organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

2-Hy­dr­oxy-3-nitro­benzaldehyde

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 ππ stacking [centroid–centroid distance = 3.754 (4) Å] help to establish the packing.

Related literature

For medicinal background, see: Ovenden et al. (2001[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.]); Song et al. (2007[Song, X. P., Bi, H. P. & Han, C. R. (2007). Nat. Prod. Res. Dev. 19, 254-255.]). For related structures, see: Rizal et al. (2008[Rizal, M. R., Azizul, I. & Ng, S. W. (2008). Acta Cryst. E64, o915.]); Garden et al. (2004[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.]).

[Scheme 1]

Experimental

Crystal data
  • C7H5NO4

  • Mr = 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)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.119

  • S = 1.07

  • 1230 reflections

  • 109 parameters

  • H-atom parameters constrained

  • Δρmax = 0.16 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2003[Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

H atoms bonded to C atoms were palced in geometrically calculated position and were refined using a riding model, with Uiso(H) = 1.2 Ueq(C). H atoms attached to O atoms were found in a difference Fourier synthesis and were refined using a riding model, with the O—H distances fixed as initially found and with Uiso(H) values set at 1.5 Ueq(O).

Structure description 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.

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
[Figure 1] Fig. 1. View of (I) with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. A view of the molecular packing.
2-hydroxy-3-nitrobenzaldehyde top
Crystal data top
C7H5NO4F(000) = 344
Mr = 167.12Dx = 1.599 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1493 reflections
a = 8.8276 (7) Åθ = 2.3–27.7°
b = 8.7296 (8) ŵ = 0.13 mm1
c = 9.011 (9) ÅT = 298 K
β = 90.124 (1)°Block, colourless
V = 694.4 (7) Å30.48 × 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 tubeRint = 0.026
Graphite monochromatorθmax = 25.0°, θmin = 3.2°
phi and ω scansh = 610
3289 measured reflectionsk = 910
1230 independent reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0617P)2 + 0.1126P]
where P = (Fo2 + 2Fc2)/3
1230 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C7H5NO4V = 694.4 (7) Å3
Mr = 167.12Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.8276 (7) ŵ = 0.13 mm1
b = 8.7296 (8) ÅT = 298 K
c = 9.011 (9) Å0.48 × 0.48 × 0.42 mm
β = 90.124 (1)°
Data collection top
Bruker SMART CCD
diffractometer
929 reflections with I > 2σ(I)
3289 measured reflectionsRint = 0.026
1230 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.119H-atom parameters constrained
S = 1.07Δρmax = 0.16 e Å3
1230 reflectionsΔρmin = 0.18 e Å3
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
xyzUiso*/Ueq
N10.50055 (17)0.84855 (17)0.75856 (18)0.0503 (5)
O10.29576 (16)0.32129 (17)0.56300 (17)0.0660 (5)
O20.33112 (14)0.61257 (16)0.61024 (14)0.0548 (4)
H20.29480.53460.57390.082*
O30.4312 (2)0.89120 (17)0.6494 (2)0.0793 (5)
O40.55192 (19)0.93655 (17)0.85100 (18)0.0769 (5)
C10.3983 (2)0.2987 (2)0.6511 (2)0.0519 (5)
H10.42610.19780.66980.062*
C20.48004 (18)0.4189 (2)0.72888 (18)0.0391 (4)
C30.44390 (18)0.5747 (2)0.70290 (18)0.0376 (4)
C40.52863 (19)0.68465 (19)0.77951 (19)0.0390 (4)
C50.64236 (19)0.6430 (2)0.8776 (2)0.0440 (5)
H50.69650.71840.92770.053*
C60.67596 (19)0.4909 (2)0.9015 (2)0.0490 (5)
H60.75290.46340.96690.059*
C70.5946 (2)0.3804 (2)0.8277 (2)0.0451 (5)
H70.61680.27760.84440.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0559 (10)0.0375 (9)0.0574 (11)0.0026 (7)0.0013 (8)0.0013 (8)
O10.0698 (10)0.0569 (9)0.0712 (10)0.0092 (7)0.0219 (8)0.0111 (7)
O20.0597 (8)0.0466 (8)0.0580 (8)0.0000 (6)0.0271 (7)0.0031 (6)
O30.1053 (13)0.0440 (9)0.0886 (12)0.0024 (8)0.0348 (10)0.0140 (8)
O40.1027 (13)0.0452 (9)0.0828 (11)0.0027 (8)0.0148 (9)0.0167 (8)
C10.0595 (12)0.0415 (10)0.0546 (12)0.0029 (9)0.0042 (10)0.0039 (9)
C20.0439 (10)0.0373 (10)0.0362 (9)0.0015 (7)0.0008 (7)0.0003 (7)
C30.0403 (9)0.0396 (9)0.0329 (9)0.0007 (7)0.0037 (7)0.0014 (7)
C40.0433 (9)0.0344 (9)0.0392 (9)0.0012 (7)0.0007 (7)0.0004 (7)
C50.0413 (10)0.0477 (11)0.0429 (10)0.0058 (8)0.0039 (8)0.0032 (8)
C60.0440 (10)0.0569 (12)0.0461 (11)0.0047 (8)0.0091 (8)0.0014 (9)
C70.0486 (10)0.0429 (10)0.0438 (10)0.0094 (8)0.0007 (8)0.0036 (8)
Geometric parameters (Å, º) top
N1—O31.216 (2)C2—C31.416 (2)
N1—O41.220 (2)C3—C41.399 (3)
N1—C41.464 (2)C4—C51.384 (2)
O1—C11.219 (2)C5—C61.377 (3)
O2—C31.340 (2)C5—H50.9300
O2—H20.8200C6—C71.374 (3)
C1—C21.452 (3)C6—H60.9300
C1—H10.9300C7—H70.9300
C2—C71.388 (2)
O3—N1—O4123.06 (18)C5—C4—C3121.42 (17)
O3—N1—C4119.23 (15)C5—C4—N1117.45 (15)
O4—N1—C4117.69 (17)C3—C4—N1121.13 (16)
C3—O2—H2109.5C6—C5—C4120.55 (16)
O1—C1—C2124.42 (19)C6—C5—H5119.7
O1—C1—H1117.8C4—C5—H5119.7
C2—C1—H1117.8C7—C6—C5119.31 (17)
C7—C2—C3120.15 (16)C7—C6—H6120.3
C7—C2—C1119.71 (18)C5—C6—H6120.3
C3—C2—C1120.14 (17)C6—C7—C2121.32 (18)
O2—C3—C4122.28 (16)C6—C7—H7119.3
O2—C3—C2120.47 (16)C2—C7—H7119.3
C4—C3—C2117.24 (16)
O1—C1—C2—C7179.64 (18)O3—N1—C4—C5161.56 (17)
O1—C1—C2—C30.9 (3)O4—N1—C4—C516.7 (2)
C7—C2—C3—O2178.44 (15)O3—N1—C4—C318.3 (3)
C1—C2—C3—O22.1 (2)O4—N1—C4—C3163.53 (16)
C7—C2—C3—C40.5 (2)C3—C4—C5—C60.5 (3)
C1—C2—C3—C4178.95 (15)N1—C4—C5—C6179.32 (16)
O2—C3—C4—C5178.41 (15)C4—C5—C6—C70.5 (3)
C2—C3—C4—C50.5 (2)C5—C6—C7—C20.5 (3)
O2—C3—C4—N11.8 (3)C3—C2—C7—C60.5 (3)
C2—C3—C4—N1179.32 (14)C1—C2—C7—C6178.94 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.821.862.597 (3)148
C5—H5···O2i0.932.513.422 (4)168
Symmetry code: (i) x+1/2, y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC7H5NO4
Mr167.12
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)8.8276 (7), 8.7296 (8), 9.011 (9)
β (°) 90.124 (1)
V3)694.4 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.48 × 0.48 × 0.42
Data collection
DiffractometerBruker SMART CCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3289, 1230, 929
Rint0.026
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.119, 1.07
No. of reflections1230
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
O2—H2···O10.821.862.597 (3)148
C5—H5···O2i0.932.513.422 (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

First citationBruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationGarden, 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
First citationOvenden, 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
First citationRizal, M. R., Azizul, I. & Ng, S. W. (2008). Acta Cryst. E64, o915.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSong, X. P., Bi, H. P. & Han, C. R. (2007). Nat. Prod. Res. Dev. 19, 254–255.  CAS Google Scholar

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ISSN: 2056-9890
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