2-Chloro-3-nitro­pyridine

Ng, S.W.

doi:10.1107/S1600536810011955

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1020

https://doi.org/10.1107/S1600536810011955

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2-Chloro-3-nitropyridine

Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 22 February 2010; accepted 30 March 2010; online 2 April 2010)

In the title compound, C₅H₃ClN₂O₂, the nitro group is twisted by 38.5 (2)° with respect to the pyridine ring. In the crystal, adjacent molecules are linked by non-classical C—H⋯N and C—H⋯O hydrogen bonds, forming a layer motif.

Related literature

For the crystal structure of isostructural 2-iodo-3-nitropyridine, see: Mao & Chen (2009 ). For the crystal structure of 2-chloro-5-nitropyridine, see: Ng (2010 ).

Experimental

Crystal data

C₅H₃ClN₂O₂
M_r = 158.54
Monoclinic, P 2₁ /n
a = 7.613 (1) Å
b = 12.232 (2) Å
c = 7.716 (1) Å
β = 118.485 (2)°
V = 631.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.771, T_max = 0.862
5889 measured reflections
1445 independent reflections
1061 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.108
S = 1.02
1445 reflections
103 parameters
3 restraints
All H-atom parameters refined
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.93 (1)	2.53 (1)	3.430 (3)	166 (2)
C4—H4⋯O1ⁱⁱ	0.93 (1)	2.64 (2)	3.327 (3)	132 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y, z-1.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810011955/im2183sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810011955/im2183Isup2.hkl

checkCIF report

Comment top

According to a recent report on the crystal structure of 2-chloro-5-nitropyridine the respective molecule is planar (maximum r.m.s. deviation of non-hydrogen atoms is 0.090 Å). This molecule has the electron withdrawing substituents para to each other. The substituents interact through a short Cl···O contact of 3.068 (4) Å to generate a chain motif (Ng, 2010).

In the title compound 2-chloro-3-nitropyridine with the nitro group ortho to the chlorine substituent (Scheme I, Fig. 1), a similar Cl···O contact is also observed but the nitro group is twisted to avoid repulsion. Adjacent molecules are linked by non-classical C–H···N and C–H···O hydrogen bonds to form a layer motif (Fig. 2, Table 1). The C–H···N interaction is almost linear (Table 1).

2-Chloro-3-nitropyridine is isostructural with the iodo analog. In the iodo compound, the I···O contact is necessarily longer (Mao & Chen, 2009).

Related literature top

For the crystal structure of isostructural 2-iodo-3-nitropyridine, see: Mao & Chen (2009). For the crystal structure of 2-chloro-5-nitropyridine, see: Ng (2010).

Experimental top

2-Chloro-3-nitropyridine was obtained from the Aldrich Chemical Company, and was recrystallized from ethyl acetate.

Structure description top

2-Chloro-3-nitropyridine is isostructural with the iodo analog. In the iodo compound, the I···O contact is necessarily longer (Mao & Chen, 2009).

For the crystal structure of isostructural 2-iodo-3-nitropyridine, see: Mao & Chen (2009). For the crystal structure of 2-chloro-5-nitropyridine, see: Ng (2010).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₅H₃ClNO₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Non-classical hydrogen-bonded layer motif.

2-chloro-3-nitropyridine top

Crystal data top

C₅H₃ClN₂O₂	F(000) = 320
M_r = 158.54	D_x = 1.668 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1393 reflections
a = 7.613 (1) Å	θ = 3.3–24.8°
b = 12.232 (2) Å	µ = 0.53 mm⁻¹
c = 7.716 (1) Å	T = 293 K
β = 118.485 (2)°	Block, faint yellow
V = 631.5 (2) Å³	0.30 × 0.20 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1445 independent reflections
Radiation source: fine-focus sealed tube	1061 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.771, T_max = 0.862	k = −15→15
5889 measured reflections	l = −9→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	All H-atom parameters refined
S = 1.02	w = 1/[σ²(F_o²) + (0.0539P)² + 0.1169P] where P = (F_o² + 2F_c²)/3
1445 reflections	(Δ/σ)_max = 0.001
103 parameters	Δρ_max = 0.22 e Å⁻³
3 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₅H₃ClN₂O₂	V = 631.5 (2) Å³
M_r = 158.54	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.613 (1) Å	µ = 0.53 mm⁻¹
b = 12.232 (2) Å	T = 293 K
c = 7.716 (1) Å	0.30 × 0.20 × 0.05 mm
β = 118.485 (2)°

Data collection top

Bruker SMART APEX diffractometer	1445 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1061 reflections with I > 2σ(I)
T_min = 0.771, T_max = 0.862	R_int = 0.040
5889 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	3 restraints
wR(F²) = 0.108	All H-atom parameters refined
S = 1.02	Δρ_max = 0.22 e Å⁻³
1445 reflections	Δρ_min = −0.29 e Å⁻³
103 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.67770 (9)	0.67094 (4)	0.54558 (9)	0.0583 (2)
O1	0.5971 (3)	0.89254 (15)	0.6322 (3)	0.0793 (6)
O2	0.8242 (3)	1.00241 (15)	0.6464 (3)	0.0804 (6)
N1	0.6852 (3)	0.71189 (13)	0.2214 (3)	0.0471 (4)
N2	0.7123 (3)	0.92525 (15)	0.5760 (3)	0.0514 (5)
C1	0.6891 (3)	0.75880 (14)	0.3767 (3)	0.0381 (4)
C2	0.7109 (3)	0.87120 (14)	0.4062 (3)	0.0375 (4)
C3	0.7322 (3)	0.93592 (16)	0.2719 (3)	0.0468 (5)
C4	0.7252 (4)	0.88674 (18)	0.1090 (3)	0.0522 (5)
C5	0.7011 (3)	0.77541 (19)	0.0896 (3)	0.0516 (5)
H3	0.751 (3)	1.0104 (9)	0.294 (3)	0.060 (7)*
H4	0.740 (3)	0.9261 (17)	0.013 (3)	0.061 (7)*
H5	0.693 (3)	0.7407 (18)	−0.021 (2)	0.060 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0742 (4)	0.0455 (3)	0.0605 (4)	−0.0024 (2)	0.0366 (3)	0.0121 (2)
O1	0.1151 (16)	0.0782 (12)	0.0759 (13)	0.0077 (11)	0.0709 (13)	−0.0011 (9)
O2	0.0855 (13)	0.0709 (11)	0.0755 (12)	−0.0105 (10)	0.0308 (11)	−0.0382 (10)
N1	0.0558 (11)	0.0367 (8)	0.0490 (10)	−0.0028 (7)	0.0252 (9)	−0.0068 (7)
N2	0.0605 (12)	0.0499 (10)	0.0427 (10)	0.0115 (8)	0.0236 (9)	−0.0031 (8)
C1	0.0370 (10)	0.0354 (9)	0.0399 (10)	0.0002 (7)	0.0168 (8)	0.0023 (7)
C2	0.0385 (10)	0.0340 (8)	0.0378 (10)	0.0031 (7)	0.0164 (8)	−0.0014 (7)
C3	0.0585 (13)	0.0324 (9)	0.0497 (12)	−0.0014 (8)	0.0260 (10)	−0.0009 (8)
C4	0.0671 (14)	0.0491 (12)	0.0507 (13)	−0.0024 (10)	0.0366 (11)	0.0038 (9)
C5	0.0640 (14)	0.0520 (12)	0.0447 (12)	−0.0029 (10)	0.0307 (11)	−0.0083 (9)

Geometric parameters (Å, º) top

Cl1—C1	1.7226 (18)	C2—C3	1.374 (3)
O1—N2	1.217 (2)	C3—C4	1.371 (3)
O2—N2	1.213 (2)	C3—H3	0.925 (9)
N1—C1	1.317 (2)	C4—C5	1.373 (3)
N1—C5	1.330 (3)	C4—H4	0.930 (10)
N2—C2	1.462 (2)	C5—H5	0.929 (10)
C1—C2	1.391 (3)

C1—N1—C5	118.07 (17)	C4—C3—C2	118.15 (18)
O2—N2—O1	124.60 (19)	C4—C3—H3	122.2 (15)
O2—N2—C2	117.20 (19)	C2—C3—H3	119.7 (15)
O1—N2—C2	118.15 (18)	C3—C4—C5	118.67 (19)
N1—C1—C2	121.95 (16)	C3—C4—H4	122.2 (15)
N1—C1—Cl1	115.43 (14)	C5—C4—H4	119.2 (15)
C2—C1—Cl1	122.55 (14)	N1—C5—C4	123.54 (18)
C3—C2—C1	119.58 (17)	N1—C5—H5	116.5 (15)
C3—C2—N2	117.52 (16)	C4—C5—H5	120.0 (15)
C1—C2—N2	122.90 (17)

C5—N1—C1—C2	−0.5 (3)	O2—N2—C2—C1	143.2 (2)
C5—N1—C1—Cl1	−177.56 (15)	O1—N2—C2—C1	−39.3 (3)
N1—C1—C2—C3	−1.1 (3)	C1—C2—C3—C4	1.9 (3)
Cl1—C1—C2—C3	175.72 (15)	N2—C2—C3—C4	−178.09 (19)
N1—C1—C2—N2	178.96 (18)	C2—C3—C4—C5	−1.2 (3)
Cl1—C1—C2—N2	−4.2 (3)	C1—N1—C5—C4	1.3 (3)
O2—N2—C2—C3	−36.8 (3)	C3—C4—C5—N1	−0.4 (4)
O1—N2—C2—C3	140.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.93 (1)	2.53 (1)	3.430 (3)	166 (2)
C4—H4···O1ⁱⁱ	0.93 (1)	2.64 (2)	3.327 (3)	132 (2)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₅H₃ClN₂O₂
M_r	158.54
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.613 (1), 12.232 (2), 7.716 (1)
β (°)	118.485 (2)
V (Å³)	631.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.30 × 0.20 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.771, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	5889, 1445, 1061
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.108, 1.02
No. of reflections	1445
No. of parameters	103
No. of restraints	3
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.29

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.93 (1)	2.53 (1)	3.430 (3)	166 (2)
C4—H4···O1ⁱⁱ	0.93 (1)	2.64 (2)	3.327 (3)	132 (2)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x, y, z−1.

Acknowledgements

I thank the University of Malaya for supporting this study.

References

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