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access2-Chloro-5-nitropyridine
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my
The non-H atoms of the title compound, C5H3ClN2O2, almost lie in a common plane (r.m.s. deviation = 0.090 Å). In the crystal, adjacent molecules feature a short Cl⋯O contact [3.068 (4) Å], forming a chain; these chains are consolidated into a layer structure by non-classical C—H⋯O interactions.
Related literature
For the mechanism of the reaction between 2-chloro-5-nitropyridine and aryloxide ions, see: El-Bardan (1999![[El-Bardan, A. A. (1999). J. Phys. Org. Chem. 13, 347-353.]](../../../../../../logos/arrows/e_arr.gif "El-Bardan, A. A. (1999). J. Phys. Org. Chem. 13, 347-353.")
); Haynes & Pett (2007); Zeller et al. (2007).
![[Scheme 1]](bt5214scheme1.gif)
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); 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, 2010).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536810008974/bt5214sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536810008974/bt5214Isup2.hkl
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 checking program PLATON detects some However, as the refined to nearly zero, the non-centric must be the correct one. Nevertheless, an attempt was made to treat the structure as a whole-molecule-disordered structure but this gave a model with bad bond dimensions.
Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 2010).
![[Figure 1]](./bt5214fig1thm.gif) | Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of 2-chloro-5-nitropyridine at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. |
| C5H3ClN2O2 | Z = 1 |
| Mr = 158.54 | F(000) = 80 |
| Triclinic, P1 | Dx = 1.761 Mg m−3 |
| Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 3.7599 (8) Å | Cell parameters from 637 reflections |
| b = 5.8641 (13) Å | θ = 2.9–28.2° |
| c = 7.0189 (15) Å | µ = 0.56 mm−1 |
| α = 84.687 (3)° | T = 100 K |
| β = 89.668 (3)° | Plate, colorless |
| γ = 76.020 (3)° | 0.45 × 0.15 × 0.03 mm |
| V = 149.50 (6) Å3 |
| Bruker SMART APEX diffractometer | 1114 independent reflections |
| Radiation source: fine-focus sealed tube | 1071 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.022 |
| ω scans | θmax = 27.5°, θmin = 2.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −4→4 |
| Tmin = 0.786, Tmax = 0.983 | k = −7→7 |
| 1379 measured reflections | l = −9→9 |
| 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)] = 0.056 | H-atom parameters constrained |
| wR(F2) = 0.143 | w = 1/[σ2(Fo2) + (0.070P)2 + 0.2047P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.17 | (Δ/σ)max = 0.001 |
| 1114 reflections | Δρmax = 0.63 e Å−3 |
| 91 parameters | Δρmin = −0.59 e Å−3 |
| 3 restraints | Absolute structure: Flack (1983), 449 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.05 (14) |
| C5H3ClN2O2 | γ = 76.020 (3)° |
| Mr = 158.54 | V = 149.50 (6) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 3.7599 (8) Å | Mo Kα radiation |
| b = 5.8641 (13) Å | µ = 0.56 mm−1 |
| c = 7.0189 (15) Å | T = 100 K |
| α = 84.687 (3)° | 0.45 × 0.15 × 0.03 mm |
| β = 89.668 (3)° |
| Bruker SMART APEX diffractometer | 1114 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1071 reflections with I > 2σ(I) |
| Tmin = 0.786, Tmax = 0.983 | Rint = 0.022 |
| 1379 measured reflections |
| R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
| wR(F2) = 0.143 | Δρmax = 0.63 e Å−3 |
| S = 1.17 | Δρmin = −0.59 e Å−3 |
| 1114 reflections | Absolute structure: Flack (1983), 449 Friedel pairs |
| 91 parameters | Absolute structure parameter: −0.05 (14) |
| 3 restraints |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.5000 (2) | 0.50003 (18) | 0.49998 (17) | 0.0193 (3) | |
| O1 | 0.8088 (11) | 0.9486 (7) | 1.2731 (6) | 0.0254 (9) | |
| O2 | 0.3611 (12) | 1.2366 (7) | 1.1607 (7) | 0.0259 (10) | |
| N1 | 0.7126 (12) | 0.5558 (8) | 0.8407 (7) | 0.0161 (10) | |
| N2 | 0.5729 (13) | 1.0408 (10) | 1.1526 (7) | 0.0170 (11) | |
| C1 | 0.5156 (14) | 0.6688 (11) | 0.6894 (8) | 0.0180 (11) | |
| C2 | 0.3197 (14) | 0.9038 (9) | 0.6723 (8) | 0.0137 (11) | |
| H2 | 0.1837 | 0.9735 | 0.5592 | 0.016* | |
| C3 | 0.3320 (17) | 1.0316 (12) | 0.8277 (10) | 0.0182 (13) | |
| H3 | 0.2017 | 1.1922 | 0.8260 | 0.022* | |
| C4 | 0.5415 (15) | 0.9162 (10) | 0.9860 (8) | 0.0146 (11) | |
| C5 | 0.7254 (14) | 0.6800 (10) | 0.9887 (8) | 0.0173 (11) | |
| H5 | 0.8644 | 0.6050 | 1.0995 | 0.021* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0220 (6) | 0.0165 (6) | 0.0198 (6) | −0.0033 (4) | −0.0008 (4) | −0.0072 (4) |
| O1 | 0.028 (2) | 0.024 (2) | 0.023 (2) | −0.0037 (17) | −0.0085 (18) | −0.0027 (18) |
| O2 | 0.034 (2) | 0.015 (2) | 0.024 (2) | 0.0062 (16) | −0.0050 (17) | −0.0097 (17) |
| N1 | 0.015 (2) | 0.014 (2) | 0.019 (2) | −0.0011 (18) | −0.0014 (18) | −0.0041 (18) |
| N2 | 0.018 (2) | 0.016 (3) | 0.018 (3) | −0.005 (2) | 0.002 (2) | −0.006 (2) |
| C1 | 0.016 (2) | 0.019 (3) | 0.020 (3) | −0.004 (2) | 0.003 (2) | −0.005 (2) |
| C2 | 0.013 (2) | 0.014 (2) | 0.013 (3) | 0.001 (2) | −0.0043 (18) | 0.001 (2) |
| C3 | 0.017 (3) | 0.016 (3) | 0.021 (3) | −0.002 (2) | 0.000 (2) | −0.004 (2) |
| C4 | 0.015 (2) | 0.013 (2) | 0.016 (3) | −0.003 (2) | 0.0011 (19) | −0.005 (2) |
| C5 | 0.017 (2) | 0.015 (3) | 0.018 (3) | −0.003 (2) | 0.001 (2) | −0.003 (2) |
| Cl1—C1 | 1.739 (6) | C2—C3 | 1.387 (9) |
| O1—N2 | 1.219 (7) | C2—H2 | 0.9500 |
| O2—N2 | 1.235 (7) | C3—C4 | 1.387 (9) |
| N1—C1 | 1.325 (7) | C3—H3 | 0.9500 |
| N1—C5 | 1.330 (7) | C4—C5 | 1.389 (8) |
| N2—C4 | 1.455 (8) | C5—H5 | 0.9500 |
| C1—C2 | 1.391 (7) | ||
| C1—N1—C5 | 116.7 (5) | C2—C3—C4 | 117.6 (6) |
| O1—N2—O2 | 124.1 (6) | C2—C3—H3 | 121.2 |
| O1—N2—C4 | 118.4 (6) | C4—C3—H3 | 121.2 |
| O2—N2—C4 | 117.4 (5) | C3—C4—C5 | 120.8 (5) |
| N1—C1—C2 | 126.0 (5) | C3—C4—N2 | 120.5 (5) |
| N1—C1—Cl1 | 115.4 (4) | C5—C4—N2 | 118.7 (5) |
| C2—C1—Cl1 | 118.6 (4) | N1—C5—C4 | 122.0 (5) |
| C3—C2—C1 | 117.0 (5) | N1—C5—H5 | 119.0 |
| C3—C2—H2 | 121.5 | C4—C5—H5 | 119.0 |
| C1—C2—H2 | 121.5 | ||
| C5—N1—C1—C2 | −0.6 (7) | O1—N2—C4—C3 | −166.8 (5) |
| C5—N1—C1—Cl1 | −179.2 (4) | O2—N2—C4—C3 | 11.9 (9) |
| N1—C1—C2—C3 | 0.1 (8) | O1—N2—C4—C5 | 13.1 (8) |
| Cl1—C1—C2—C3 | 178.6 (4) | O2—N2—C4—C5 | −168.1 (5) |
| C1—C2—C3—C4 | 0.8 (8) | C1—N1—C5—C4 | 0.1 (8) |
| C2—C3—C4—C5 | −1.2 (8) | C3—C4—C5—N1 | 0.8 (8) |
| C2—C3—C4—N2 | 178.7 (4) | N2—C4—C5—N1 | −179.2 (5) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···O1i | 0.95 | 2.50 | 3.361 (7) | 151 |
| Symmetry code: (i) x−1, y, z−1. |
Experimental details
| Crystal data | |
| Chemical formula | C5H3ClN2O2 |
| Mr | 158.54 |
| Crystal system, space group | Triclinic, P1 |
| Temperature (K) | 100 |
| a, b, c (Å) | 3.7599 (8), 5.8641 (13), 7.0189 (15) |
| α, β, γ (°) | 84.687 (3), 89.668 (3), 76.020 (3) |
| V (Å3) | 149.50 (6) |
| Z | 1 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.56 |
| Crystal size (mm) | 0.45 × 0.15 × 0.03 |
| Data collection | |
| Diffractometer | Bruker SMART APEX diffractometer |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
| Tmin, Tmax | 0.786, 0.983 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 1379, 1114, 1071 |
| Rint | 0.022 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.143, 1.17 |
| No. of reflections | 1114 |
| No. of parameters | 91 |
| No. of restraints | 3 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.63, −0.59 |
| Absolute structure | Flack (1983), 449 Friedel pairs |
| Absolute structure parameter | −0.05 (14) |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···O1i | 0.95 | 2.50 | 3.361 (7) | 151 |
| Symmetry code: (i) x−1, y, z−1. |
Acknowledgements
I thank the University of Malaya for supporting this study.
References
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
El-Bardan, A. A. (1999). J. Phys. Org. Chem. 13, 347–353. CrossRef Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Haynes, L. R. W. & Pett, V. B. (2007). J. Org. Chem. 72, 633–635. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar
Zeller, M., Pett, V. B. & Haynes, L. R. W. (2007). Acta Cryst. C63, o343–o346. Web of Science CSD CrossRef IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
We have synthesized some nitropyridyl aryl ethers by the reaction of the aryloxide ion with the chlorine-substituted nitropyridine. The mechanism of this reaction has been reported (El-Bardan, 1999). With 2-chloro-5-nitropyridine, additional hydroxide base should not be used as the compound undergoes ring opening (Haynes & Pett, 2007; Zeller et al., 2007).
2-Chloro-5-nitropyridine (Scheme I, Fig. 1) is a flat molecule; the non-hydrogen atoms all lie in a common plane (r.m.s. deviation 0.090 Å). Adjacent molecules interact by a Cl···O contact [3.068 (4) Å] to form a chain. The chains are consolidated into a layer structure by a non-classical C–H···O interaction; this interaction involves the second oxygen atom of the nitro group.