2-Hy­droxy-3-nitro­benzaldehyde

Tang, B.; Chen, G.; Song, X.; Cen, C.; Han, C.

doi:10.1107/S1600536810025110

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o1912

https://doi.org/10.1107/S1600536810025110

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2-Hydroxy-3-nitrobenzaldehyde

Bei Tang,^a Guangying Chen,^a ^* Xiaoping Song,^a ^* Changchun Cen ^a and Changri Han ^a

^aKey Laboratory of Tropical Medicinal Plant Chemistry of the Ministry of Education, Hainan Normal University, College of Chemistry & Chemical Engineering, Hainan Normal University, Haikou 571158, People's Republic of China
^*Correspondence e-mail: chgying123@163.com, sxp628@126.com

(Received 11 June 2010; accepted 26 June 2010; online 3 July 2010)

The title compound, C₇H₅NO₄, isolated from the leaves of Actephila merrilliana, is essentially planar (r.m.s. deviation = 0.026 Å). The conformation is supported by an intramolecular O—H⋯O hydrogen bond, which generates an S(6) ring. In the crystal, C—H⋯O interactions and aromatic π–π stacking [centroid–centroid distance = 3.754 (4) Å] help to establish the packing.

Related literature

For medicinal background, see: Ovenden et al. (2001 ); Song et al. (2007 ). For related structures, see: Rizal et al. (2008 ); Garden et al. (2004 ).

Experimental

Crystal data

C₇H₅NO₄
M_r = 167.12
Monoclinic, P 2₁ /n
a = 8.8276 (7) Å
b = 8.7296 (8) Å
c = 9.011 (9) Å
β = 90.124 (1)°
V = 694.4 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.48 × 0.48 × 0.42 mm

Data collection

Bruker SMART CCD diffractometer
3289 measured reflections
1230 independent reflections
929 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.119
S = 1.07
1230 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.82	1.86	2.597 (3)	148
C5—H5⋯O2ⁱ	0.93	2.51	3.422 (4)	168
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2003); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810025110/hb5495sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810025110/hb5495Isup2.hkl

checkCIF report

Comment top

Although chemical investigations into specimens of the plant family Euphorbiaceae are very common, there have been no related reports on chemical constituents of Actephila merrilliana (Ovenden et al., 2001). The plants in this family were used in folk medicine such as, for the treatment of hemorrhoids and as anti-inflammatory agents (Song et al., 2007). The title compound was isolated from the 75% EtOH extract of the leaves of Actephila merrilliana which were collected from Sanya City, Hainan Province, P. R. China. We have undertaken the X-ray crystal structure analysis of the title compound in order to establish its molecular structure and relative stereochemistry. In the title compound, the bond lengths and angles in (I) have normal values, and are comparable with those in the related structures (Rizal et al., 2008; Garden et al., 2004). An intramolecular O—H···O hydrogen bond helps to establish an essentially planar conformation for the molecule (r.m.s. deviation = 0.0258 Å).

In the crystal, molecules are linked by intermolecular C–H···O hydrogen bonds into chains (Fig.2). The hydrogen bonds and angles are listed in Table 1.

Related literature top

For medicinal background, see: Ovenden et al. (2001); Song et al. (2007). For related structures, see: Rizal et al. (2008); Garden et al. (2004).

Experimental top

Air-dried leaves of Actephila merrilliana (14.0 kg) were ground and percolated (3 × 3 h) with 75% EtOH at 60°C, which was suspended in 6 L water and then partitioned with petroleum ether, chloroform, ethyl acetate and n-BuOH, successively, yielding a petroleum ether extract, a chloroform extract, an ethyl acetate extract and a n-BuOH extract, respectively. The chloroform extract was subjected to a silica gel CC column using petroleum ether as first eluent and then increasing the polarity with EtOAc, to afford 23 fractions (A—W). Fraction M was further separated by column chromatography with a gradient of petroleum ether-EtOAc to give the title compound. The crude product was dissolved in a small amount of chloroform to obtain colourless blocks of (I) by slow evaporation of a chloroform solution at 298 K.

Structure description top

In the crystal, molecules are linked by intermolecular C–H···O hydrogen bonds into chains (Fig.2). The hydrogen bonds and angles are listed in Table 1.

For medicinal background, see: Ovenden et al. (2001); Song et al. (2007). For related structures, see: Rizal et al. (2008); Garden et al. (2004).

Computing details top

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

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the molecular packing.

2-hydroxy-3-nitrobenzaldehyde top

Crystal data top

C₇H₅NO₄	F(000) = 344
M_r = 167.12	D_x = 1.599 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1493 reflections
a = 8.8276 (7) Å	θ = 2.3–27.7°
b = 8.7296 (8) Å	µ = 0.13 mm⁻¹
c = 9.011 (9) Å	T = 298 K
β = 90.124 (1)°	Block, colourless
V = 694.4 (7) Å³	0.48 × 0.48 × 0.42 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	929 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.0°, θ_min = 3.2°
phi and ω scans	h = −6→10
3289 measured reflections	k = −9→10
1230 independent reflections	l = −10→10

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0617P)² + 0.1126P] where P = (F_o² + 2F_c²)/3
1230 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₇H₅NO₄	V = 694.4 (7) Å³
M_r = 167.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.8276 (7) Å	µ = 0.13 mm⁻¹
b = 8.7296 (8) Å	T = 298 K
c = 9.011 (9) Å	0.48 × 0.48 × 0.42 mm
β = 90.124 (1)°

Data collection top

Bruker SMART CCD diffractometer	929 reflections with I > 2σ(I)
3289 measured reflections	R_int = 0.026
1230 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.07	Δρ_max = 0.16 e Å⁻³
1230 reflections	Δρ_min = −0.18 e Å⁻³
109 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
N1	0.50055 (17)	0.84855 (17)	0.75856 (18)	0.0503 (5)
O1	0.29576 (16)	0.32129 (17)	0.56300 (17)	0.0660 (5)
O2	0.33112 (14)	0.61257 (16)	0.61024 (14)	0.0548 (4)
H2	0.2948	0.5346	0.5739	0.082*
O3	0.4312 (2)	0.89120 (17)	0.6494 (2)	0.0793 (5)
O4	0.55192 (19)	0.93655 (17)	0.85100 (18)	0.0769 (5)
C1	0.3983 (2)	0.2987 (2)	0.6511 (2)	0.0519 (5)
H1	0.4261	0.1978	0.6698	0.062*
C2	0.48004 (18)	0.4189 (2)	0.72888 (18)	0.0391 (4)
C3	0.44390 (18)	0.5747 (2)	0.70290 (18)	0.0376 (4)
C4	0.52863 (19)	0.68465 (19)	0.77951 (19)	0.0390 (4)
C5	0.64236 (19)	0.6430 (2)	0.8776 (2)	0.0440 (5)
H5	0.6965	0.7184	0.9277	0.053*
C6	0.67596 (19)	0.4909 (2)	0.9015 (2)	0.0490 (5)
H6	0.7529	0.4634	0.9669	0.059*
C7	0.5946 (2)	0.3804 (2)	0.8277 (2)	0.0451 (5)
H7	0.6168	0.2776	0.8444	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0559 (10)	0.0375 (9)	0.0574 (11)	−0.0026 (7)	−0.0013 (8)	−0.0013 (8)
O1	0.0698 (10)	0.0569 (9)	0.0712 (10)	−0.0092 (7)	−0.0219 (8)	−0.0111 (7)
O2	0.0597 (8)	0.0466 (8)	0.0580 (8)	0.0000 (6)	−0.0271 (7)	0.0031 (6)
O3	0.1053 (13)	0.0440 (9)	0.0886 (12)	0.0024 (8)	−0.0348 (10)	0.0140 (8)
O4	0.1027 (13)	0.0452 (9)	0.0828 (11)	−0.0027 (8)	−0.0148 (9)	−0.0167 (8)
C1	0.0595 (12)	0.0415 (10)	0.0546 (12)	−0.0029 (9)	−0.0042 (10)	−0.0039 (9)
C2	0.0439 (10)	0.0373 (10)	0.0362 (9)	0.0015 (7)	0.0008 (7)	0.0003 (7)
C3	0.0403 (9)	0.0396 (9)	0.0329 (9)	0.0007 (7)	−0.0037 (7)	0.0014 (7)
C4	0.0433 (9)	0.0344 (9)	0.0392 (9)	−0.0012 (7)	−0.0007 (7)	0.0004 (7)
C5	0.0413 (10)	0.0477 (11)	0.0429 (10)	−0.0058 (8)	−0.0039 (8)	−0.0032 (8)
C6	0.0440 (10)	0.0569 (12)	0.0461 (11)	0.0047 (8)	−0.0091 (8)	0.0014 (9)
C7	0.0486 (10)	0.0429 (10)	0.0438 (10)	0.0094 (8)	−0.0007 (8)	0.0036 (8)

Geometric parameters (Å, º) top

N1—O3	1.216 (2)	C2—C3	1.416 (2)
N1—O4	1.220 (2)	C3—C4	1.399 (3)
N1—C4	1.464 (2)	C4—C5	1.384 (2)
O1—C1	1.219 (2)	C5—C6	1.377 (3)
O2—C3	1.340 (2)	C5—H5	0.9300
O2—H2	0.8200	C6—C7	1.374 (3)
C1—C2	1.452 (3)	C6—H6	0.9300
C1—H1	0.9300	C7—H7	0.9300
C2—C7	1.388 (2)

O3—N1—O4	123.06 (18)	C5—C4—C3	121.42 (17)
O3—N1—C4	119.23 (15)	C5—C4—N1	117.45 (15)
O4—N1—C4	117.69 (17)	C3—C4—N1	121.13 (16)
C3—O2—H2	109.5	C6—C5—C4	120.55 (16)
O1—C1—C2	124.42 (19)	C6—C5—H5	119.7
O1—C1—H1	117.8	C4—C5—H5	119.7
C2—C1—H1	117.8	C7—C6—C5	119.31 (17)
C7—C2—C3	120.15 (16)	C7—C6—H6	120.3
C7—C2—C1	119.71 (18)	C5—C6—H6	120.3
C3—C2—C1	120.14 (17)	C6—C7—C2	121.32 (18)
O2—C3—C4	122.28 (16)	C6—C7—H7	119.3
O2—C3—C2	120.47 (16)	C2—C7—H7	119.3
C4—C3—C2	117.24 (16)

O1—C1—C2—C7	179.64 (18)	O3—N1—C4—C5	161.56 (17)
O1—C1—C2—C3	−0.9 (3)	O4—N1—C4—C5	−16.7 (2)
C7—C2—C3—O2	−178.44 (15)	O3—N1—C4—C3	−18.3 (3)
C1—C2—C3—O2	2.1 (2)	O4—N1—C4—C3	163.53 (16)
C7—C2—C3—C4	0.5 (2)	C3—C4—C5—C6	0.5 (3)
C1—C2—C3—C4	−178.95 (15)	N1—C4—C5—C6	−179.32 (16)
O2—C3—C4—C5	178.41 (15)	C4—C5—C6—C7	−0.5 (3)
C2—C3—C4—C5	−0.5 (2)	C5—C6—C7—C2	0.5 (3)
O2—C3—C4—N1	−1.8 (3)	C3—C2—C7—C6	−0.5 (3)
C2—C3—C4—N1	179.32 (14)	C1—C2—C7—C6	178.94 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.86	2.597 (3)	148
C5—H5···O2ⁱ	0.93	2.51	3.422 (4)	168

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

Experimental details

Crystal data
Chemical formula	C₇H₅NO₄
M_r	167.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	8.8276 (7), 8.7296 (8), 9.011 (9)
β (°)	90.124 (1)
V (Å³)	694.4 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.48 × 0.48 × 0.42

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3289, 1230, 929
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.119, 1.07
No. of reflections	1230
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1	0.82	1.86	2.597 (3)	148
C5—H5···O2ⁱ	0.93	2.51	3.422 (4)	168

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (20862005), the Program for New Century Excellent Talents in Universities (NCET-08–0656) and the Natural Science Foundation of Hainan Province (No. 070207). We thank Daqi Wang for collecting the crystal data.

References

Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Garden, S. J., da Cunha, F. R., Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2004). Acta Cryst. C60, o12–o14. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ovenden, S. P. B., Alex, L. S., Robert, P. G., Ng, S. C. J. R., Jacinto, C. R. Jr, Doel, D. S., Antony, D. B. & Mark, S. B. (2001). Tetrahedron Lett. 42, 7695–7697. Web of Science CrossRef CAS Google Scholar
Rizal, M. R., Azizul, I. & Ng, S. W. (2008). Acta Cryst. E64, o915. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, X. P., Bi, H. P. & Han, C. R. (2007). Nat. Prod. Res. Dev. 19, 254–255. CAS Google Scholar