3-Hydr­oxy-4-nitro­phenyl acetate

Liu, C.; Cheng, C.; Ji, X.

doi:10.1107/S1600536808040981

organic compounds

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Volume 65| Part 1| January 2009| Page o46

doi:10.1107/S1600536808040981

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3-Hydroxy-4-nitrophenyl acetate

Chao Liu,^a ^* Chunqing Cheng ^b and Xiujie Ji ^c ^*

^aSchool of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, People's Republic of China, ^bSchool of Pharmacy, Jiangxi Science and Technology, Normal University, Jiangxi 330013, People's Republic of China, and ^cTianjin Municipal Key Laboratory of Fiber Modification and Functional Fibers, Tianjin Polytechnic University, Tianjin 300160, People's Republic of China
^*Correspondence e-mail: liuchao_tj@yahoo.com, jxjchem@yahoo.com

(Received 21 November 2008; accepted 4 December 2008; online 10 December 2008)

In the molecule of the title compound, C₈H₇NO₅, the acetate group is oriented with respect to the aromatic ring at a dihedral angle of 85.30 (3)°. An intramolecular O—H⋯O hydrogen bond results in the formation of a non-planar six-membered ring, adopting an envelope conformation. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules.

Related literature

For general background to phenolic esters as intermediates in organic synthesis, see: Trollsås et al. (1996 ); Svensson et al. (1998 ); Atkinson et al. (2005 ); Hu et al. (2001 ). For a related structure, see: Ji et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₇NO₅
M_r = 197.15
Monoclinic, P 2₁ /n
a = 10.881 (2) Å
b = 5.0543 (10) Å
c = 15.318 (3) Å
β = 93.75 (3)°
V = 840.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 153 (2) K
0.24 × 0.20 × 0.16 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.969, T_max = 0.979
5058 measured reflections
1449 independent reflections
1232 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.083
S = 1.12
1449 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4	0.82	1.91	2.605 (2)	142
C5—H5⋯O1ⁱ	0.93	2.58	3.229 (2)	127
C8—H8⋯O3ⁱⁱ	0.93	2.56	3.481 (2)	170
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+2, -z+2.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808040981/hk2582sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040981/hk2582Isup2.hkl

checkCIF report

Comment top

Phenolic esters are useful intermediates in organic synthesis (Trollsås et al., 1996; Svensson et al., 1998; Atkinson et al., 2005; Hu et al., 2001). We have developed a new method for the syntheses of some phenolic esters (Ji et al., 2006). The title compound is one of the products, and we report herein its crystal structure.

In the molecule of the title compound (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. The acetate group is oriented with respect to the aromatic ring at a dihedral angle of 85.30 (3)°. The intramolecular O-H···O hydrogen bond (Table 1) results in the formation of a nonplanar six-membered ring (N1/O3/O4/C6/C7/H3), adopting envelope conformation.

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background to phenolic esters as intermediates in organic synthesis, see: Trollsås et al. (1996); Svensson et al. (1998); Atkinson et al. (2005); Hu et al. (2001). For a related structure, see: Ji et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, 2-nitroresorcin acetate (239 mg, 1.0 mmol) was dissolved in chloroform (20 ml). At 273-278 K, anhydrous AlCl₃ (133.5 mg, 1 mmol) was added to this solution, the reaction was stirred at room temperature for 1 h, and then hydrochloric acid (5 ml, 10%) was added. The reaction mixture was extracted with chloroform and dried with anhydrous sodium sulfate. After concentration, the residue was separated by flash column chromatography and purified by recrystallization from chloroform (yield; 144 mg, 73%, m.p. 360 K). Spectroscopic analysis: IR (KBr, ν, cm^-1): 3253, 3083, 2946, 1758, 1530, 1204, 1138, 978, 847. Analysis required for C₈H₇NO₅: C 48.74; H 3.58; N 7.10%. Found: C 48.80; H 3.61; N 7.08%.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bond is shown as ashed line.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

3-Hydroxy-4-nitrophenyl acetate top

Crystal data top

C₈H₇NO₅	F(000) = 408
M_r = 197.15	D_x = 1.558 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 360 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.881 (2) Å	Cell parameters from 2650 reflections
b = 5.0543 (10) Å	θ = 2.2–27.5°
c = 15.318 (3) Å	µ = 0.13 mm⁻¹
β = 93.75 (3)°	T = 153 K
V = 840.6 (3) Å³	Block, colorless
Z = 4	0.24 × 0.20 × 0.16 mm

Data collection top

Bruker P4 diffractometer	1449 independent reflections
Radiation source: fine-focus sealed tube	1232 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.969, T_max = 0.979	k = −6→5
5058 measured reflections	l = −18→15

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0475P)² + 0.1223P] where P = (F_o² + 2F_c²)/3
1449 reflections	(Δ/σ)_max = 0.001
129 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₈H₇NO₅	V = 840.6 (3) Å³
M_r = 197.15	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.881 (2) Å	µ = 0.13 mm⁻¹
b = 5.0543 (10) Å	T = 153 K
c = 15.318 (3) Å	0.24 × 0.20 × 0.16 mm
β = 93.75 (3)°

Data collection top

Bruker P4 diffractometer	1449 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1232 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.979	R_int = 0.027
5058 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.12	Δρ_max = 0.18 e Å⁻³
1449 reflections	Δρ_min = −0.20 e Å⁻³
129 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
O1	0.14195 (8)	0.58036 (19)	0.89666 (6)	0.0279 (3)
O2	0.31702 (7)	0.35401 (18)	0.93249 (5)	0.0244 (3)
O3	0.59843 (8)	1.04495 (18)	0.88687 (5)	0.0223 (2)
H3	0.6350	1.1192	0.8486	0.033*
O4	0.67226 (8)	1.08418 (17)	0.72904 (5)	0.0230 (2)
O5	0.63078 (8)	0.77288 (18)	0.63478 (5)	0.0247 (2)
N1	0.61633 (9)	0.8778 (2)	0.70551 (6)	0.0179 (3)
C1	0.13908 (11)	0.2225 (3)	1.00085 (8)	0.0213 (3)
H1A	0.0532	0.2620	1.0041	0.032*
H1B	0.1807	0.2425	1.0577	0.032*
H1C	0.1482	0.0438	0.9810	0.032*
C2	0.19373 (11)	0.4079 (2)	0.93821 (7)	0.0179 (3)
C3	0.38267 (10)	0.5030 (3)	0.87381 (8)	0.0195 (3)
C4	0.38272 (11)	0.4184 (3)	0.78716 (8)	0.0207 (3)
H4	0.3323	0.2804	0.7666	0.025*
C5	0.46001 (11)	0.5463 (2)	0.73292 (8)	0.0194 (3)
H5	0.4633	0.4919	0.6751	0.023*
C6	0.53337 (10)	0.7573 (2)	0.76450 (7)	0.0164 (3)
C7	0.53043 (10)	0.8455 (2)	0.85126 (7)	0.0168 (3)
C8	0.45238 (10)	0.7116 (2)	0.90598 (7)	0.0189 (3)
H8	0.4480	0.7643	0.9639	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0222 (5)	0.0277 (6)	0.0342 (5)	0.0061 (4)	0.0054 (4)	0.0129 (4)
O2	0.0180 (5)	0.0266 (5)	0.0290 (5)	0.0010 (4)	0.0041 (3)	0.0131 (4)
O3	0.0269 (5)	0.0225 (5)	0.0177 (4)	−0.0062 (4)	0.0019 (4)	−0.0023 (3)
O4	0.0233 (5)	0.0224 (5)	0.0232 (5)	−0.0057 (4)	0.0018 (3)	−0.0005 (4)
O5	0.0302 (5)	0.0282 (5)	0.0164 (4)	0.0030 (4)	0.0064 (4)	−0.0034 (4)
N1	0.0165 (5)	0.0200 (6)	0.0171 (5)	0.0032 (4)	0.0004 (4)	0.0005 (4)
C1	0.0219 (6)	0.0208 (7)	0.0216 (6)	−0.0008 (5)	0.0033 (5)	0.0030 (5)
C2	0.0176 (6)	0.0169 (6)	0.0190 (6)	−0.0003 (5)	0.0003 (5)	−0.0026 (5)
C3	0.0143 (6)	0.0208 (7)	0.0235 (6)	0.0042 (5)	0.0021 (5)	0.0071 (5)
C4	0.0177 (6)	0.0182 (7)	0.0255 (7)	−0.0008 (5)	−0.0033 (5)	0.0010 (5)
C5	0.0204 (6)	0.0191 (7)	0.0180 (6)	0.0029 (5)	−0.0022 (5)	−0.0012 (5)
C6	0.0150 (6)	0.0177 (6)	0.0166 (6)	0.0033 (5)	0.0012 (4)	0.0018 (4)
C7	0.0162 (6)	0.0158 (6)	0.0182 (6)	0.0035 (5)	−0.0016 (4)	−0.0003 (5)
C8	0.0197 (6)	0.0211 (7)	0.0159 (6)	0.0043 (5)	0.0022 (5)	0.0017 (5)

Geometric parameters (Å, º) top

O1—C2	1.1982 (15)	C1—H1C	0.9600
O2—C2	1.3773 (15)	C3—C8	1.3716 (18)
O2—C3	1.4032 (14)	C3—C4	1.3944 (17)
O3—C7	1.3447 (15)	C4—C5	1.3807 (17)
O3—H3	0.8200	C4—H4	0.9300
O4—N1	1.2489 (13)	C5—C6	1.3994 (17)
O5—N1	1.2255 (12)	C5—H5	0.9300
N1—C6	1.4521 (15)	C6—C7	1.4041 (16)
C1—C2	1.4923 (16)	C7—C8	1.4054 (17)
C1—H1A	0.9600	C8—H8	0.9300
C1—H1B	0.9600

C2—O2—C3	118.26 (9)	C4—C3—O2	118.51 (11)
C7—O3—H3	109.5	C5—C4—C3	117.87 (12)
O5—N1—O4	121.88 (10)	C5—C4—H4	121.1
O5—N1—C6	119.32 (10)	C3—C4—H4	121.1
O4—N1—C6	118.79 (9)	C4—C5—C6	120.33 (11)
C2—C1—H1A	109.5	C4—C5—H5	119.8
C2—C1—H1B	109.5	C6—C5—H5	119.8
H1A—C1—H1B	109.5	C5—C6—C7	121.42 (11)
C2—C1—H1C	109.5	C5—C6—N1	117.92 (10)
H1A—C1—H1C	109.5	C7—C6—N1	120.63 (11)
H1B—C1—H1C	109.5	O3—C7—C6	125.16 (10)
O1—C2—O2	122.43 (11)	O3—C7—C8	117.20 (10)
O1—C2—C1	127.24 (11)	C6—C7—C8	117.62 (11)
O2—C2—C1	110.33 (10)	C3—C8—C7	119.85 (11)
C8—C3—C4	122.88 (11)	C3—C8—H8	120.1
C8—C3—O2	118.37 (10)	C7—C8—H8	120.1

C3—O2—C2—O1	−1.83 (17)	O5—N1—C6—C7	169.13 (10)
C3—O2—C2—C1	177.59 (10)	O4—N1—C6—C7	−9.92 (16)
C2—O2—C3—C8	98.78 (13)	C5—C6—C7—O3	179.46 (10)
C2—O2—C3—C4	−86.75 (14)	N1—C6—C7—O3	1.57 (18)
C8—C3—C4—C5	2.32 (18)	C5—C6—C7—C8	0.95 (17)
O2—C3—C4—C5	−171.88 (10)	N1—C6—C7—C8	−176.94 (10)
C3—C4—C5—C6	−1.34 (18)	C4—C3—C8—C7	−1.64 (18)
C4—C5—C6—C7	−0.25 (18)	O2—C3—C8—C7	172.57 (10)
C4—C5—C6—N1	177.70 (10)	O3—C7—C8—C3	−178.67 (10)
O5—N1—C6—C5	−8.83 (15)	C6—C7—C8—C3	−0.03 (17)
O4—N1—C6—C5	172.12 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4	0.82	1.91	2.605 (2)	142
C5—H5···O1ⁱ	0.93	2.58	3.229 (2)	127
C8—H8···O3ⁱⁱ	0.93	2.56	3.481 (2)	170

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

Experimental details

Crystal data
Chemical formula	C₈H₇NO₅
M_r	197.15
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	153
a, b, c (Å)	10.881 (2), 5.0543 (10), 15.318 (3)
β (°)	93.75 (3)
V (Å³)	840.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.24 × 0.20 × 0.16

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.969, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5058, 1449, 1232
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.083, 1.12
No. of reflections	1449
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4	0.82	1.91	2.605 (2)	142
C5—H5···O1ⁱ	0.93	2.58	3.229 (2)	127
C8—H8···O3ⁱⁱ	0.93	2.56	3.481 (2)	170

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

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o46

doi:10.1107/S1600536808040981

Open

access