organic compounds
4-Hydroxy-3-nitrobenzaldehyde
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
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). For the structure of 4-hydroxybenzaldehyde, see: Jasinski et al. (2008).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).
Supporting information
10.1107/S1600536808011148/fl2191sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808011148/fl2191Isup2.hkl
Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and were included in the
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.Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).C7H5NO4 | Z = 4 |
Mr = 167.12 | F(000) = 344 |
Triclinic, P1 | Dx = 1.647 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.042 (1) Å | Cell parameters from 1123 reflections |
b = 8.036 (1) Å | θ = 3.0–28.8° |
c = 12.242 (2) Å | µ = 0.14 mm−1 |
α = 71.975 (2)° | T = 100 K |
β = 70.820 (2)° | Prism, yellow |
γ = 67.323 (2)° | 0.40 × 0.05 × 0.05 mm |
V = 674.1 (2) Å3 |
Bruker SMART APEXII diffractometer | 2134 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.016 |
Graphite monochromator | θmax = 27.5°, θmin = 1.8° |
ϕ and ω scans | h = −10→10 |
4245 measured reflections | k = −10→9 |
3068 independent reflections | l = −15→15 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0598P)2 + 0.2315P] where P = (Fo2 + 2Fc2)/3 |
3068 reflections | (Δ/σ)max = 0.001 |
225 parameters | Δρmax = 0.31 e Å−3 |
2 restraints | Δρmin = −0.32 e Å−3 |
C7H5NO4 | γ = 67.323 (2)° |
Mr = 167.12 | V = 674.1 (2) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.042 (1) Å | Mo Kα radiation |
b = 8.036 (1) Å | µ = 0.14 mm−1 |
c = 12.242 (2) Å | T = 100 K |
α = 71.975 (2)° | 0.40 × 0.05 × 0.05 mm |
β = 70.820 (2)° |
Bruker SMART APEXII diffractometer | 2134 reflections with I > 2σ(I) |
4245 measured reflections | Rint = 0.016 |
3068 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 2 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.31 e Å−3 |
3068 reflections | Δρmin = −0.32 e Å−3 |
225 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.4321 (2) | 0.8384 (2) | 0.8786 (1) | 0.0221 (3) | |
O2 | 0.9772 (2) | 0.2412 (2) | 1.1704 (1) | 0.0225 (4) | |
O3 | 1.1859 (2) | 0.0816 (2) | 1.0449 (1) | 0.0224 (4) | |
O4 | 1.1227 (2) | 0.1121 (2) | 0.8402 (1) | 0.0204 (3) | |
O5 | 1.0630 (2) | 0.6755 (2) | 0.4971 (1) | 0.0220 (3) | |
O6 | 0.4719 (2) | 1.2568 (2) | 0.7806 (1) | 0.0277 (4) | |
O7 | 0.2851 (2) | 1.4257 (2) | 0.6664 (1) | 0.0231 (4) | |
O8 | 0.3813 (2) | 1.4045 (2) | 0.4424 (1) | 0.0199 (3) | |
N1 | 1.0379 (2) | 0.2049 (2) | 1.0719 (2) | 0.0173 (4) | |
N2 | 0.4272 (2) | 1.2985 (2) | 0.6866 (2) | 0.0189 (4) | |
C1 | 0.5276 (3) | 0.7418 (3) | 0.9488 (2) | 0.0175 (4) | |
C2 | 0.6821 (3) | 0.5734 (3) | 0.9247 (2) | 0.0157 (4) | |
C3 | 0.7856 (3) | 0.4675 (3) | 1.0075 (2) | 0.0160 (4) | |
C4 | 0.9342 (3) | 0.3115 (3) | 0.9816 (2) | 0.0153 (4) | |
C5 | 0.9815 (3) | 0.2577 (3) | 0.8741 (2) | 0.0162 (4) | |
C6 | 0.8705 (3) | 0.3642 (3) | 0.7931 (2) | 0.0193 (4) | |
C7 | 0.7247 (3) | 0.5181 (3) | 0.8181 (2) | 0.0185 (4) | |
C8 | 0.9568 (3) | 0.7675 (3) | 0.5691 (2) | 0.0181 (4) | |
C9 | 0.8044 (3) | 0.9364 (3) | 0.5399 (2) | 0.0157 (4) | |
C10 | 0.6886 (3) | 1.0378 (3) | 0.6244 (2) | 0.0157 (4) | |
C11 | 0.5444 (3) | 1.1966 (3) | 0.5950 (2) | 0.0157 (4) | |
C12 | 0.5144 (3) | 1.2565 (3) | 0.4804 (2) | 0.0155 (4) | |
C13 | 0.6380 (3) | 1.1535 (3) | 0.3950 (2) | 0.0174 (4) | |
C14 | 0.7784 (3) | 0.9973 (3) | 0.4242 (2) | 0.0173 (4) | |
H4o | 1.185 (4) | 0.068 (4) | 0.892 (2) | 0.06 (1)* | |
H8o | 0.308 (3) | 1.452 (4) | 0.499 (2) | 0.05 (1)* | |
H1 | 0.5013 | 0.7765 | 1.0216 | 0.021* | |
H3 | 0.7557 | 0.5010 | 1.0812 | 0.019* | |
H6 | 0.8969 | 0.3290 | 0.7203 | 0.023* | |
H7 | 0.6514 | 0.5884 | 0.7623 | 0.022* | |
H8 | 0.9724 | 0.7290 | 0.6477 | 0.022* | |
H10 | 0.7070 | 0.9998 | 0.7023 | 0.019* | |
H13 | 0.6238 | 1.1931 | 0.3161 | 0.021* | |
H14 | 0.8593 | 0.9290 | 0.3655 | 0.021* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0187 (8) | 0.0176 (8) | 0.0236 (8) | 0.0041 (6) | −0.0081 (6) | −0.0052 (6) |
O2 | 0.0246 (8) | 0.0218 (8) | 0.0174 (7) | −0.0016 (7) | −0.0057 (6) | −0.0057 (6) |
O3 | 0.0171 (8) | 0.0177 (8) | 0.0261 (8) | 0.0048 (6) | −0.0082 (6) | −0.0059 (6) |
O4 | 0.0169 (8) | 0.0172 (8) | 0.0234 (8) | 0.0048 (6) | −0.0073 (6) | −0.0096 (6) |
O5 | 0.0191 (8) | 0.0171 (8) | 0.0251 (8) | 0.0038 (6) | −0.0071 (6) | −0.0083 (6) |
O6 | 0.0294 (9) | 0.0283 (9) | 0.0199 (8) | 0.0037 (7) | −0.0080 (7) | −0.0121 (7) |
O7 | 0.0175 (8) | 0.0186 (8) | 0.0241 (8) | 0.0047 (6) | −0.0035 (6) | −0.0075 (6) |
O8 | 0.0155 (8) | 0.0171 (7) | 0.0197 (8) | 0.0049 (6) | −0.0051 (6) | −0.0060 (6) |
N1 | 0.0170 (9) | 0.0152 (9) | 0.0187 (9) | −0.0028 (7) | −0.0058 (7) | −0.0035 (7) |
N2 | 0.0171 (9) | 0.0166 (9) | 0.0189 (9) | −0.0004 (7) | −0.0029 (7) | −0.0063 (7) |
C1 | 0.0149 (10) | 0.0145 (10) | 0.0201 (10) | −0.0005 (8) | −0.0023 (8) | −0.0065 (8) |
C2 | 0.0104 (9) | 0.0135 (10) | 0.0198 (10) | −0.0007 (8) | −0.0025 (8) | −0.0040 (8) |
C3 | 0.0149 (10) | 0.0149 (10) | 0.0163 (10) | −0.0025 (8) | −0.0033 (8) | −0.0038 (8) |
C4 | 0.0134 (10) | 0.0138 (10) | 0.0167 (10) | −0.0026 (8) | −0.0055 (8) | −0.0006 (8) |
C5 | 0.0117 (10) | 0.0142 (10) | 0.0204 (10) | −0.0006 (8) | −0.0038 (8) | −0.0048 (8) |
C6 | 0.0177 (11) | 0.0187 (11) | 0.0197 (10) | 0.0010 (8) | −0.0060 (9) | −0.0085 (8) |
C7 | 0.0149 (10) | 0.0175 (10) | 0.0202 (10) | −0.0001 (8) | −0.0070 (8) | −0.0034 (8) |
C8 | 0.0167 (10) | 0.0153 (10) | 0.0199 (10) | −0.0018 (8) | −0.0057 (8) | −0.0034 (8) |
C9 | 0.0145 (10) | 0.0119 (10) | 0.0195 (10) | −0.0020 (8) | −0.0054 (8) | −0.0031 (8) |
C10 | 0.0154 (10) | 0.0147 (10) | 0.0155 (10) | −0.0034 (8) | −0.0047 (8) | −0.0017 (8) |
C11 | 0.0132 (10) | 0.0135 (10) | 0.0182 (10) | −0.0018 (8) | −0.0021 (8) | −0.0053 (8) |
C12 | 0.0123 (10) | 0.0121 (9) | 0.0196 (10) | −0.0013 (8) | −0.0040 (8) | −0.0032 (8) |
C13 | 0.0153 (10) | 0.0170 (10) | 0.0171 (10) | 0.0000 (8) | −0.0057 (8) | −0.0043 (8) |
C14 | 0.0150 (10) | 0.0152 (10) | 0.0189 (10) | 0.0006 (8) | −0.0033 (8) | −0.0075 (8) |
O1—C1 | 1.222 (2) | C8—C9 | 1.475 (3) |
O2—N1 | 1.223 (2) | C9—C10 | 1.380 (3) |
O3—N1 | 1.242 (2) | C9—C14 | 1.406 (3) |
O4—C5 | 1.341 (2) | C10—C11 | 1.397 (3) |
O5—C8 | 1.214 (3) | C11—C12 | 1.405 (3) |
O6—N2 | 1.226 (2) | C12—C13 | 1.408 (3) |
O7—N2 | 1.241 (2) | C13—C14 | 1.368 (3) |
O8—C12 | 1.335 (2) | O4—H4o | 0.84 (1) |
N1—C4 | 1.457 (3) | O8—H8o | 0.84 (1) |
N2—C11 | 1.447 (3) | C1—H1 | 0.9500 |
C1—C2 | 1.473 (3) | C3—H3 | 0.9500 |
C2—C3 | 1.385 (3) | C6—H6 | 0.9500 |
C2—C7 | 1.403 (3) | C7—H7 | 0.9500 |
C3—C4 | 1.394 (3) | C8—H8 | 0.9500 |
C4—C5 | 1.399 (3) | C10—H10 | 0.9500 |
C5—C6 | 1.408 (3) | C13—H13 | 0.9500 |
C6—C7 | 1.370 (3) | C14—H14 | 0.9500 |
O2—N1—O3 | 122.8 (2) | C10—C11—N2 | 117.7 (2) |
O2—N1—C4 | 119.0 (2) | C12—C11—N2 | 121.0 (2) |
O3—N1—C4 | 118.1 (2) | O8—C12—C11 | 126.7 (2) |
O6—N2—O7 | 122.6 (2) | O8—C12—C13 | 115.7 (2) |
O6—N2—C11 | 119.1 (2) | C11—C12—C13 | 117.7 (2) |
O7—N2—C11 | 118.3 (2) | C14—C13—C12 | 120.9 (2) |
O1—C1—C2 | 122.4 (2) | C13—C14—C9 | 120.9 (2) |
C3—C2—C7 | 119.4 (2) | C5—O4—H4o | 106 (2) |
C3—C2—C1 | 120.4 (2) | C12—O8—H8o | 110 (2) |
C7—C2—C1 | 120.3 (2) | O1—C1—H1 | 118.8 |
C2—C3—C4 | 119.4 (2) | C2—C1—H1 | 118.8 |
C3—C4—C5 | 121.8 (2) | C2—C3—H3 | 120.3 |
C3—C4—N1 | 117.1 (2) | C4—C3—H3 | 120.3 |
C5—C4—N1 | 121.1 (2) | C7—C6—H6 | 119.7 |
O4—C5—C4 | 126.4 (2) | C5—C6—H6 | 119.7 |
O4—C5—C6 | 115.9 (2) | C6—C7—H7 | 119.5 |
C4—C5—C6 | 117.7 (2) | C2—C7—H7 | 119.5 |
C7—C6—C5 | 120.6 (2) | O5—C8—H8 | 118.5 |
C6—C7—C2 | 121.1 (2) | C9—C8—H8 | 118.5 |
O5—C8—C9 | 122.9 (2) | C9—C10—H10 | 120.1 |
C10—C9—C14 | 119.4 (2) | C11—C10—H10 | 120.1 |
C10—C9—C8 | 120.8 (2) | C14—C13—H13 | 119.5 |
C14—C9—C8 | 119.8 (2) | C12—C13—H13 | 119.5 |
C9—C10—C11 | 119.8 (2) | C13—C14—H14 | 119.6 |
C10—C11—C12 | 121.3 (2) | C9—C14—H14 | 119.6 |
O1—C1—C2—C3 | −179.5 (2) | O5—C8—C9—C10 | −179.1 (2) |
O1—C1—C2—C7 | 0.0 (3) | O5—C8—C9—C14 | −0.3 (3) |
C7—C2—C3—C4 | 2.1 (3) | C14—C9—C10—C11 | 1.7 (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—C3 | 9.5 (3) | O6—N2—C11—C10 | 9.2 (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—C5 | 10.7 (3) | O7—N2—C11—C12 | 9.4 (3) |
C3—C4—C5—O4 | 179.0 (2) | C10—C11—C12—O8 | 179.6 (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—C6 | 177.8 (2) | N2—C11—C12—C13 | 177.9 (2) |
O4—C5—C6—C7 | −178.7 (2) | O8—C12—C13—C14 | −179.0 (2) |
C4—C5—C6—C7 | 1.9 (3) | C11—C12—C13—C14 | 2.1 (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—C6 | 178.5 (2) | C8—C9—C14—C13 | 180.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4o···O1i | 0.84 (1) | 2.13 (3) | 2.676 (2) | 122 (3) |
O4—H4o···O3 | 0.84 (1) | 1.91 (2) | 2.638 (2) | 144 (3) |
O8—H8o···O5ii | 0.84 (1) | 2.10 (3) | 2.687 (2) | 128 (3) |
O8—H8o···O7 | 0.84 (1) | 1.94 (2) | 2.635 (2) | 139 (3) |
Symmetry codes: (i) x+1, y−1, z; (ii) x−1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C7H5NO4 |
Mr | 167.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 8.042 (1), 8.036 (1), 12.242 (2) |
α, β, γ (°) | 71.975 (2), 70.820 (2), 67.323 (2) |
V (Å3) | 674.1 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.40 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART APEXII diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4245, 3068, 2134 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.121, 0.99 |
No. of reflections | 3068 |
No. of parameters | 225 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.32 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4o···O1i | 0.84 (1) | 2.13 (3) | 2.676 (2) | 122 (3) |
O4—H4o···O3 | 0.84 (1) | 1.91 (2) | 2.638 (2) | 144 (3) |
O8—H8o···O5ii | 0.84 (1) | 2.10 (3) | 2.687 (2) | 128 (3) |
O8—H8o···O7 | 0.84 (1) | 1.94 (2) | 2.635 (2) | 139 (3) |
Symmetry codes: (i) x+1, y−1, z; (ii) x−1, y+1, z. |
Acknowledgements
We thank the University of Malaya for the purchase of the diffractometer.
References
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Iwasaki, F. & Kawano, Y. (1978). Acta Cryst. B34, 1286–1290. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Jasinski, J. P., Butcher, R. J., Narayana, B., Swamy, M. T. & Yathirajan, H. S. (2008). Acta Cryst. E64, o187. 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
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
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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).