2-Chloro-3-nitro­pyridine

Abstract

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,

• a = 7.613 (1) Å

• b = 12.232 (2) Å

• c = 7.716 (1) Å

• β = 118.485 (2)°

• V = 631.5 (2) ų

• 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[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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

Refinement

Carbon bound H-atoms were located in a difference Fourier map. They were refined with a distance restraint of C–H 0.93±0.01 Å; their temperature factors were refined without constraints.

Figures

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.

Crystal data

C5H3ClN2O2	F(000) = 320
Mr = 158.54	Dx = 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

Bruker SMART APEX diffractometer	1445 independent reflections
Radiation source: fine-focus sealed tube	1061 reflections with I > 2σ(I)
graphite	Rint = 0.040
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.771, Tmax = 0.862	k = −15→15
5889 measured reflections	l = −9→10

Refinement

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(Fo2) + (0.0539P)2 + 0.1169P] where P = (Fo2 + 2Fc2)/3
1445 reflections	(Δ/σ)max = 0.001
103 parameters	Δρmax = 0.22 e Å−3
3 restraints	Δρmin = −0.28 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.