Acta Cryst. (2007). E63, o3950 [ doi:10.1107/S160053680703992X ]
The title compound, C7H5NO5, was obtained as rectangular prism-like crystals by the hydroponic method. It displays a planar one-dimensional chain structure stabilized via inter- and intramolecular O-H
O hydrogen bonds.
Glacial acetic acid (30 ml) and cold hydrogen peroxide (15 ml) were shaken in a round-bottomed flask, followed by the addition of pyridine-2,4- dicarboxylic acid monohydrate (2 g; 11 mmol), and the mixture was heated (Li et al., 1987). After the excess acetic acid and water were removed under reduced pressure, the title compound was obtained as a white powder (0.95 g, yield 48%). Slow evaporation at room temperature, following dissolution of the white powder (0.2 g, 1 mmol) in a mixture of boiling mixture of methanol (10 ml) and dichloromethane(15 ml) and careful filtration, yielded colorless crystals after 4 days.
The C-bound H atoms were included in the riding model approximation with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C) and the O2-bound H atom was included in the riding model approximation with O—H = 0.82 Å. The O4-bound H atom was located from a difference Fourier map and refined isotropically.
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
![[Figure 1]](./rt2012fig1thm.gif)
| Fig. 1. ORTEP drawing (at 50% probability) of (I); hydrogen atoms at arbitrary size. |
![[Figure 2]](./rt2012fig2thm.gif)
| Fig. 2. Illustration of the hydrogen bonding in the one-dimensional chain. |
| C7H5NO5 | F000 = 376 |
| Mr = 183.12 | Dx = 1.709 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1853 reflections |
| a = 7.323 (3) Å | θ = 2.8–27.5º |
| b = 6.985 (3) Å | µ = 0.15 mm−1 |
| c = 13.982 (6) Å | T = 293 (2) K |
| β = 95.614 (4)º | Prism, colorless |
| V = 711.8 (5) Å3 | 0.45 × 0.40 × 0.25 mm |
| Z = 4 |
| Bruker P4 diffractometer | 1472 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.011 |
| Monochromator: graphite | θmax = 27.5º |
| T = 293(2) K | θmin = 3.0º |
| CCD_Profile_fitting scans | h = −4→9 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | k = −9→9 |
| Tmin = 0.920, Tmax = 0.963 | l = −18→18 |
| 4998 measured reflections | Standard reflections: ? |
| 1619 independent reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0503P)2 + 0.2243P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 1619 reflections | Δρmax = 0.31 e Å−3 |
| 122 parameters | Δρmin = −0.19 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C7H5NO5 | V = 711.8 (5) Å3 |
| Mr = 183.12 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 7.323 (3) Å | µ = 0.15 mm−1 |
| b = 6.985 (3) Å | T = 293 (2) K |
| c = 13.982 (6) Å | 0.45 × 0.40 × 0.25 mm |
| β = 95.614 (4)º |
| Bruker P4 diffractometer | 1619 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 1472 reflections with I > 2σ(I) |
| Tmin = 0.920, Tmax = 0.963 | Rint = 0.011 |
| 4998 measured reflections | Standard reflections: ? |
| R[F2 > 2σ(F2)] = 0.035 | 122 parameters |
| wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | Δρmax = 0.31 e Å−3 |
| 1619 reflections | Δρmin = −0.19 e Å−3 |
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 > 2sigma(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. |
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.48719 (13) | 0.26168 (14) | 0.73729 (7) | 0.0278 (2) | |
| O1 | 0.41895 (14) | 0.39139 (13) | 0.79298 (7) | 0.0398 (3) | |
| O2 | 0.31826 (15) | 0.13474 (15) | 0.89520 (7) | 0.0448 (3) | |
| H2B | 0.3347 | 0.2406 | 0.8721 | 0.067* | |
| O3 | 0.40768 (15) | −0.16328 (14) | 0.86771 (7) | 0.0426 (3) | |
| O4 | 0.79194 (13) | −0.07382 (13) | 0.48418 (6) | 0.0353 (2) | |
| H4B | 0.838 (2) | −0.169 (3) | 0.4549 (13) | 0.052 (5)* | |
| O5 | 0.72985 (14) | −0.31254 (13) | 0.58244 (7) | 0.0405 (3) | |
| C1 | 0.48397 (15) | 0.07171 (16) | 0.75937 (8) | 0.0257 (2) | |
| C2 | 0.56127 (15) | −0.05789 (16) | 0.70098 (8) | 0.0257 (2) | |
| H2A | 0.5580 | −0.1878 | 0.7152 | 0.031* | |
| C3 | 0.64396 (14) | 0.00290 (16) | 0.62119 (7) | 0.0245 (2) | |
| C4 | 0.64456 (16) | 0.19734 (17) | 0.60040 (8) | 0.0291 (3) | |
| H4A | 0.6993 | 0.2416 | 0.5473 | 0.035* | |
| C5 | 0.56388 (17) | 0.32411 (17) | 0.65864 (9) | 0.0315 (3) | |
| H5A | 0.5619 | 0.4540 | 0.6439 | 0.038* | |
| C6 | 0.39838 (16) | 0.00556 (18) | 0.84741 (8) | 0.0317 (3) | |
| C7 | 0.72671 (15) | −0.14509 (16) | 0.56115 (8) | 0.0261 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0339 (5) | 0.0248 (5) | 0.0261 (5) | 0.0013 (4) | 0.0099 (4) | −0.0030 (4) |
| O1 | 0.0562 (6) | 0.0290 (5) | 0.0371 (5) | 0.0081 (4) | 0.0188 (4) | −0.0071 (4) |
| O2 | 0.0598 (6) | 0.0413 (5) | 0.0384 (5) | 0.0010 (4) | 0.0303 (5) | −0.0032 (4) |
| O3 | 0.0616 (6) | 0.0355 (5) | 0.0346 (5) | −0.0033 (4) | 0.0248 (4) | 0.0067 (4) |
| O4 | 0.0485 (5) | 0.0322 (5) | 0.0288 (4) | 0.0024 (4) | 0.0213 (4) | −0.0002 (3) |
| O5 | 0.0585 (6) | 0.0273 (5) | 0.0391 (5) | 0.0033 (4) | 0.0216 (4) | 0.0014 (4) |
| C1 | 0.0301 (5) | 0.0257 (6) | 0.0226 (5) | −0.0022 (4) | 0.0089 (4) | 0.0003 (4) |
| C2 | 0.0322 (6) | 0.0227 (5) | 0.0234 (5) | −0.0017 (4) | 0.0085 (4) | 0.0003 (4) |
| C3 | 0.0265 (5) | 0.0269 (6) | 0.0210 (5) | −0.0006 (4) | 0.0069 (4) | −0.0007 (4) |
| C4 | 0.0349 (6) | 0.0289 (6) | 0.0250 (5) | −0.0037 (5) | 0.0114 (4) | 0.0027 (4) |
| C5 | 0.0425 (6) | 0.0230 (5) | 0.0305 (6) | −0.0019 (5) | 0.0111 (5) | 0.0033 (4) |
| C6 | 0.0372 (6) | 0.0346 (6) | 0.0256 (5) | −0.0040 (5) | 0.0142 (5) | −0.0010 (5) |
| C7 | 0.0286 (5) | 0.0275 (5) | 0.0232 (5) | −0.0009 (4) | 0.0080 (4) | −0.0011 (4) |
| N1—O1 | 1.3240 (13) | C1—C2 | 1.3773 (15) |
| N1—C5 | 1.3549 (15) | C1—C6 | 1.5076 (15) |
| N1—C1 | 1.3630 (16) | C2—C3 | 1.3869 (15) |
| O2—C6 | 1.2968 (15) | C2—H2A | 0.9300 |
| O2—H2B | 0.8200 | C3—C4 | 1.3890 (17) |
| O3—C6 | 1.2134 (17) | C3—C7 | 1.4967 (15) |
| O4—C7 | 1.3170 (14) | C4—C5 | 1.3750 (17) |
| O4—H4B | 0.866 (19) | C4—H4A | 0.9300 |
| O5—C7 | 1.2066 (15) | C5—H5A | 0.9300 |
| O1—N1—C5 | 117.86 (10) | C4—C3—C7 | 123.24 (10) |
| O1—N1—C1 | 121.14 (9) | C5—C4—C3 | 119.69 (10) |
| C5—N1—C1 | 120.99 (10) | C5—C4—H4A | 120.2 |
| C6—O2—H2B | 109.5 | C3—C4—H4A | 120.2 |
| C7—O4—H4B | 106.4 (12) | N1—C5—C4 | 120.65 (11) |
| N1—C1—C2 | 119.24 (10) | N1—C5—H5A | 119.7 |
| N1—C1—C6 | 120.07 (10) | C4—C5—H5A | 119.7 |
| C2—C1—C6 | 120.69 (10) | O3—C6—O2 | 125.01 (11) |
| C1—C2—C3 | 120.84 (10) | O3—C6—C1 | 118.07 (11) |
| C1—C2—H2A | 119.6 | O2—C6—C1 | 116.92 (11) |
| C3—C2—H2A | 119.6 | O5—C7—O4 | 124.64 (11) |
| C2—C3—C4 | 118.58 (10) | O5—C7—C3 | 122.00 (10) |
| C2—C3—C7 | 118.19 (10) | O4—C7—C3 | 113.35 (10) |
| O1—N1—C1—C2 | −178.11 (10) | C1—N1—C5—C4 | −1.63 (18) |
| C5—N1—C1—C2 | 0.49 (17) | C3—C4—C5—N1 | 1.41 (19) |
| O1—N1—C1—C6 | 1.23 (17) | N1—C1—C6—O3 | −175.79 (12) |
| C5—N1—C1—C6 | 179.83 (11) | C2—C1—C6—O3 | 3.54 (18) |
| N1—C1—C2—C3 | 0.86 (17) | N1—C1—C6—O2 | 4.94 (17) |
| C6—C1—C2—C3 | −178.47 (11) | C2—C1—C6—O2 | −175.74 (11) |
| C1—C2—C3—C4 | −1.06 (17) | C2—C3—C7—O5 | −3.10 (17) |
| C1—C2—C3—C7 | 179.52 (10) | C4—C3—C7—O5 | 177.50 (12) |
| C2—C3—C4—C5 | −0.07 (17) | C2—C3—C7—O4 | 176.24 (10) |
| C7—C3—C4—C5 | 179.32 (11) | C4—C3—C7—O4 | −3.16 (16) |
| O1—N1—C5—C4 | 177.01 (11) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2B···O1 | 0.82 | 1.69 | 2.4508 (15) | 154 |
| O4—H4B···O3i | 0.866 (19) | 1.80 (2) | 2.6481 (14) | 165.6 (18) |
| Symmetry codes: (i) x+1/2, −y−1/2, z−1/2. |
| N1—O1 | 1.3240 (13) | O4—C7 | 1.3170 (14) |
| N1—C1 | 1.3630 (16) | O4—H4B | 0.866 (19) |
| O2—C6 | 1.2968 (15) | O5—C7 | 1.2066 (15) |
| O2—H2B | 0.8200 | C1—C2 | 1.3773 (15) |
| O3—C6 | 1.2134 (17) | C1—C6 | 1.5076 (15) |
| O1—N1—C1 | 121.14 (9) | O3—C6—C1 | 118.07 (11) |
| C6—O2—H2B | 109.5 | O2—C6—C1 | 116.92 (11) |
| C7—O4—H4B | 106.4 (12) | O5—C7—O4 | 124.64 (11) |
| N1—C1—C6 | 120.07 (10) | O5—C7—C3 | 122.00 (10) |
| O3—C6—O2 | 125.01 (11) | O4—C7—C3 | 113.35 (10) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2B···O1 | 0.82 | 1.69 | 2.4508 (15) | 154 |
| O4—H4B···O3i | 0.866 (19) | 1.80 (2) | 2.6481 (14) | 165.6 (18) |
| Symmetry codes: (i) x+1/2, −y−1/2, z−1/2. |
The project was supported by the National Science Foundation of Fujian Province of China (Nos. 2006 J164 and 2003 F006) and the National Science Foundation of the Overseas Chinese Affairs Office of the State Council, China (No. 05QZR01).
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1992). International Tables of Crystallography, Vol. 3, pp. 685–706. Dordrecht: Kluwer Academic Publishers.
Bruker (1997). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Dideberg, O. & Dupont, L. (1975). Acta Cryst. B31, 2719–2720.
Li, S. X., Liu, S. X. & Wu, W. S. (1987). J. Struct. Chem. 6, 20–24.
Rigaku (2000). CrystalClear. Version 1.3. Rigaku Corporation, Tokyo, Japan.
Rychlewska, U. & Gdaniec, M. (1977). Acta Cryst. B33, 3555–3558.
Sheldrick, G. M. (1990). Acta Cryst. A46, 467–473.
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany.
Steiner, T., Schreurs, A. M. M., Lutz, M. & Kroon, J. (2000). Acta Cryst. C56, 577–579.
The structure of the title compound, (I) reveals a virtually planar molecule with r.m.s. of 0.0061 Å. All bond distances and angles are normal and the structure is stabilized by inter- and intramolecular hydrogen bonds. The molecules are linked in one-dimensional zigzag chains via intermolecular carboxylic hydrogen bonds (Figure 2; Table 2) between O4 and O3. On the other hand, there is a weaker but prominent intermolecular hydrogen bond between H5A and O5 which provides inter chain stabilization, yielding a planar two-dimensional arrangement. Furthermore, the structure displays a strong, almost ideal intramolecular carboxylic hydrogen bond (Figure 1; Table 2) between O2 and O1 (Dideberg & Dupont, 1975; Rychlewska & Gdaniec, 1977; Steiner et al., 2000). The carboxyl C—O and C═O bonds are normal (Table 1), while the N—O distance of 1.324 (1)Å is slightly elongated compared to the average value of 1.304Å in pyridine N-oxides (Allen et al., 1992). The carboxylic hydrogen bonds display O—H···O angles around 160° (Table 2) due to stereochemical restriction of the C—O—H angle.