Methyl 2-hydr­oxy-3-nitro­benzoate

Liu, Y.-Z.; Li, Y.-X.; Zhang, L.; Li, X.

doi:10.1107/S1600536809024301

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1716

doi:10.1107/S1600536809024301

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Methyl 2-hydroxy-3-nitrobenzoate

Yan-Zhu Liu,^a ^* Yong-Xiu Li,^a Ling Zhang ^a and Xia Li ^a

^aDepartment of Chemistry, Nanchang University, Nanchang 330031, People's Republic of China
^*Correspondence e-mail: liuyanzhu2001@yahoo.com.cn

(Received 22 May 2009; accepted 24 June 2009; online 27 June 2009)

The title compound, C₈H₇NO₅, assumes an approximately planar molecular structure with an intramolecular O—H⋯O hydrogen bond between the hydroxy and carboxylate groups. Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For the properties of 2-hydroxybenzoyl compounds, see: Konopacka et al. (2005 ); Sonar et al. (2007 ); Willian & Layne (2001 ); Huang et al. (1996 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₇NO₅
M_r = 197.15
Monoclinic, P 2₁ /c
a = 7.6120 (10) Å
b = 11.716 (2) Å
c = 9.656 (2) Å
β = 101.830 (10)°
V = 842.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 291 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
4045 measured reflections
1473 independent reflections
965 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.110
S = 1.02
1655 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O4	0.96	1.70	2.554 (2)	146
C4—H4A⋯O2ⁱ	0.93	2.57	3.321 (3)	138
C6—H6A⋯O4ⁱⁱ	0.93	2.49	3.336 (3)	151
C8—H8B⋯O1ⁱⁱ	0.96	2.59	3.305 (3)	131
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024301/xu2532sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024301/xu2532Isup2.hkl

checkCIF report

Comment top

Methyl salicylate and its analogues are useful intermediates in organic synthesis and show potential applications for functional materials and drugs (Konopacka et al., 2005; Sonar et al., 2007; Willian & Layne, 2001; Huang et al., 1996). In this paper, the structure of the title compound is reported.

The molecular structure of (I) is shown in Fig. 1. The bond lengths and angles are within normal ranges (Allen et al., 1987). There is an intramolecular hydrogen bond between the hydroxy group and the carboxyl group, and the whole molecule is planar except for the methyl H atoms. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonding (Table 1).

Related literature top

For the properties of 2-hydroxybenzoyl compounds, see: Konopacka et al. (2005); Sonar et al. (2007); Willian & Layne (2001); Huang et al. (1996). For bond-length data, see: Allen et al. (1987).

Experimental top

The methyl salicylate (3 ml) and Fe(NO₃)₃.9(H₂O) (3 g) were dissolved in ethyl acetate (50 ml), and the solution was refluxed for 1 h. The resulting mixture was cooled and filtered. The yellow single crystals were obtained from the filtrate by slowly evaporating ethyl acetate.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids at the 30% probability level. The dashed line indicates hydrogen bonding.

Methyl 2-hydroxy-3-nitrobenzoate top

Crystal data top

C₈H₇NO₅	F(000) = 408
M_r = 197.15	D_x = 1.554 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1211 reflections
a = 7.612 (1) Å	θ = 2.7–22.6°
b = 11.716 (2) Å	µ = 0.13 mm⁻¹
c = 9.656 (2) Å	T = 291 K
β = 101.83 (1)°	Block, yellow
V = 842.9 (3) Å³	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	965 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.046
Graphite monochromator	θ_max = 26.0°, θ_min = 2.7°
ϕ and ω scans	h = −8→9
4045 measured reflections	k = −13→13
1473 independent reflections	l = −11→6

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.02P)² + 0.55P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1655 reflections	Δρ_max = 0.48 e Å⁻³
129 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (3)

Crystal data top

C₈H₇NO₅	V = 842.9 (3) Å³
M_r = 197.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.612 (1) Å	µ = 0.13 mm⁻¹
b = 11.716 (2) Å	T = 291 K
c = 9.656 (2) Å	0.30 × 0.20 × 0.20 mm
β = 101.83 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	965 reflections with I > 2σ(I)
4045 measured reflections	R_int = 0.046
1473 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.02	Δρ_max = 0.48 e Å⁻³
1655 reflections	Δρ_min = −0.40 e Å⁻³
129 parameters

Special details top

Experimental. ¹H-NMR (CDCl₃, 500 MHz): δ4.03 (s, 3 H), 7.20(s, 1 H), 8.15-8.19 (d, 2 H), 12.02 (s, 1 H).

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
C3	0.6545 (3)	0.9162 (2)	−0.0890 (2)	0.0465 (6)
C4	0.6080 (3)	0.8030 (2)	−0.1125 (3)	0.0541 (7)
H4A	0.5248	0.7822	−0.1931	0.065*
C5	0.6836 (4)	0.7212 (2)	−0.0176 (3)	0.0581 (8)
H5A	0.6523	0.6448	−0.0337	0.070*
C6	0.8059 (3)	0.7525 (2)	0.1011 (3)	0.0504 (7)
H6A	0.8577	0.6966	0.1649	0.060*
C1	0.8541 (3)	0.8654 (2)	0.1281 (2)	0.0433 (6)
C2	0.7769 (3)	0.9507 (2)	0.0320 (2)	0.0449 (6)
C7	0.9867 (3)	0.8997 (2)	0.2543 (3)	0.0499 (7)
C8	1.1859 (4)	0.8424 (2)	0.4632 (3)	0.0654 (9)
H8C	1.2856	0.8819	0.4384	0.098*
H8B	1.2277	0.7740	0.5140	0.098*
H8A	1.1297	0.8907	0.5217	0.098*
N1	0.5694 (4)	0.9981 (2)	−0.1954 (3)	0.0726 (8)
O2	0.6026 (3)	1.09798 (19)	−0.1803 (2)	0.0830 (7)
O3	0.4677 (4)	0.96270 (19)	−0.2983 (2)	0.1045 (9)
O1	0.8187 (3)	1.06068 (13)	0.05425 (19)	0.0651 (6)
H1A	0.9073	1.0676	0.1402	0.098*
O4	1.0286 (3)	0.99828 (15)	0.2831 (2)	0.0692 (6)
O5	1.0566 (2)	0.81316 (14)	0.33514 (18)	0.0564 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0456 (15)	0.0474 (15)	0.0452 (15)	0.0024 (12)	0.0064 (12)	0.0044 (12)
C4	0.0541 (17)	0.0566 (18)	0.0479 (16)	−0.0064 (14)	0.0016 (13)	−0.0055 (13)
C5	0.0686 (19)	0.0408 (15)	0.0602 (17)	−0.0089 (14)	0.0021 (15)	−0.0062 (13)
C6	0.0570 (17)	0.0389 (14)	0.0523 (16)	0.0003 (12)	0.0043 (13)	0.0024 (12)
C1	0.0445 (14)	0.0380 (14)	0.0454 (14)	0.0009 (11)	0.0047 (11)	−0.0006 (11)
C2	0.0461 (15)	0.0383 (14)	0.0490 (15)	−0.0006 (12)	0.0064 (12)	−0.0027 (12)
C7	0.0510 (16)	0.0417 (15)	0.0537 (16)	0.0010 (13)	0.0032 (12)	0.0006 (13)
C8	0.0645 (19)	0.0666 (18)	0.0539 (17)	−0.0020 (15)	−0.0143 (14)	0.0017 (14)
N1	0.088 (2)	0.0614 (17)	0.0573 (16)	0.0015 (15)	−0.0116 (14)	0.0065 (14)
O2	0.1039 (18)	0.0617 (14)	0.0704 (14)	0.0079 (13)	−0.0123 (12)	0.0118 (11)
O3	0.130 (2)	0.0832 (17)	0.0741 (16)	−0.0058 (15)	−0.0405 (15)	0.0098 (13)
O1	0.0776 (14)	0.0355 (10)	0.0703 (13)	−0.0033 (9)	−0.0130 (10)	0.0026 (9)
O4	0.0805 (14)	0.0404 (11)	0.0720 (13)	−0.0043 (10)	−0.0188 (11)	−0.0055 (9)
O5	0.0603 (12)	0.0469 (11)	0.0532 (11)	−0.0018 (9)	−0.0089 (9)	0.0030 (9)

Geometric parameters (Å, º) top

C3—C4	1.380 (3)	C2—O1	1.334 (3)
C3—C2	1.396 (3)	C7—O4	1.215 (3)
C3—N1	1.457 (3)	C7—O5	1.323 (3)
C4—C5	1.369 (3)	C8—O5	1.455 (3)
C4—H4A	0.9300	C8—H8C	0.9600
C5—C6	1.371 (3)	C8—H8B	0.9600
C5—H5A	0.9300	C8—H8A	0.9600
C6—C1	1.383 (3)	N1—O2	1.200 (3)
C6—H6A	0.9300	N1—O3	1.201 (3)
C1—C2	1.408 (3)	O1—H1A	0.9600
C1—C7	1.470 (3)

C4—C3—C2	121.4 (2)	O1—C2—C1	121.7 (2)
C4—C3—N1	117.0 (2)	C3—C2—C1	117.6 (2)
C2—C3—N1	121.6 (2)	O4—C7—O5	122.6 (2)
C5—C4—C3	120.3 (2)	O4—C7—C1	123.6 (2)
C5—C4—H4A	119.8	O5—C7—C1	113.8 (2)
C3—C4—H4A	119.8	O5—C8—H8C	109.5
C4—C5—C6	119.5 (2)	O5—C8—H8B	109.5
C4—C5—H5A	120.3	H8C—C8—H8B	109.5
C6—C5—H5A	120.3	O5—C8—H8A	109.5
C5—C6—C1	121.5 (2)	H8C—C8—H8A	109.5
C5—C6—H6A	119.2	H8B—C8—H8A	109.5
C1—C6—H6A	119.2	O2—N1—O3	121.4 (2)
C6—C1—C2	119.7 (2)	O2—N1—C3	120.2 (2)
C6—C1—C7	121.9 (2)	O3—N1—C3	118.3 (3)
C2—C1—C7	118.4 (2)	C2—O1—H1A	108.9
O1—C2—C3	120.7 (2)	C7—O5—C8	116.16 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.96	1.70	2.554 (2)	146
C4—H4A···O2ⁱ	0.93	2.57	3.321 (3)	138
C6—H6A···O4ⁱⁱ	0.93	2.49	3.336 (3)	151
C8—H8B···O1ⁱⁱ	0.96	2.59	3.305 (3)	131

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

Experimental details

Crystal data
Chemical formula	C₈H₇NO₅
M_r	197.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	7.612 (1), 11.716 (2), 9.656 (2)
β (°)	101.83 (1)
V (Å³)	842.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4045, 1473, 965
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.110, 1.02
No. of reflections	1655
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.40

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O4	0.96	1.70	2.554 (2)	146
C4—H4A···O2ⁱ	0.93	2.57	3.321 (3)	138
C6—H6A···O4ⁱⁱ	0.93	2.49	3.336 (3)	151
C8—H8B···O1ⁱⁱ	0.96	2.59	3.305 (3)	131

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

Acknowledgements

This work is supported by the Program for Innovative Research Team of Nanchang University, the Open Foundation of CAS Key Laboratory of Organic Solids and the Natural Science Foundation of Education Department of Jiangxi Province, China.

References

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