Acta Cryst. (2009). E65, o2154 [ doi:10.1107/S1600536809031407 ]
In the crystal structure of the title compound, C6H4ClN3O5, the two nitro groups are twisted with respect to the pyridine ring, making dihedral angles of 33.12 (13) and 63.66 (14)°.
The title compound was prepared according to a literature method (Chen et al., 2008). Crystals suitable for X-ray analysis were obtained by slow evaporation of 1,2-dichloroethane.
H atoms were positioned geometrically and refined using a ride model with C—H = 0.93 Å for aromatic H and 0.96 Å for methyl H atoms, Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for aromatic H atom.
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./xu2586fig1thm.gif)
| Fig. 1. The molecular structure of title compound, with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). |
| C6H4ClN3O5 | F(000) = 472 |
| Mr = 233.57 | Dx = 1.701 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 5866 reflections |
| a = 6.6490 (13) Å | θ = 2.5–27.5° |
| b = 10.842 (2) Å | µ = 0.43 mm−1 |
| c = 12.715 (3) Å | T = 293 K |
| β = 95.55 (3)° | Block, colorless |
| V = 912.3 (3) Å3 | 0.50 × 0.40 × 0.28 mm |
| Z = 4 |
| Rigaku R-AXIS RAPID IP diffractometer | 2062 independent reflections |
| Radiation source: fine-focus sealed tube | 1275 reflections with I > 2σ(I) |
| graphite | Rint = 0.050 |
| Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
| ω scans | h = −8→8 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −13→13 |
| Tmin = 0.808, Tmax = 0.887 | l = −16→16 |
| 5866 measured 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)] = 0.048 | H-atom parameters constrained |
| wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.08P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.99 | (Δ/σ)max < 0.001 |
| 2062 reflections | Δρmax = 0.26 e Å−3 |
| 138 parameters | Δρmin = −0.30 e Å−3 |
| 0 restraints | Extinction correction: SHELXTL (Version 4.2; Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.157 (11) |
| C6H4ClN3O5 | V = 912.3 (3) Å3 |
| Mr = 233.57 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 6.6490 (13) Å | µ = 0.43 mm−1 |
| b = 10.842 (2) Å | T = 293 K |
| c = 12.715 (3) Å | 0.50 × 0.40 × 0.28 mm |
| β = 95.55 (3)° |
| Rigaku R-AXIS RAPID IP diffractometer | 2062 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1275 reflections with I > 2σ(I) |
| Tmin = 0.808, Tmax = 0.887 | Rint = 0.050 |
| 5866 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
| wR(F2) = 0.135 | Δρmax = 0.26 e Å−3 |
| S = 0.99 | Δρmin = −0.30 e Å−3 |
| 2062 reflections | Absolute structure: ? |
| 138 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 > 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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.17055 (10) | 0.52802 (8) | 0.42365 (6) | 0.0756 (3) | |
| O1 | 0.8010 (3) | 0.77739 (16) | 0.37270 (12) | 0.0536 (5) | |
| O2 | 0.2241 (4) | 0.3362 (2) | 0.27062 (18) | 0.0939 (8) | |
| O3 | 0.2590 (3) | 0.4071 (2) | 0.11455 (16) | 0.0716 (6) | |
| O4 | 0.8115 (4) | 0.7839 (2) | 0.14363 (19) | 0.0949 (8) | |
| O5 | 0.9482 (4) | 0.6061 (2) | 0.1524 (2) | 0.1051 (9) | |
| N1 | 0.5510 (3) | 0.55114 (17) | 0.20338 (15) | 0.0439 (5) | |
| N2 | 0.2845 (3) | 0.4126 (2) | 0.2107 (2) | 0.0590 (6) | |
| N3 | 0.8230 (3) | 0.6789 (2) | 0.17477 (16) | 0.0556 (6) | |
| C1 | 0.4068 (3) | 0.5141 (2) | 0.25985 (18) | 0.0440 (5) | |
| C2 | 0.3749 (3) | 0.5646 (2) | 0.35677 (18) | 0.0453 (6) | |
| C3 | 0.5061 (3) | 0.6544 (2) | 0.39881 (17) | 0.0443 (5) | |
| H3 | 0.4898 | 0.6885 | 0.4645 | 0.053* | |
| C4 | 0.6614 (3) | 0.6929 (2) | 0.34246 (16) | 0.0407 (5) | |
| C5 | 0.6705 (3) | 0.6373 (2) | 0.24397 (16) | 0.0412 (5) | |
| C6 | 0.7921 (5) | 0.8349 (3) | 0.47424 (19) | 0.0657 (8) | |
| H6A | 0.6641 | 0.8754 | 0.4761 | 0.099* | |
| H6B | 0.8989 | 0.8944 | 0.4857 | 0.099* | |
| H6C | 0.8073 | 0.7732 | 0.5286 | 0.099* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0570 (4) | 0.0974 (6) | 0.0777 (5) | −0.0107 (4) | 0.0343 (4) | 0.0139 (4) |
| O1 | 0.0575 (10) | 0.0580 (10) | 0.0474 (9) | −0.0144 (8) | 0.0153 (8) | −0.0112 (8) |
| O2 | 0.1109 (18) | 0.0831 (15) | 0.0882 (15) | −0.0542 (15) | 0.0115 (13) | 0.0088 (12) |
| O3 | 0.0704 (12) | 0.0772 (13) | 0.0661 (13) | −0.0183 (10) | 0.0006 (10) | −0.0065 (10) |
| O4 | 0.1047 (18) | 0.0908 (18) | 0.0946 (16) | −0.0134 (14) | 0.0377 (14) | 0.0320 (13) |
| O5 | 0.0869 (16) | 0.1075 (19) | 0.133 (2) | 0.0047 (15) | 0.0717 (15) | −0.0076 (16) |
| N1 | 0.0418 (10) | 0.0451 (10) | 0.0457 (10) | −0.0002 (9) | 0.0083 (8) | −0.0001 (8) |
| N2 | 0.0494 (12) | 0.0609 (14) | 0.0666 (15) | −0.0129 (11) | 0.0060 (10) | 0.0026 (11) |
| N3 | 0.0526 (12) | 0.0688 (15) | 0.0481 (11) | −0.0127 (11) | 0.0182 (9) | −0.0061 (11) |
| C1 | 0.0400 (11) | 0.0430 (12) | 0.0492 (12) | −0.0024 (10) | 0.0053 (10) | 0.0060 (10) |
| C2 | 0.0388 (11) | 0.0492 (13) | 0.0493 (13) | 0.0041 (10) | 0.0121 (9) | 0.0141 (10) |
| C3 | 0.0468 (12) | 0.0476 (13) | 0.0405 (12) | 0.0064 (11) | 0.0150 (9) | 0.0035 (10) |
| C4 | 0.0415 (11) | 0.0395 (11) | 0.0422 (12) | 0.0038 (10) | 0.0096 (9) | 0.0035 (9) |
| C5 | 0.0364 (10) | 0.0460 (12) | 0.0423 (11) | 0.0004 (10) | 0.0097 (9) | 0.0037 (9) |
| C6 | 0.0845 (19) | 0.0678 (17) | 0.0463 (14) | −0.0182 (15) | 0.0138 (13) | −0.0125 (12) |
| Cl1—C2 | 1.717 (2) | N3—C5 | 1.476 (3) |
| O1—C4 | 1.334 (3) | C1—C2 | 1.384 (3) |
| O1—C6 | 1.440 (3) | C2—C3 | 1.380 (3) |
| O2—N2 | 1.219 (3) | C3—C4 | 1.378 (3) |
| O3—N2 | 1.219 (3) | C3—H3 | 0.9300 |
| O4—N3 | 1.206 (3) | C4—C5 | 1.396 (3) |
| O5—N3 | 1.201 (3) | C6—H6A | 0.9600 |
| N1—C5 | 1.300 (3) | C6—H6B | 0.9600 |
| N1—C1 | 1.315 (3) | C6—H6C | 0.9600 |
| N2—C1 | 1.472 (3) | ||
| C4—O1—C6 | 117.90 (18) | C4—C3—H3 | 120.3 |
| C5—N1—C1 | 116.89 (19) | C2—C3—H3 | 120.3 |
| O3—N2—O2 | 124.9 (2) | O1—C4—C3 | 126.4 (2) |
| O3—N2—C1 | 118.7 (2) | O1—C4—C5 | 117.78 (18) |
| O2—N2—C1 | 116.4 (2) | C3—C4—C5 | 115.8 (2) |
| O5—N3—O4 | 124.5 (2) | N1—C5—C4 | 126.05 (19) |
| O5—N3—C5 | 118.2 (2) | N1—C5—N3 | 114.31 (18) |
| O4—N3—C5 | 117.3 (2) | C4—C5—N3 | 119.6 (2) |
| N1—C1—C2 | 123.3 (2) | O1—C6—H6A | 109.5 |
| N1—C1—N2 | 113.5 (2) | O1—C6—H6B | 109.5 |
| C2—C1—N2 | 123.2 (2) | H6A—C6—H6B | 109.5 |
| C3—C2—C1 | 118.6 (2) | O1—C6—H6C | 109.5 |
| C3—C2—Cl1 | 118.16 (18) | H6A—C6—H6C | 109.5 |
| C1—C2—Cl1 | 123.13 (19) | H6B—C6—H6C | 109.5 |
| C4—C3—C2 | 119.3 (2) | ||
| C5—N1—C1—C2 | 1.9 (3) | C6—O1—C4—C5 | −180.0 (2) |
| C5—N1—C1—N2 | −177.3 (2) | C2—C3—C4—O1 | −179.3 (2) |
| O3—N2—C1—N1 | −31.5 (3) | C2—C3—C4—C5 | 1.0 (3) |
| O2—N2—C1—N1 | 145.0 (2) | C1—N1—C5—C4 | 0.9 (3) |
| O3—N2—C1—C2 | 149.3 (2) | C1—N1—C5—N3 | −177.3 (2) |
| O2—N2—C1—C2 | −34.2 (4) | O1—C4—C5—N1 | 178.0 (2) |
| N1—C1—C2—C3 | −3.1 (3) | C3—C4—C5—N1 | −2.3 (3) |
| N2—C1—C2—C3 | 176.0 (2) | O1—C4—C5—N3 | −4.0 (3) |
| N1—C1—C2—Cl1 | 172.71 (17) | C3—C4—C5—N3 | 175.7 (2) |
| N2—C1—C2—Cl1 | −8.2 (3) | O5—N3—C5—N1 | −64.2 (3) |
| C1—C2—C3—C4 | 1.4 (3) | O4—N3—C5—N1 | 115.0 (3) |
| Cl1—C2—C3—C4 | −174.58 (16) | O5—N3—C5—C4 | 117.5 (3) |
| C6—O1—C4—C3 | 0.3 (3) | O4—N3—C5—C4 | −63.3 (3) |
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Chen, J., Li, Q.-L. & Wang, J.-L. (2008). Chin. J. Org. Chem. 28, 123–126.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Pyridine derivatives are important intermediates used to synthesize pesticide, medicine and play important roles in fine chemical field. 3-Chloro-5-methoxyl- 2,6-dinitro-pyridine was synthesized from 3,5-dichloropyridine N-oxide by substitution and nitration (Bissell et al., 1987), and the process was improved by Chen et al. (2008). The crystal structure of the title compound is presented here.
The molecular structure of the title compound is shown in Fig. 1. While the methoxyl group, except H atoms, is co-planar with the pyridine ring, the two nitro groups are twisted with respect to the pyridine ring with dihedral angles of 33.12 (13) and 63.66 (14)°, respectively. Neither hydrogen bonding nor π-π stacking is observed in the crystal structure.