2,6-Dichloro-3-nitro­pyridine

Hoong-Kun Fun; Suhana Arshad; B Chandrakantha; Arun M Isloor; Prakash Shetty

doi:10.1107/S1600536811023683

. 2011 Jun 25;67(Pt 7):o1785. doi: 10.1107/S1600536811023683

2,6-Dichloro-3-nitropyridine

Hoong-Kun Fun ^a,^*,^‡, Suhana Arshad ^a, B Chandrakantha ^b, Arun M Isloor ^c, Prakash Shetty ^d

PMCID: PMC3152078 PMID: 21837158

Abstract

The asymmetric unit of the title compound, C₅H₂Cl₂N₂O₂, consists of two crystallographically independent molecules. The pyridine ring in each molecule is essentially planar, with maximum deviations of 0.004 (4) and 0.007 (4) Å. Short Cl⋯O [3.09 (3) and 3.13 (4) Å] and Cl⋯Cl [3.38 (12) Å] contacts were observed. No significant intermolecular interactions were observed in the crystal packing.

Related literature

For the role of the nitropyridine nucleus in the development of medicinal agents and in the field of agrochemicals, see: Davis et al. (1996 ▶). For the properties and use of pyridine derivatives, see: Vacher et al. (1998 ▶); Olah et al. (1980 ▶); Bare et al. (1989 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For the melting point, see: Johnson et al. (1967 ▶).

Experimental

Crystal data

C₅H₂Cl₂N₂O₂
M _r = 192.99
Monoclinic,
a = 7.9021 (8) Å
b = 19.166 (2) Å
c = 11.0987 (9) Å
β = 122.072 (5)°
V = 1424.4 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 296 K
0.40 × 0.27 × 0.24 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.727, T _max = 0.821
16845 measured reflections
4817 independent reflections
2323 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.180
S = 1.08
4817 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811023683/ng5183sup1.cif

e-67-o1785-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023683/ng5183Isup2.hkl

e-67-o1785-Isup2.hkl^{(236KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811023683/ng5183Isup3.cml

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). SA thanks the Malaysian Government and USM for the award of a research scholarship. AMI thanks the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India for a Young Scientist award.

supplementary crystallographic information

Comment

Nitropyridine nucleus played a pivotal role in the development of different medicinal agents and in the field of agrochemicals (Davis et al., 1996). It is seen from the current literature that pyridine derivatives have been developed and used as insecticidal agents (Vacher et al., 1998). Nitrated pyridines and their derivatives are important intermediates in synthesis of heterocyclic compounds in dyes and pharmaceutical products (Olah et al., 1980). Fused heterocycles containing nitropyridine systems have been associated with several biological and medicinal activities including antiolytic (Olah et al., 1980), antiviral and anti-inflammatory (Bare et al., 1989) profiles.

The asymmetric unit of the tittle compound (Fig. 1), consists of two crystallographically independent molecules A and B. The pyridine rings (N1/C1–C5) for molecules A and B are essentially planar with maximum deviations of 0.004 (4) Å at atom C1A and 0.007 (4) Å at atom C3B, respectively. The bond lengths (Allen et al., 1987) and angles are within normal ranges. In addition, short Cl···O [Cl1A···O2A (1 - x, -1/2 + y, 1/2 - z) = 3.093 (3) Å and Cl2A···O2A (1 - x, 2 - y, -z) = 3.132 (4) Å] and Cl···Cl [Cl2A···Cl2A (1 - x, 2 - y, -z) = 3.3839 (12) Å] contacts were observed.

The crystal packing is shown in Fig. 2. No significant intermolecular interactions were observed in the crystal packing.

Experimental

2,6-Dichloropyridine (5 g, 0.033 mol) was added lotwise to mixture of concentrated H₂SO₄ (25 ml) and fuming nitric acid (10 ml) at 0 °C. After the addition, the reaction mixture was heated to 65 °C for 2 h. After completion of the reaction, the reaction mixture was cooled to room temperature and quenched with ice water. The solid that separated out was filtered and dried under vacuum. The crude product was purified by column chromatography using silica gel 60–120 mesh size and petroleum ether: ethyl acetate as eluent to afford title compound as a pale yellow solid. Yield: 3.0 g, 46.0%. M.p.: 333–338 K (Johnson et al., 1967).