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Acta Crystallogr Sect E Struct Rep Online. 2008 May 1; 64(Pt 5): o915.
Published online 2008 April 26. doi:  10.1107/S1600536808011148
PMCID: PMC2961275

4-Hydr­oxy-3-nitro­benzaldehyde

Abstract

The hydroxyl group in each of the two independent mol­ecules of the title compound, C7H5NO4, participates in two O—H(...)O hydrogen bonds, viz. one intra­molecular bond to the nitro group and one inter­molecular bond to the aldehyde group of the same mol­ecule in the next unit, resulting in a linear chain structure. The dihedral angle between the aromatic ring and the nitro group is 10.9 (3)° in one mol­ecule and 9.9 (2)° in the other.

Related literature

For the structure of 2-nitro­phenol, see: Iwasaki & Kawano (1978 [triangle]). For the structure of 4-hydroxy­benzaldehyde, see: Jasinski et al. (2008 [triangle]).

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Object name is e-64-0o915-scheme1.jpg

Experimental

Crystal data

  • C7H5NO4
  • M r = 167.12
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o915-efi1.jpg
  • a = 8.042 (1) Å
  • b = 8.036 (1) Å
  • c = 12.242 (2) Å
  • α = 71.975 (2)°
  • β = 70.820 (2)°
  • γ = 67.323 (2)°
  • V = 674.1 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.14 mm−1
  • T = 100 (2) K
  • 0.40 × 0.05 × 0.05 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 4245 measured reflections
  • 3068 independent reflections
  • 2134 reflections with I > 2σ(I)
  • R int = 0.016

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.121
  • S = 0.99
  • 3068 reflections
  • 225 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011148/fl2191sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011148/fl2191Isup2.hkl

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

Acknowledgments

We thank the University of Malaya for the purchase of the diffractometer.

supplementary crystallographic information

Comment

A nitro group either ortho or para to a hydroxyl group can significantly increase the acidity of the resulting phenol. The crystal structures of a large number of 2-nitrophenol compounds have reported; the title compound represents another example. The hydroxyl group of the two independent molecules of the title compound (Fig. 1) is intramolecularly linked to the nitro group by an O–H···O hydrogen bond; the hydroxy group is intermolecularly linked to the aldehyde group of the molecule in the next unit cell by an similar hydrogen bond to result in a linear chain structure (Fig. 2). 2-Nitrophenol itself features an intramolecular hydrogen bond of 2.602 Å (Iwasaki & Kawano, 1978). On the other hand, 4-hydroxybenzaldehyde exists as a hydrogen-bonded chain [O–H···O 2.731 (2) Å] (Jasinski et al., 2008).

Experimental

The commercially available compound (Sigma Aldrich) was recrystallized from water.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The hydroxy H-atoms were located in a difference Fourier map, and were refined with an O–H distance restraint of 0.84±0.01 Å; their temperature factors were freely refined.

Figures

Fig. 1.
Thermal ellipsoid plot of the two independent molecules of the title compound at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Fig. 2.
Chain structure of 4-hydroxy-3-nitrobenzaldehyde. Dashed lines denote hydrogen bonds.

Crystal data

C7H5NO4Z = 4
Mr = 167.12F000 = 344
Triclinic, P1Dx = 1.647 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.042 (1) ÅCell parameters from 1123 reflections
b = 8.036 (1) Åθ = 3.0–28.8º
c = 12.242 (2) ŵ = 0.14 mm1
α = 71.975 (2)ºT = 100 (2) K
β = 70.820 (2)ºPrism, yellow
γ = 67.323 (2)º0.40 × 0.05 × 0.05 mm
V = 674.1 (2) Å3

Data collection

Bruker SMART APEXII diffractometer2134 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.016
Monochromator: graphiteθmax = 27.5º
T = 100(2) Kθmin = 1.8º
[var phi] and ω scansh = −10→10
Absorption correction: nonek = −10→9
4245 measured reflectionsl = −15→15
3068 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.121  w = 1/[σ2(Fo2) + (0.0598P)2 + 0.2315P] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3068 reflectionsΔρmax = 0.31 e Å3
225 parametersΔρmin = −0.32 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.4321 (2)0.8384 (2)0.8786 (1)0.0221 (3)
O20.9772 (2)0.2412 (2)1.1704 (1)0.0225 (4)
O31.1859 (2)0.0816 (2)1.0449 (1)0.0224 (4)
O41.1227 (2)0.1121 (2)0.8402 (1)0.0204 (3)
O51.0630 (2)0.6755 (2)0.4971 (1)0.0220 (3)
O60.4719 (2)1.2568 (2)0.7806 (1)0.0277 (4)
O70.2851 (2)1.4257 (2)0.6664 (1)0.0231 (4)
O80.3813 (2)1.4045 (2)0.4424 (1)0.0199 (3)
N11.0379 (2)0.2049 (2)1.0719 (2)0.0173 (4)
N20.4272 (2)1.2985 (2)0.6866 (2)0.0189 (4)
C10.5276 (3)0.7418 (3)0.9488 (2)0.0175 (4)
C20.6821 (3)0.5734 (3)0.9247 (2)0.0157 (4)
C30.7856 (3)0.4675 (3)1.0075 (2)0.0160 (4)
C40.9342 (3)0.3115 (3)0.9816 (2)0.0153 (4)
C50.9815 (3)0.2577 (3)0.8741 (2)0.0162 (4)
C60.8705 (3)0.3642 (3)0.7931 (2)0.0193 (4)
C70.7247 (3)0.5181 (3)0.8181 (2)0.0185 (4)
C80.9568 (3)0.7675 (3)0.5691 (2)0.0181 (4)
C90.8044 (3)0.9364 (3)0.5399 (2)0.0157 (4)
C100.6886 (3)1.0378 (3)0.6244 (2)0.0157 (4)
C110.5444 (3)1.1966 (3)0.5950 (2)0.0157 (4)
C120.5144 (3)1.2565 (3)0.4804 (2)0.0155 (4)
C130.6380 (3)1.1535 (3)0.3950 (2)0.0174 (4)
C140.7784 (3)0.9973 (3)0.4242 (2)0.0173 (4)
H4o1.185 (4)0.068 (4)0.892 (2)0.06 (1)*
H8o0.308 (3)1.452 (4)0.499 (2)0.05 (1)*
H10.50130.77651.02160.021*
H30.75570.50101.08120.019*
H60.89690.32900.72030.023*
H70.65140.58840.76230.022*
H80.97240.72900.64770.022*
H100.70700.99980.70230.019*
H130.62381.19310.31610.021*
H140.85930.92900.36550.021*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0187 (8)0.0176 (8)0.0236 (8)0.0041 (6)−0.0081 (6)−0.0052 (6)
O20.0246 (8)0.0218 (8)0.0174 (7)−0.0016 (7)−0.0057 (6)−0.0057 (6)
O30.0171 (8)0.0177 (8)0.0261 (8)0.0048 (6)−0.0082 (6)−0.0059 (6)
O40.0169 (8)0.0172 (8)0.0234 (8)0.0048 (6)−0.0073 (6)−0.0096 (6)
O50.0191 (8)0.0171 (8)0.0251 (8)0.0038 (6)−0.0071 (6)−0.0083 (6)
O60.0294 (9)0.0283 (9)0.0199 (8)0.0037 (7)−0.0080 (7)−0.0121 (7)
O70.0175 (8)0.0186 (8)0.0241 (8)0.0047 (6)−0.0035 (6)−0.0075 (6)
O80.0155 (8)0.0171 (7)0.0197 (8)0.0049 (6)−0.0051 (6)−0.0060 (6)
N10.0170 (9)0.0152 (9)0.0187 (9)−0.0028 (7)−0.0058 (7)−0.0035 (7)
N20.0171 (9)0.0166 (9)0.0189 (9)−0.0004 (7)−0.0029 (7)−0.0063 (7)
C10.0149 (10)0.0145 (10)0.0201 (10)−0.0005 (8)−0.0023 (8)−0.0065 (8)
C20.0104 (9)0.0135 (10)0.0198 (10)−0.0007 (8)−0.0025 (8)−0.0040 (8)
C30.0149 (10)0.0149 (10)0.0163 (10)−0.0025 (8)−0.0033 (8)−0.0038 (8)
C40.0134 (10)0.0138 (10)0.0167 (10)−0.0026 (8)−0.0055 (8)−0.0006 (8)
C50.0117 (10)0.0142 (10)0.0204 (10)−0.0006 (8)−0.0038 (8)−0.0048 (8)
C60.0177 (11)0.0187 (11)0.0197 (10)0.0010 (8)−0.0060 (9)−0.0085 (8)
C70.0149 (10)0.0175 (10)0.0202 (10)−0.0001 (8)−0.0070 (8)−0.0034 (8)
C80.0167 (10)0.0153 (10)0.0199 (10)−0.0018 (8)−0.0057 (8)−0.0034 (8)
C90.0145 (10)0.0119 (10)0.0195 (10)−0.0020 (8)−0.0054 (8)−0.0031 (8)
C100.0154 (10)0.0147 (10)0.0155 (10)−0.0034 (8)−0.0047 (8)−0.0017 (8)
C110.0132 (10)0.0135 (10)0.0182 (10)−0.0018 (8)−0.0021 (8)−0.0053 (8)
C120.0123 (10)0.0121 (9)0.0196 (10)−0.0013 (8)−0.0040 (8)−0.0032 (8)
C130.0153 (10)0.0170 (10)0.0171 (10)0.0000 (8)−0.0057 (8)−0.0043 (8)
C140.0150 (10)0.0152 (10)0.0189 (10)0.0006 (8)−0.0033 (8)−0.0075 (8)

Geometric parameters (Å, °)

O1—C11.222 (2)C8—C91.475 (3)
O2—N11.223 (2)C9—C101.380 (3)
O3—N11.242 (2)C9—C141.406 (3)
O4—C51.341 (2)C10—C111.397 (3)
O5—C81.214 (3)C11—C121.405 (3)
O6—N21.226 (2)C12—C131.408 (3)
O7—N21.241 (2)C13—C141.368 (3)
O8—C121.335 (2)O4—H4o0.84 (1)
N1—C41.457 (3)O8—H8o0.84 (1)
N2—C111.447 (3)C1—H10.9500
C1—C21.473 (3)C3—H30.9500
C2—C31.385 (3)C6—H60.9500
C2—C71.403 (3)C7—H70.9500
C3—C41.394 (3)C8—H80.9500
C4—C51.399 (3)C10—H100.9500
C5—C61.408 (3)C13—H130.9500
C6—C71.370 (3)C14—H140.9500
O2—N1—O3122.8 (2)C10—C11—N2117.7 (2)
O2—N1—C4119.0 (2)C12—C11—N2121.0 (2)
O3—N1—C4118.1 (2)O8—C12—C11126.7 (2)
O6—N2—O7122.6 (2)O8—C12—C13115.7 (2)
O6—N2—C11119.1 (2)C11—C12—C13117.7 (2)
O7—N2—C11118.3 (2)C14—C13—C12120.9 (2)
O1—C1—C2122.4 (2)C13—C14—C9120.9 (2)
C3—C2—C7119.4 (2)C5—O4—H4o106 (2)
C3—C2—C1120.4 (2)C12—O8—H8o110 (2)
C7—C2—C1120.3 (2)O1—C1—H1118.8
C2—C3—C4119.4 (2)C2—C1—H1118.8
C3—C4—C5121.8 (2)C2—C3—H3120.3
C3—C4—N1117.1 (2)C4—C3—H3120.3
C5—C4—N1121.1 (2)C7—C6—H6119.7
O4—C5—C4126.4 (2)C5—C6—H6119.7
O4—C5—C6115.9 (2)C6—C7—H7119.5
C4—C5—C6117.7 (2)C2—C7—H7119.5
C7—C6—C5120.6 (2)O5—C8—H8118.5
C6—C7—C2121.1 (2)C9—C8—H8118.5
O5—C8—C9122.9 (2)C9—C10—H10120.1
C10—C9—C14119.4 (2)C11—C10—H10120.1
C10—C9—C8120.8 (2)C14—C13—H13119.5
C14—C9—C8119.8 (2)C12—C13—H13119.5
C9—C10—C11119.8 (2)C13—C14—H14119.6
C10—C11—C12121.3 (2)C9—C14—H14119.6
O1—C1—C2—C3−179.5 (2)O5—C8—C9—C10−179.1 (2)
O1—C1—C2—C70.0 (3)O5—C8—C9—C14−0.3 (3)
C7—C2—C3—C42.1 (3)C14—C9—C10—C111.7 (3)
C1—C2—C3—C4−178.3 (2)C8—C9—C10—C11−179.5 (2)
C2—C3—C4—C5−0.4 (3)C9—C10—C11—C12−0.3 (3)
C2—C3—C4—N1−179.8 (2)C9—C10—C11—N2−179.8 (2)
O2—N1—C4—C39.5 (3)O6—N2—C11—C109.2 (3)
O3—N1—C4—C3−169.8 (2)O7—N2—C11—C10−171.1 (2)
O2—N1—C4—C5−170.0 (2)O6—N2—C11—C12−170.3 (2)
O3—N1—C4—C510.7 (3)O7—N2—C11—C129.4 (3)
C3—C4—C5—O4179.0 (2)C10—C11—C12—O8179.6 (2)
N1—C4—C5—O4−1.6 (3)N2—C11—C12—O8−0.9 (3)
C3—C4—C5—C6−1.6 (3)C10—C11—C12—C13−1.6 (3)
N1—C4—C5—C6177.8 (2)N2—C11—C12—C13177.9 (2)
O4—C5—C6—C7−178.7 (2)O8—C12—C13—C14−179.0 (2)
C4—C5—C6—C71.9 (3)C11—C12—C13—C142.1 (3)
C5—C6—C7—C2−0.1 (3)C12—C13—C14—C9−0.8 (3)
C3—C2—C7—C6−2.0 (3)C10—C9—C14—C13−1.2 (3)
C1—C2—C7—C6178.5 (2)C8—C9—C14—C13180.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H4o···O1i0.84 (1)2.13 (3)2.676 (2)122 (3)
O4—H4o···O30.84 (1)1.91 (2)2.638 (2)144 (3)
O8—H8o···O5ii0.84 (1)2.10 (3)2.687 (2)128 (3)
O8—H8o···O70.84 (1)1.94 (2)2.635 (2)139 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2191).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Iwasaki, F. & Kawano, Y. (1978). Acta Cryst. B34, 1286–1290.
  • Jasinski, J. P., Butcher, R. J., Narayana, B., Swamy, M. T. & Yathirajan, H. S. (2008). Acta Cryst. E64, o187.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

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