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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3056–o3057.
Published online 2009 November 11. doi:  10.1107/S1600536809046807
PMCID: PMC2971860

2-Hydr­oxy-5-nitro­benzaldehyde

Abstract

The title compound, C7H5NO4, is essentially planar, with a maximum deviation from the mean plane of 0.0116 (11) Å for the hydr­oxy O atom. The mol­ecular and crystal structure are stabilized by intra- and inter­molecular inter­actions. An intra­molecular O—H(...)O hydrogen bond generates a six-membered ring, producing an S(6) ring motif. The C—H(...)O inter­actions result in the formation of C(5) chains and R 2 2(8) rings forming an approximately planar network parallel to (10An external file that holds a picture, illustration, etc.
Object name is e-65-o3056-efi4.jpg). These planes are inter­connected through π–π inter­actions [centroid–centroid distance 3.582 (2) Å].

Related literature

Nitro­aromatics are widely used as inter­mediates in explosives, dyestuffs, pesticides and organic synthesis, see: Yan et al. (2006 [triangle]). They occur in industrial wastes and as direct pollutants in the environment and are relatively soluble in water and detecta­ble in rivers, ponds and soil, see: Yan et al. (2006 [triangle]); Soojhawon et al. (2005 [triangle]). Aromatic compounds with multiple nitro substituents are known to be resistant to electrophilic attack by oxygenases, see: Halas et al. (1983 [triangle]). For comparison bond lengths and angles in related structures, see: Rizal et al. (2008 [triangle]); Garden et al. (2004 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

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Object name is e-65-o3056-scheme1.jpg

Experimental

Crystal data

  • C7H5NO4
  • M r = 167.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3056-efi5.jpg
  • a = 7.2580 (17) Å
  • b = 8.3960 (13) Å
  • c = 11.704 (3) Å
  • β = 95.165 (18)°
  • V = 710.3 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.13 mm−1
  • T = 296 K
  • 0.54 × 0.28 × 0.15 mm

Data collection

  • Stoe IPDS II diffractometer
  • Absorption correction: integration (X-RED32; Stoe & Cie, 2002 [triangle]) T min = 0.979, T max = 0.992
  • 4345 measured reflections
  • 1396 independent reflections
  • 944 reflections with I > 2σ(I)
  • R int = 0.062

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.119
  • S = 1.06
  • 1396 reflections
  • 112 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.15 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046807/dn2510sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809046807/dn2510Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This study was supported financially by the Research Center of Ondokuz Mayıs University (Project No. F-476). The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund).

supplementary crystallographic information

Comment

Nitroaromatics are widely used either as materials or as intermediates in explosives, dyestuffs, pesticides and organic synthesis (Yan et al., 2006). Nitroaromatics occur as industrial wastes and direct pollutants in the environment, and are relatively soluble in water and detectable in rivers, ponds and soil (Yan et al., 2006; Soojhawon et al., 2005). Morover, aromatic compounds with multiple nitro substituents are known to be resistant to electrophilic attack by oxygenases (Halas et al., 1983).

In the title compound (I, Fig. 1), the molecule is essentially planar with a maximum deviation from the mean plane of 0.0116 (11) Å for atom O3. 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). The dihedral angle between the aromatic ring and the nitro group is 3.83 (3)°.

An intramolecular O3-H33···O4 interaction (Table 1, and Fig. 1) generates an S(6) ring motif (Bernstein et al., 1995). In the crystal structure, the molecules are linked by intermolecular C2-H2···O4, C6-H6···O3 and C7-H7···O7 interactions into a three-dimensional framework. The C-H···O interactions result in the formation of C(5) chain but also R22(8) ring forming an approximately planar network parallel to the (1 0 -1) plane (Fig. 2). These planes are interconnected through π-π interaction which occurs between Cg1 (the centroid of the C1-C6 ring) and its symmetry equivalent at (-x,-y,-z), with a centroid-to-centroid distance of 3.582 (2) Å, a plane-to-plane separation of 3.367 (1) Å and a slippage of 1.22 Å.

Experimental

The commercially available compound (Acros Organics) was recrystallized from ethanol.

Refinement

C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The position of the H3A atom was obtained from a difference map of the electron density in the unit-cell and its coordinates were refined freely with Uiso(H) = 1.5Ueq(O) .

Figures

Fig. 1.
The molecular structure of the title compound, showing the atom-numbering scheme and 50% probability diplacement ellipsoids. H atoms are represented as small spheres of arbitrary radii.
Fig. 2.
Partial packing view showing the formation of C-H···O hydrogen bonds represented as dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry codes: (i) x, y-1, z; (ii) x+1/2, -y+1/2, z+1/2; ...

Crystal data

C7H5NO4F(000) = 344
Mr = 167.12Dx = 1.563 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8368 reflections
a = 7.2580 (17) Åθ = 1.8–27.3°
b = 8.3960 (13) ŵ = 0.13 mm1
c = 11.704 (3) ÅT = 296 K
β = 95.165 (18)°Prism., red
V = 710.3 (3) Å30.54 × 0.28 × 0.15 mm
Z = 4

Data collection

Stoe IPDS II diffractometer1396 independent reflections
Radiation source: fine-focus sealed tube944 reflections with I > 2σ(I)
graphiteRint = 0.062
Detector resolution: 6.67 pixels mm-1θmax = 26.0°, θmin = 3.0°
rotation method scansh = −8→8
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)k = −10→10
Tmin = 0.979, Tmax = 0.992l = −14→14
4345 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H atoms treated by a mixture of independent and constrained refinement
S = 1.06w = 1/[σ2(Fo2) + (0.05P)2 + 0.0581P] where P = (Fo2 + 2Fc2)/3
1396 reflections(Δ/σ)max < 0.001
112 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = −0.15 e Å3

Special details

Experimental. 168 frames, detector distance = 120 mm
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 > 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)

xyzUiso*/Ueq
O10.4340 (3)−0.1006 (2)0.25586 (14)0.0788 (6)
O20.3658 (3)−0.3022 (2)0.15003 (16)0.0819 (6)
O30.1019 (3)0.2346 (2)−0.19209 (14)0.0702 (6)
H3A0.130 (4)0.336 (4)−0.162 (3)0.105*
O40.2251 (3)0.4736 (2)−0.06415 (16)0.0895 (7)
N10.3709 (3)−0.1591 (2)0.16564 (16)0.0524 (5)
C10.3019 (3)−0.0545 (2)0.07198 (17)0.0425 (5)
C20.2232 (3)−0.1209 (2)−0.03011 (17)0.0459 (5)
H20.2154−0.2309−0.03850.055*
C30.1574 (3)−0.0228 (3)−0.11799 (18)0.0494 (5)
H30.1037−0.0659−0.18630.059*
C40.1711 (3)0.1417 (2)−0.10464 (18)0.0471 (5)
C50.2551 (3)0.2073 (2)−0.00295 (17)0.0437 (5)
C60.3190 (3)0.1067 (2)0.08585 (17)0.0431 (5)
H60.37300.14850.15440.052*
C70.2771 (3)0.3784 (3)0.0104 (2)0.0631 (7)
H70.33380.41720.07920.076*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.1123 (15)0.0673 (12)0.0522 (10)−0.0024 (11)−0.0171 (10)0.0069 (9)
O20.1202 (16)0.0391 (10)0.0829 (13)0.0026 (9)−0.0101 (11)0.0101 (8)
O30.0914 (13)0.0556 (11)0.0590 (11)0.0048 (9)−0.0195 (9)0.0061 (8)
O40.1338 (17)0.0423 (10)0.0871 (14)0.0022 (11)−0.0199 (12)0.0094 (9)
N10.0593 (11)0.0433 (12)0.0547 (11)−0.0005 (9)0.0047 (9)0.0071 (9)
C10.0418 (11)0.0382 (12)0.0475 (12)−0.0002 (9)0.0041 (9)0.0023 (9)
C20.0486 (12)0.0355 (10)0.0535 (12)−0.0007 (9)0.0046 (9)−0.0025 (9)
C30.0526 (12)0.0492 (13)0.0453 (12)−0.0032 (10)−0.0013 (9)−0.0086 (10)
C40.0463 (11)0.0458 (13)0.0480 (12)0.0029 (9)−0.0018 (9)0.0028 (10)
C50.0468 (11)0.0366 (11)0.0470 (12)−0.0014 (9)0.0007 (9)−0.0008 (9)
C60.0457 (11)0.0418 (12)0.0413 (11)−0.0031 (9)0.0009 (9)−0.0049 (9)
C70.0805 (17)0.0424 (13)0.0643 (15)−0.0020 (12)−0.0045 (12)−0.0008 (12)

Geometric parameters (Å, °)

O1—N11.216 (2)C2—H20.9300
O2—N11.215 (2)C3—C41.392 (3)
O3—C41.348 (2)C3—H30.9300
O3—H3A0.93 (3)C4—C51.401 (3)
O4—C71.218 (3)C5—C61.386 (3)
N1—C11.458 (3)C5—C71.452 (3)
C1—C61.367 (3)C6—H60.9300
C1—C21.394 (3)C7—H70.9300
C2—C31.370 (3)
C4—O3—H3A100.5 (19)O3—C4—C3118.12 (19)
O2—N1—O1122.27 (19)O3—C4—C5121.43 (19)
O2—N1—C1118.59 (19)C3—C4—C5120.45 (19)
O1—N1—C1119.13 (18)C6—C5—C4119.19 (18)
C6—C1—C2121.56 (19)C6—C5—C7119.77 (19)
C6—C1—N1119.05 (18)C4—C5—C7121.04 (19)
C2—C1—N1119.38 (18)C1—C6—C5119.59 (19)
C3—C2—C1119.5 (2)C1—C6—H6120.2
C3—C2—H2120.3C5—C6—H6120.2
C1—C2—H2120.3O4—C7—C5123.3 (2)
C2—C3—C4119.71 (19)O4—C7—H7118.4
C2—C3—H3120.1C5—C7—H7118.4
C4—C3—H3120.1

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···O4i0.932.503.427 (3)175
C6—H6···O3ii0.932.533.433 (3)163
C7—H7···O2iii0.932.503.176 (3)130
O3—H3A···O40.93 (3)1.73 (3)2.613 (3)157 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2510).

References

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