18)	0.1045 (2)	0.0428 (6)
H4A	0.6900	0.4778	0.1272	0.051*
H4B	0.8082	0.5467	0.2008	0.051*
C5	0.69929 (19)	0.65258 (17)	0.0481 (2)	0.0344 (5)
O5	0.40459 (18)	0.86915 (17)	−0.2870 (2)	0.0748 (7)
C6	0.60137 (19)	0.65579 (17)	−0.0694 (2)	0.0357 (5)
H6A	0.5693	0.5828	−0.1137	0.043*
C7	0.55121 (18)	0.76775 (18)	−0.1209 (2)	0.0360 (5)
C8	0.5979 (2)	0.87793 (19)	−0.0587 (3)	0.0396 (5)
H8A	0.5650	0.9525	−0.0968	0.048*
C9	0.6931 (2)	0.87561 (18)	0.0595 (2)	0.0391 (5)
H9A	0.7243	0.9491	0.1032	0.047*
C10	0.74381 (18)	0.76365 (17)	0.1149 (2)	0.0332 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.0430 (11)	0.0481 (11)	0.0477 (12)	0.0049 (9)	0.0104 (9)	0.0045 (9)
O1	0.0551 (10)	0.0265 (7)	0.0436 (9)	0.0072 (6)	0.0143 (7)	0.0031 (6)
C1	0.100 (2)	0.0364 (13)	0.0666 (18)	0.0172 (13)	0.0056 (16)	−0.0105 (12)
O2	0.0520 (9)	0.0380 (8)	0.0525 (10)	0.0080 (7)	0.0201 (7)	0.0112 (7)
C2	0.0547 (15)	0.0494 (13)	0.0546 (15)	0.0148 (11)	0.0232 (12)	−0.0012 (11)
O3	0.0476 (9)	0.0418 (9)	0.0440 (9)	0.0038 (7)	0.0040 (7)	−0.0097 (7)
C3	0.0372 (11)	0.0253 (9)	0.0353 (11)	0.0013 (8)	0.0026 (8)	0.0022 (8)
O4	0.0566 (11)	0.0569 (11)	0.0692 (12)	−0.0035 (9)	−0.0048 (9)	−0.0059 (9)
C4	0.0644 (15)	0.0314 (11)	0.0344 (11)	0.0096 (10)	0.0134 (10)	0.0023 (8)
C5	0.0467 (12)	0.0283 (10)	0.0318 (10)	0.0064 (8)	0.0181 (9)	−0.0006 (8)
O5	0.0697 (13)	0.0553 (11)	0.0918 (15)	0.0148 (9)	−0.0167 (11)	0.0160 (10)
C6	0.0454 (12)	0.0273 (10)	0.0371 (11)	0.0010 (8)	0.0162 (9)	−0.0039 (8)
C7	0.0378 (11)	0.0347 (10)	0.0381 (12)	0.0027 (8)	0.0149 (9)	−0.0021 (8)
C8	0.0487 (13)	0.0310 (10)	0.0424 (12)	0.0093 (9)	0.0178 (10)	0.0040 (9)
C9	0.0527 (13)	0.0268 (10)	0.0407 (12)	−0.0027 (9)	0.0169 (10)	−0.0037 (8)
C10	0.0372 (11)	0.0352 (10)	0.0307 (10)	0.0036 (8)	0.0171 (9)	−0.0032 (8)

Geometric parameters (Å, º) top

N—O5	1.213 (2)	C3—C4	1.498 (3)
N—O4	1.228 (2)	C4—C5	1.495 (3)
N—C7	1.455 (3)	C4—H4A	0.9700
O1—C3	1.313 (2)	C4—H4B	0.9700
O1—C2	1.456 (2)	C5—C6	1.385 (3)
C1—C2	1.466 (3)	C5—C10	1.399 (3)
C1—H1A	0.9600	C6—C7	1.385 (3)
C1—H1B	0.9600	C6—H6A	0.9300
C1—H1C	0.9600	C7—C8	1.384 (3)
O2—C3	1.208 (2)	C8—C9	1.369 (3)
C2—H2A	0.9700	C8—H8A	0.9300
C2—H2B	0.9700	C9—C10	1.397 (3)
O3—C10	1.351 (3)	C9—H9A	0.9300
O3—H3A	0.8200

O5—N—O4	122.4 (2)	C3—C4—H4A	108.7
O5—N—C7	118.79 (18)	C5—C4—H4B	108.7
O4—N—C7	118.85 (17)	C3—C4—H4B	108.7
C3—O1—C2	117.42 (16)	H4A—C4—H4B	107.6
C2—C1—H1A	109.5	C6—C5—C10	118.72 (17)
C2—C1—H1B	109.5	C6—C5—C4	120.57 (18)
H1A—C1—H1B	109.5	C10—C5—C4	120.70 (19)
C2—C1—H1C	109.5	C5—C6—C7	119.96 (18)
H1A—C1—H1C	109.5	C5—C6—H6A	120.0
H1B—C1—H1C	109.5	C7—C6—H6A	120.0
O1—C2—C1	108.58 (19)	C8—C7—C6	121.4 (2)
O1—C2—H2A	110.0	C8—C7—N	118.96 (18)
C1—C2—H2A	110.0	C6—C7—N	119.64 (18)
O1—C2—H2B	110.0	C9—C8—C7	119.06 (18)
C1—C2—H2B	110.0	C9—C8—H8A	120.5
H2A—C2—H2B	108.4	C7—C8—H8A	120.5
C10—O3—H3A	109.5	C8—C9—C10	120.47 (18)
O2—C3—O1	122.96 (19)	C8—C9—H9A	119.8
O2—C3—C4	125.33 (17)	C10—C9—H9A	119.8
O1—C3—C4	111.71 (17)	O3—C10—C9	121.81 (18)
C5—C4—C3	114.36 (17)	O3—C10—C5	117.85 (17)
C5—C4—H4A	108.7	C9—C10—C5	120.34 (19)

C3—O1—C2—C1	−176.2 (2)	O4—N—C7—C8	−179.8 (2)
C2—O1—C3—O2	−5.6 (3)	O5—N—C7—C6	179.8 (2)
C2—O1—C3—C4	174.94 (19)	O4—N—C7—C6	0.5 (3)
O2—C3—C4—C5	15.6 (3)	C6—C7—C8—C9	−2.1 (3)
O1—C3—C4—C5	−164.98 (18)	N—C7—C8—C9	178.19 (18)
C3—C4—C5—C6	71.4 (3)	C7—C8—C9—C10	1.0 (3)
C3—C4—C5—C10	−109.9 (2)	C8—C9—C10—O3	−178.73 (19)
C10—C5—C6—C7	1.4 (3)	C8—C9—C10—C5	1.3 (3)
C4—C5—C6—C7	−179.79 (18)	C6—C5—C10—O3	177.52 (17)
C5—C6—C7—C8	0.9 (3)	C4—C5—C10—O3	−1.3 (3)
C5—C6—C7—N	−179.43 (17)	C6—C5—C10—C9	−2.5 (3)
O5—N—C7—C8	−0.4 (3)	C4—C5—C10—C9	178.75 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.82	1.93	2.749 (2)	180
C2—H2A···O3ⁱⁱ	0.97	2.60	3.340 (3)	134
C4—H4A···O4ⁱⁱⁱ	0.97	2.54	3.431 (3)	153
C6—H6A···O5^iv	0.93	2.51	3.351 (3)	151
C8—H8A···O4^v	0.93	2.59	3.430 (3)	150

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+2, −y+1, −z; (iii) −x+1, −y+1, −z; (iv) −x+1, y−1/2, −z−1/2; (v) −x+1, y+1/2, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NO₅
M_r	225.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.066 (2), 10.860 (2), 8.6970 (17)
β (°)	97.85 (3)
V (Å³)	1035.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.966, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	3894, 1905, 1382
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.153, 1.00
No. of reflections	1905
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.19

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), 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
O3—H3A···O2ⁱ	0.82	1.93	2.749 (2)	180
C2—H2A···O3ⁱⁱ	0.97	2.60	3.340 (3)	134
C4—H4A···O4ⁱⁱⁱ	0.97	2.54	3.431 (3)	153
C6—H6A···O5^iv	0.93	2.51	3.351 (3)	151
C8—H8A···O4^v	0.93	2.59	3.430 (3)	150

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+2, −y+1, −z; (iii) −x+1, −y+1, −z; (iv) −x+1, y−1/2, −z−1/2; (v) −x+1, y+1/2, −z−1/2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 EXPRESS. Enraf–Nonius, Delft. The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Omar, M. M. & Eusebio, J. (2003). Tetrahedron, 59, 4223–4229. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 67| Part 2| February 2011| Page o509

doi:10.1107/S1600536811000389

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