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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1718.
Published online 2009 June 27. doi:  10.1107/S1600536809024179
PMCID: PMC2969386

2-All­yloxy-5-nitro­benzoic acid

Abstract

The mol­ecule of the title compound, C10H9NO5, is approximately planar, with the mean planes of the nitro, carboxyl and all­yloxy groups rotated by 8.1 (3), 7.9 (3) and 4.52 (18)°, respectively, from the plane of the benzene ring. Bond lengths in the aromatic ring are influenced by both electronic effects and strain induced by ortho-substitution. In the crystal structure, centrosymmetrically related mol­ecules are paired into dimers through strong O—H(...)O hydrogen bonds.

Related literature

For information about chorismate mutase catalysis, see: Ziegler (1977 [triangle]); Castro (2004 [triangle]); Zhang et al. (2005 [triangle]). For related compounds, see: Ferreira et al. (2007 [triangle]); Jones et al. (1984 [triangle]). For the synthetic procedure, see: White et al. (1958 [triangle]).

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Object name is e-65-o1718-scheme1.jpg

Experimental

Crystal data

  • C10H9NO5
  • M r = 223.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1718-efi1.jpg
  • a = 3.9438 (6) Å
  • b = 9.0409 (7) Å
  • c = 28.804 (4) Å
  • β = 92.227 (11)°
  • V = 1026.2 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 293 K
  • 0.50 × 0.40 × 0.26 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 2036 measured reflections
  • 2000 independent reflections
  • 1382 reflections with I > 2σ(I)
  • R int = 0.023
  • 3 standard reflections every 200 reflections intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.153
  • S = 1.06
  • 2000 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: SET4 in CAD-4 Software; data reduction: HELENA (Spek, 1996 [triangle]); program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024179/rz2336sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024179/rz2336Isup2.hkl

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

Acknowledgments

The authors are grateful to Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and Instituto Nacional de Ciência e Tecnologia (INCT) – Catálize for financial assistance.

supplementary crystallographic information

Comment

The unimolecular rearrangement of chorismate to prephenate, catalyzed by chorismate mutase, is a rare case of a [3,3] sigmatropic shift reaction in live organisms and it is a natural target in drug development, since corresponds to a key step in the pathway to form aromatic amino acids in plants, bacteria and fungi (Ziegler, 1977; Castro, 2004; Zhang et al., 2005). Chorismate mutase catalyzes this intramolecular reaction without formation of an enzyme-substrate covalent intermediate and the proposed transition state structures in the gas phase, water and enzyme are characteristic of a concerted pericyclic rearrangement. Transition state stabilization seems to be responsible for only 10% of the enzymatic advantage over the water reaction (106-fold catalytic effect). Since we are interested in the systematic analysis of the influence of electrostatic stabilization and intramolecular hydrogen bonding in [3,3] sigmatropic Claisen rearrangements, a series of ethers derived from salicylic acid has been synthesized. The 2-allyloxy-5-nitrobenzoic acid (I, scheme 2) is a new synthesized compound and here we report its X-ray crystal structure.

A projection of the molecular structure and the numbering of the non-hydrogen atoms are shown in Fig. 1. Bond length data show that in the aromatic ring the C3—C4, C4—C5 and C5—C6 bonds are the strongest (shortest) C—C ring bonds, as a consequence of both electronic effects and strain induced by ortho-substitution at C1 and C2. The mean plane of nitro, carboxyl and allyloxy groups are deviated from the best plane of the phenyl ring by 8.1 (3)°, 7.9 (3)° and 44.52 (18)°, respectively. The electron withdrawing influence of the carboxyl group, combined with the strain introduced by the allyl ether, weakens the C1—C2 and C1—C6 bonds significantly and makes them longer than the other ring bonds. These effects in both bond lengths and coplanarity of the aromatic ring and the carboxyl group are similar to those found in the crystal structure of 2-allyloxy-5-chlorobenzoic acid (II) (Ferreira et al., 2007). The nitro group in 1 has a small effect on the C3—C4—-C5 angle (121.5 (2)°), but the COOH group reduces the C1—C2—C3 angle from 120° (normal benzene ring) to 119.10 (18)°. The effect is practically identical to that found in compound (II, scheme 2), where the C3—C4—C5 angle is 120.4 (2)° and C1—C2—C3 angle is 119.37 (19)°. In both compounds, the observed effect evidently results from the presence of the allyloxy group in (I), lengthening both C1—C2 and C1—C6 bonds, and reducing the C2—C1—C6 angle to 119.09 (19)°. Closely similar effects are observed for 2-methoxymethoxybenzoic acid, where the ortho-substituent is electronically and sterically similar (Jones et al., 1984).

In the carboxylic group, the C—O distances are very similar to each other. This indicates a high degree of delocalization of the π-electrons over the COOH backbone. Once the acid group is protonated, the similarity in bond lengths can be attributed to the very strong hydrogen bond (see Table 1). These intermolecular interactions also induce the formation of dimeric structures through center of symmetry. In the three-dimensional packing, the pairs of molecules are perfectly stacked along crystallographic a axis (Fig. 2).

Experimental

Preparation of (I) followed closely the procedure described by White et al. (1958). A mixture of 9.15 g (0.05 mol) of 5-nitrosalycilic acid, 6.05 g (0.05 mol) of allyl bromide, 8.29 g (0.06 mol) of dry, powdered potassium carbonate, and sufficient dry acetone (about 30 ml) to give an easily stirred mass was stirred and refluxed for eight hours. Then the mixture was filtered, acidified with diluted acetic acid and the acetone removed by distillation under reduced pressure. The residue was initially obtained as an amorphous solid and yellow crystals of (I) were grown from aqueous acetone solution by slow evaporation at room temperature (m.p. 120–121°C).

Refinement

All non-H atoms were refined with anisotropic displacement parameters. H atoms were placed at their idealized positions with distances of 0.93 and 0.97 Å and Ueq fixed at 1.2 times Uiso of the preceding atom for C—HAr and CH2, respectively. The H atom of the COOH group was found in a Fourier difference map and treated with riding model and its Ueq was also fixed at 1.2 times Uiso of the parent atom.

Figures

Fig. 1.
The molecular structure of the title compound with the labelling scheme. Displacement ellipsoids are shown at the 40% probability level.
Fig. 2.
Partial packing diagram of the title compound viewed along the a axis. Intermolecular O—H···O hydrogen bonds are shown as dashed lines.
Fig. 3.
Schematic representations of the structures of (I) and (II).

Crystal data

C10H9NO5F(000) = 464
Mr = 223.18Dx = 1.445 Mg m3
Monoclinic, P21/nMelting point = 393–394 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 3.9438 (6) ÅCell parameters from 25 reflections
b = 9.0409 (7) Åθ = 7.0–18.7°
c = 28.804 (4) ŵ = 0.12 mm1
β = 92.227 (11)°T = 293 K
V = 1026.2 (2) Å3Prismatic, yellow
Z = 40.50 × 0.40 × 0.26 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.023
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 1.4°
graphiteh = −4→4
ω–2θ scansk = −11→0
2036 measured reflectionsl = −35→0
2000 independent reflections3 standard reflections every 200 reflections
1382 reflections with I > 2σ(I) intensity decay: 1%

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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0699P)2 + 0.3672P] where P = (Fo2 + 2Fc2)/3
2000 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.19 e Å3

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

xyzUiso*/Ueq
C10.8059 (5)0.2710 (2)0.13044 (7)0.0456 (5)
C20.7710 (5)0.4115 (2)0.10955 (7)0.0459 (5)
C30.6348 (5)0.5267 (2)0.13471 (7)0.0489 (5)
H30.61120.62000.12130.059*
C40.5345 (5)0.5033 (2)0.17938 (7)0.0490 (5)
C50.5636 (5)0.3662 (3)0.20024 (7)0.0528 (6)
H50.49270.35200.23030.063*
C60.6985 (5)0.2510 (3)0.17597 (7)0.0514 (5)
H60.71910.15840.18990.062*
O110.9422 (4)0.16211 (16)0.10571 (5)0.0563 (4)
C120.9673 (6)0.0159 (2)0.12522 (8)0.0573 (6)
H12A0.7446−0.01860.13340.069*
H12B1.11330.01720.15310.069*
C131.1101 (6)−0.0839 (3)0.09020 (10)0.0689 (7)
H131.1140−0.18420.09740.083*
C141.2299 (8)−0.0467 (4)0.05078 (11)0.0840 (9)
H14A1.23210.05220.04190.101*
H14B1.3140−0.11870.03130.101*
C210.8708 (6)0.4455 (2)0.06121 (7)0.0515 (5)
O211.0274 (6)0.3526 (2)0.03810 (6)0.0853 (7)
O220.7886 (6)0.5704 (2)0.04562 (6)0.0942 (8)
H220.83220.59630.01240.113*
N410.3876 (6)0.6249 (3)0.20513 (7)0.0653 (6)
O410.2631 (6)0.5975 (2)0.24230 (6)0.0867 (6)
O420.3925 (7)0.7490 (3)0.18876 (7)0.1116 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0446 (11)0.0518 (12)0.0407 (11)−0.0036 (9)0.0057 (8)−0.0010 (9)
C20.0494 (11)0.0512 (12)0.0375 (10)−0.0041 (9)0.0088 (8)0.0012 (9)
C30.0573 (12)0.0506 (12)0.0390 (11)−0.0020 (10)0.0061 (9)0.0009 (9)
C40.0517 (12)0.0564 (12)0.0392 (11)−0.0022 (10)0.0065 (9)−0.0054 (9)
C50.0577 (13)0.0674 (14)0.0340 (11)−0.0063 (11)0.0101 (9)0.0005 (10)
C60.0580 (12)0.0559 (13)0.0408 (12)−0.0042 (10)0.0067 (9)0.0078 (10)
O110.0705 (10)0.0510 (9)0.0486 (9)0.0034 (7)0.0170 (7)0.0026 (7)
C120.0590 (13)0.0529 (13)0.0601 (14)0.0016 (10)0.0049 (11)0.0068 (11)
C130.0679 (16)0.0613 (15)0.0774 (18)0.0088 (12)0.0018 (13)−0.0051 (13)
C140.090 (2)0.086 (2)0.0776 (19)0.0132 (16)0.0175 (16)−0.0120 (16)
C210.0664 (13)0.0494 (12)0.0396 (11)−0.0019 (10)0.0122 (10)0.0035 (10)
O210.1322 (17)0.0749 (12)0.0518 (10)0.0252 (11)0.0437 (11)0.0109 (9)
O220.166 (2)0.0660 (12)0.0536 (10)0.0221 (12)0.0488 (12)0.0183 (9)
N410.0775 (14)0.0721 (14)0.0469 (11)0.0071 (11)0.0092 (10)−0.0126 (10)
O410.1095 (15)0.0985 (15)0.0543 (11)0.0051 (12)0.0334 (10)−0.0185 (10)
O420.192 (3)0.0707 (13)0.0742 (14)0.0405 (15)0.0377 (15)0.0007 (11)

Geometric parameters (Å, °)

C1—O111.340 (2)C12—C131.481 (3)
C1—C61.405 (3)C12—H12A0.9700
C1—C21.410 (3)C12—H12B0.9700
C2—C31.389 (3)C13—C141.291 (4)
C2—C211.493 (3)C13—H130.9300
C3—C41.377 (3)C14—H14A0.9300
C3—H30.9300C14—H14B0.9300
C4—C51.380 (3)C21—O211.250 (3)
C4—N411.459 (3)C21—O221.253 (3)
C5—C61.373 (3)O22—H221.0056
C5—H50.9300N41—O421.217 (3)
C6—H60.9300N41—O411.221 (3)
O11—C121.438 (3)
O11—C1—C6122.9 (2)O11—C12—C13108.42 (19)
O11—C1—C2118.00 (17)O11—C12—H12A110.0
C6—C1—C2119.09 (19)C13—C12—H12A110.0
C3—C2—C1119.10 (18)O11—C12—H12B110.0
C3—C2—C21116.95 (19)C13—C12—H12B110.0
C1—C2—C21123.95 (18)H12A—C12—H12B108.4
C4—C3—C2120.2 (2)C14—C13—C12127.0 (3)
C4—C3—H3119.9C14—C13—H13116.5
C2—C3—H3119.9C12—C13—H13116.5
C3—C4—C5121.5 (2)C13—C14—H14A120.0
C3—C4—N41119.5 (2)C13—C14—H14B120.0
C5—C4—N41118.92 (19)H14A—C14—H14B120.0
C6—C5—C4119.12 (18)O21—C21—O22122.7 (2)
C6—C5—H5120.4O21—C21—C2120.8 (2)
C4—C5—H5120.4O22—C21—C2116.47 (19)
C5—C6—C1121.0 (2)C21—O22—H22120.0
C5—C6—H6119.5O42—N41—O41122.7 (2)
C1—C6—H6119.5O42—N41—C4119.0 (2)
C1—O11—C12119.37 (16)O41—N41—C4118.3 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O22—H22···O21i1.011.642.639 (2)170

Symmetry codes: (i) −x+2, −y+1, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2336).

References

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