Crystal structure of 2,6-di­chloro-4-nitro­pyridine N-oxide

Prichard, A.M.; Lynch, W.E.; Padgett, C.W.

doi:10.1107/S2056989015017387

organic compounds

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Volume 71| Part 10| October 2015| Page o775

doi:10.1107/S2056989015017387

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Crystal structure of 2,6-dichloro-4-nitropyridine N-oxide

Andrew M. Prichard,^a Will E. Lynch ^a and Clifford W. Padgett ^a ^*

^aArmstrong State University, 11935 Abercorn St., Savanah, GA 31419, USA
^*Correspondence e-mail: clifford.padgett@armstrong.edu

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 11 September 2015; accepted 17 September 2015; online 26 September 2015)

In the title compound, C₅H₂Cl₂N₂O₃, the nitro group is essentially coplanar with the aromatic ring, with a twist angle of 4.00 (6)° and a fold angle of 2.28 (17)°. The crystal structure exhibits a herringbone pattern with the zigzag running along the b axis. The herringbone layer-to-layer distance is 3.0075 (15) Å, with a shift of 5.150 (4) Å. Neighboring molecules are tilted at a 57.83 (4)° (ring-to-ring) angle with each other. The nitro group on one molecule points to the N-oxide group on the neighboring one, with an intermolecular O⋯N(nitro) distance of 3.1725 (13) Å.

Keywords: crystal structure; pyridine N-oxide; herringbone pattern.

CCDC reference: 1425488

1. Related literature

For the synthesis of the title compound and related compounds, see: Rousseau & Robins (1965 ). For chemical interest in derivatives of pyridine N-oxide, including the ruthenium-catalyzed use of these compounds towards the epoxidation of olefins via an N-oxide coordinated Ru^IV=O intermediate, see: Gross & Ini (1999 ).

2. Experimental

2.1. Crystal data

C₅H₂Cl₂N₂O₃
M_r = 208.99
Orthorhombic, P b c a
a = 5.964 (4) Å
b = 9.510 (6) Å
c = 26.192 (16) Å
V = 1485.5 (16) Å³
Z = 8
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 173 K
0.6 × 0.2 × 0.1 mm

2.2. Data collection

Rigaku XtaLAB mini diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ) T_min = 0.709, T_max = 1.000
13695 measured reflections
1697 independent reflections
1512 reflections with I > 2σ(I)
R_int = 0.043

2.3. Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.078
S = 1.09
1697 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: CrystalClear-SM Expert (Rigaku, 2011 ); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 1425488

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015017387/tk5385sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015017387/tk5385Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015017387/tk5385Isup3.cml

checkCIF report

Synthesis and crystallization top

2,6-Dichloro-4-nitropyridine N-oxide was purchased from Sigma-Aldrich and 0.10 g was dissolved in approximately 50 mL of methanol. Diffraction quality crystals were obtained by slow evaporation of the solvent.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2U_equiv(C).

Related literature top

For the synthesis of the title compound and related compounds, see: Rousseau & Robins (1965). Chemical interest in derivatives of pyridine N-oxide include the ruthenium-catalyzed use of these compounds towards the epoxidation of olefins via an N-oxide coordinated Ru^IV═ O intermediate, see: Gross & Ini (1999).

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

2,6-Dichloro-4-nitropyridine N-oxide top

Crystal data top

C₅H₂Cl₂N₂O₃	D_x = 1.869 Mg m⁻³
M_r = 208.99	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3422 reflections
a = 5.964 (4) Å	θ = 2.1–27.5°
b = 9.510 (6) Å	µ = 0.84 mm⁻¹
c = 26.192 (16) Å	T = 173 K
V = 1485.5 (16) Å³	Prism, colorless
Z = 8	0.6 × 0.2 × 0.1 mm
F(000) = 832

Data collection top

Rigaku XtaLAB mini diffractometer	1697 independent reflections
Radiation source: Sealed Tube	1512 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.043
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
profile data from ω scans	h = −7→7
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −12→12
T_min = 0.709, T_max = 1.000	l = −33→34
13695 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.026P)² + 0.628P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
1697 reflections	Δρ_max = 0.23 e Å⁻³
109 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints

Crystal data top

C₅H₂Cl₂N₂O₃	V = 1485.5 (16) Å³
M_r = 208.99	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 5.964 (4) Å	µ = 0.84 mm⁻¹
b = 9.510 (6) Å	T = 173 K
c = 26.192 (16) Å	0.6 × 0.2 × 0.1 mm

Data collection top

Rigaku XtaLAB mini diffractometer	1697 independent reflections
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	1512 reflections with I > 2σ(I)
T_min = 0.709, T_max = 1.000	R_int = 0.043
13695 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.09	Δρ_max = 0.23 e Å⁻³
1697 reflections	Δρ_min = −0.34 e Å⁻³
109 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cl2	0.85784 (8)	0.45634 (5)	0.29466 (2)	0.04219 (16)
Cl1	0.76404 (10)	0.58023 (6)	0.48666 (2)	0.05096 (18)
O1	0.9698 (2)	0.47138 (13)	0.39871 (5)	0.0406 (3)
O2	0.0755 (2)	0.79615 (14)	0.39133 (6)	0.0436 (3)
O3	0.1322 (2)	0.76147 (15)	0.31036 (6)	0.0494 (4)
N1	0.7830 (2)	0.53287 (14)	0.38874 (5)	0.0278 (3)
N2	0.1835 (2)	0.74825 (15)	0.35543 (6)	0.0337 (3)
C3	0.3887 (3)	0.67006 (16)	0.36721 (6)	0.0261 (3)
C4	0.5076 (3)	0.60983 (16)	0.32781 (6)	0.0273 (3)
H4	0.4563	0.6160	0.2935	0.033*
C2	0.4594 (3)	0.66162 (17)	0.41700 (7)	0.0297 (4)
H2	0.3734	0.7017	0.4439	0.036*
C5	0.7030 (3)	0.54043 (16)	0.33971 (6)	0.0268 (3)
C1	0.6574 (3)	0.59381 (17)	0.42689 (7)	0.0302 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.0471 (3)	0.0357 (3)	0.0438 (3)	0.0101 (2)	0.0179 (2)	0.00214 (18)
Cl1	0.0628 (4)	0.0529 (3)	0.0372 (3)	0.0068 (2)	−0.0209 (2)	−0.0034 (2)
O1	0.0271 (6)	0.0318 (7)	0.0630 (9)	0.0093 (5)	−0.0097 (6)	0.0019 (6)
O2	0.0319 (7)	0.0348 (7)	0.0639 (9)	0.0093 (6)	0.0106 (6)	0.0024 (6)
O3	0.0438 (8)	0.0493 (9)	0.0552 (9)	0.0111 (7)	−0.0184 (7)	0.0051 (7)
N1	0.0229 (7)	0.0207 (7)	0.0397 (8)	0.0013 (5)	−0.0042 (6)	0.0013 (6)
N2	0.0260 (7)	0.0242 (7)	0.0508 (9)	0.0009 (6)	−0.0035 (7)	0.0047 (6)
C3	0.0223 (7)	0.0202 (7)	0.0357 (9)	0.0005 (6)	−0.0006 (6)	0.0026 (6)
C4	0.0293 (8)	0.0223 (8)	0.0303 (8)	−0.0013 (6)	−0.0016 (7)	0.0021 (6)
C2	0.0325 (9)	0.0238 (8)	0.0330 (9)	0.0021 (7)	0.0018 (7)	−0.0019 (7)
C5	0.0281 (8)	0.0204 (8)	0.0319 (9)	0.0006 (6)	0.0045 (7)	0.0012 (6)
C1	0.0341 (9)	0.0255 (8)	0.0310 (9)	−0.0005 (7)	−0.0050 (7)	−0.0006 (6)

Geometric parameters (Å, º) top

Cl2—C5	1.6984 (18)	N2—C3	1.465 (2)
Cl1—C1	1.695 (2)	C3—C4	1.377 (2)
O1—N1	1.2847 (18)	C3—C2	1.373 (2)
O2—N2	1.228 (2)	C4—H4	0.9500
O3—N2	1.226 (2)	C4—C5	1.375 (2)
N1—C5	1.372 (2)	C2—H2	0.9500
N1—C1	1.377 (2)	C2—C1	1.370 (3)

O1—N1—C5	121.03 (14)	C5—C4—H4	121.1
O1—N1—C1	121.06 (15)	C3—C2—H2	120.9
C5—N1—C1	117.90 (14)	C1—C2—C3	118.13 (16)
O2—N2—C3	117.74 (15)	C1—C2—H2	120.9
O3—N2—O2	124.65 (16)	N1—C5—Cl2	115.89 (13)
O3—N2—C3	117.61 (15)	N1—C5—C4	122.15 (15)
C4—C3—N2	118.91 (15)	C4—C5—Cl2	121.96 (14)
C2—C3—N2	119.10 (15)	N1—C1—Cl1	115.73 (13)
C2—C3—C4	121.98 (16)	C2—C1—Cl1	122.26 (14)
C3—C4—H4	121.1	C2—C1—N1	122.01 (16)
C5—C4—C3	117.79 (16)

Experimental details

Crystal data
Chemical formula	C₅H₂Cl₂N₂O₃
M_r	208.99
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	5.964 (4), 9.510 (6), 26.192 (16)
V (Å³)	1485.5 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.6 × 0.2 × 0.1

Data collection
Diffractometer	Rigaku XtaLAB mini diffractometer
Absorption correction	Multi-scan (REQAB; Rigaku, 1998)
T_min, T_max	0.709, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13695, 1697, 1512
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.078, 1.09
No. of reflections	1697
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.34

Computer programs: CrystalClear-SM Expert (Rigaku, 2011), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

The authors acknowledge financial support from Armstrong State University.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gross, Z. & Ini, S. (1999). Inorg. Chem. 38, 1446–1449. CSD CrossRef CAS Google Scholar
Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2011). CrystalClear-SM Expert. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rousseau, R. J. & Robins, R. K. (1965). J. Heterocycl. Chem. 2, 196–201. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 10| October 2015| Page o775

doi:10.1107/S2056989015017387

Open

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