2-Chloro-5-methyl-3-nitro­pyridine

Zhang, D.-T.; Huo, L.-Y.

doi:10.1107/S160053681104400X

organic compounds

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Volume 67| Part 11| November 2011| Page o3134

doi:10.1107/S160053681104400X

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2-Chloro-5-methyl-3-nitropyridine

Da-Tong Zhang ^a ^* and Ling-Yan Huo ^a

^aSchool of Chemistry and Pharmaceutical Engineering, Shandong Polytechnic University, Jinan 250353, People's Republic of China
^*Correspondence e-mail: datong_zhang2006@yahoo.com.cn

(Received 19 October 2011; accepted 23 October 2011; online 29 October 2011)

The title compound, C₆H₅ClN₂O₂, crystallizes with two independent molecules in the asymmetric unit. Intermolecular C—H⋯O hydrogen bonds stabilize the crystal structure.

Related literature

For aplication of pyridines, see: Madsen-Duggan et al. (2010 ); Meurer et al. (2005 ); Liégeois et al. (1993 ); Kagabu et al. (2005 ). For related structures, see: Ng (2010 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₆H₅ClN₂O₂
M_r = 172.57
Orthorhombic, P n a 2₁
a = 21.435 (6) Å
b = 8.151 (2) Å
c = 8.494 (2) Å
V = 1484.0 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 298 K
0.38 × 0.24 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
7071 measured reflections
2134 independent reflections
1749 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.093
S = 1.06
2134 reflections
201 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.13 e Å⁻³
Absolute structure: Flack (1983), 139 Friedel pairs
Flack parameter: −0.08 (8)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O2ⁱ	0.93	2.51	3.243 (4)	136
Symmetry code: (i) $[-x+1, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681104400X/hg5113sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104400X/hg5113Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681104400X/hg5113Isup3.cml

checkCIF report

Comment top

Substituted pyridines are often used as pharmacophores in medicinal chemistry (Madsen-Duggan et al., 2010; Meurer et al., 2005). 2-Chloro-5-methyl-3-nitropyridine (I) is important intermediate in the synthesis of some bioactive products (Liégeois, et al., 1993; Kagabu, et al., 2005). The title compound was prepared by the chlorination of 2-hydroxy-5-methyl-3-nitropyridine with thionyl chloride. We present here the crystal structure of (I).

The title compound, C₆H₅ClN₂O₂, crystallizes with two independent molecules in the asymmetric unit. All bond lengths in the molecular are normal (Allen et al., 1987) and in a good agreement with those reported previously (Ng, 2010). C—H···O intermolecular hydrogen bonds stabilize the crystal structure.(Table 1).

Related literature top

For aplication of pyridines, see: Madsen-Duggan et al. (2010); Meurer et al. (2005); Liégeois et al. (1993); Kagabu et al. (2005). For related structures, see: Ng (2010). For standard bond lengths, see: Allen et al. (1987). .

Experimental top

The title compound was synthesized by the reaction of 2-hydroxy-5-methyl-3-nitropyridine (0.01 mol) with thionyl chloride (15 ml) in the presence of a small amount of DMF at reflux (3 h). After evaporation, the reaction residue was diluted with water. The aqueous solution was extracted with dichloromethane, and the organic phase was dried and evaporated to afford the title product in 92% isolated yield. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution of the title compound in a hexane/methylene chloride mixture (1:1 v/v) at room temperature over a period of one week.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.

2-Chloro-5-methyl-3-nitropyridine top

Crystal data top

C₆H₅ClN₂O₂	F(000) = 704
M_r = 172.57	D_x = 1.545 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1564 reflections
a = 21.435 (6) Å	θ = 2.3–22.0°
b = 8.151 (2) Å	µ = 0.46 mm⁻¹
c = 8.494 (2) Å	T = 298 K
V = 1484.0 (7) Å³	Block, colorless
Z = 8	0.38 × 0.24 × 0.21 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1749 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.0°, θ_min = 1.9°
ϕ and ω scans	h = −25→25
7071 measured reflections	k = −9→9
2134 independent reflections	l = −10→6

Refinement top

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0538P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2134 reflections	Δρ_max = 0.20 e Å⁻³
201 parameters	Δρ_min = −0.13 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 139 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.08 (8)

Crystal data top

C₆H₅ClN₂O₂	V = 1484.0 (7) Å³
M_r = 172.57	Z = 8
Orthorhombic, Pna2₁	Mo Kα radiation
a = 21.435 (6) Å	µ = 0.46 mm⁻¹
b = 8.151 (2) Å	T = 298 K
c = 8.494 (2) Å	0.38 × 0.24 × 0.21 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1749 reflections with I > 2σ(I)
7071 measured reflections	R_int = 0.023
2134 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.093	Δρ_max = 0.20 e Å⁻³
S = 1.06	Δρ_min = −0.13 e Å⁻³
2134 reflections	Absolute structure: Flack (1983), 139 Friedel pairs
201 parameters	Absolute structure parameter: −0.08 (8)
1 restraint

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cl1	0.64412 (4)	0.34108 (9)	0.69639 (8)	0.0705 (3)
Cl2	0.64313 (4)	0.85811 (9)	0.70504 (10)	0.0812 (3)
O1	0.50283 (10)	0.0831 (3)	0.5349 (5)	0.1076 (10)
O2	0.51384 (10)	0.3414 (3)	0.5424 (4)	0.0821 (7)
O3	0.48112 (10)	0.7214 (3)	0.4606 (4)	0.0982 (9)
O4	0.52431 (11)	0.6869 (3)	0.6857 (4)	0.0952 (8)
N1	0.70207 (10)	0.2297 (3)	0.4520 (3)	0.0583 (6)
N2	0.53214 (10)	0.2046 (3)	0.5159 (3)	0.0572 (6)
N3	0.69533 (11)	0.7387 (3)	0.4591 (3)	0.0640 (6)
N4	0.52614 (12)	0.7020 (3)	0.5437 (4)	0.0652 (7)
C1	0.64679 (12)	0.2463 (3)	0.5147 (3)	0.0462 (6)
C2	0.59406 (10)	0.1857 (3)	0.4440 (3)	0.0404 (6)
C3	0.59813 (12)	0.1067 (3)	0.3021 (3)	0.0443 (6)
H3B	0.5626	0.0632	0.2549	0.053*
C4	0.65528 (11)	0.0926 (3)	0.2303 (3)	0.0467 (7)
C5	0.70548 (13)	0.1550 (3)	0.3124 (4)	0.0591 (7)
H5A	0.7447	0.1443	0.2670	0.071*
C6	0.66285 (14)	0.0156 (4)	0.0719 (4)	0.0673 (8)
H6A	0.6313	−0.0665	0.0572	0.101*
H6B	0.7033	−0.0343	0.0647	0.101*
H6C	0.6588	0.0982	−0.0081	0.101*
C7	0.64127 (13)	0.7526 (3)	0.5297 (3)	0.0513 (7)
C8	0.58714 (12)	0.6920 (3)	0.4649 (3)	0.0479 (7)
C9	0.58893 (12)	0.6180 (3)	0.3199 (3)	0.0482 (7)
H9A	0.5525	0.5788	0.2740	0.058*
C10	0.64506 (11)	0.6021 (3)	0.2429 (3)	0.0500 (8)
C11	0.69626 (13)	0.6619 (4)	0.3200 (4)	0.0634 (8)
H11A	0.7349	0.6480	0.2717	0.076*
C12	0.65035 (14)	0.5240 (4)	0.0832 (4)	0.0687 (8)
H12A	0.6920	0.4835	0.0684	0.103*
H12B	0.6411	0.6040	0.0035	0.103*
H12C	0.6213	0.4347	0.0755	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0895 (6)	0.0727 (5)	0.0492 (5)	0.0039 (4)	−0.0117 (4)	−0.0149 (5)
Cl2	0.1138 (7)	0.0757 (6)	0.0542 (6)	0.0059 (4)	−0.0185 (5)	−0.0151 (6)
O1	0.0742 (14)	0.0879 (17)	0.161 (3)	−0.0239 (14)	0.0468 (16)	0.006 (2)
O2	0.0775 (14)	0.0813 (15)	0.0875 (18)	0.0228 (11)	0.0239 (14)	−0.0082 (13)
O3	0.0574 (14)	0.118 (2)	0.119 (3)	0.0116 (14)	−0.0001 (14)	−0.0181 (17)
O4	0.1076 (19)	0.1013 (18)	0.0766 (19)	0.0100 (14)	0.0405 (16)	−0.0110 (17)
N1	0.0416 (12)	0.0721 (15)	0.0613 (17)	−0.0080 (11)	−0.0047 (12)	−0.0035 (13)
N2	0.0503 (13)	0.0667 (16)	0.0547 (16)	0.0012 (12)	0.0115 (12)	0.0037 (13)
N3	0.0563 (14)	0.0801 (16)	0.0555 (16)	−0.0106 (12)	−0.0083 (14)	−0.0021 (14)
N4	0.0648 (18)	0.0604 (16)	0.071 (2)	0.0057 (13)	0.0145 (16)	−0.0095 (15)
C1	0.0549 (15)	0.0421 (13)	0.0415 (16)	0.0006 (11)	−0.0035 (13)	0.0015 (12)
C2	0.0403 (13)	0.0406 (13)	0.0404 (16)	0.0003 (10)	0.0005 (11)	0.0043 (11)
C3	0.0434 (14)	0.0413 (13)	0.0483 (16)	−0.0016 (10)	−0.0047 (13)	0.0013 (12)
C4	0.0477 (14)	0.0492 (13)	0.0433 (19)	0.0028 (11)	0.0002 (13)	0.0040 (12)
C5	0.0425 (14)	0.0787 (19)	0.0563 (19)	0.0001 (13)	0.0060 (14)	0.0006 (17)
C6	0.0776 (18)	0.074 (2)	0.0503 (18)	0.0075 (16)	0.0082 (16)	−0.0046 (16)
C7	0.0661 (17)	0.0473 (15)	0.0406 (16)	0.0024 (12)	−0.0097 (14)	0.0052 (12)
C8	0.0515 (15)	0.0444 (14)	0.0479 (17)	0.0034 (11)	0.0037 (13)	0.0076 (13)
C9	0.0498 (15)	0.0443 (13)	0.0505 (18)	−0.0049 (11)	−0.0076 (13)	0.0049 (13)
C10	0.0553 (17)	0.0498 (15)	0.0449 (19)	−0.0011 (12)	0.0034 (13)	0.0076 (13)
C11	0.0455 (15)	0.084 (2)	0.061 (2)	−0.0082 (14)	0.0031 (15)	0.0033 (18)
C12	0.0832 (19)	0.076 (2)	0.0468 (18)	−0.0011 (17)	0.0098 (16)	−0.0015 (16)

Geometric parameters (Å, º) top

Cl1—C1	1.727 (3)	C4—C5	1.380 (4)
Cl2—C7	1.720 (3)	C4—C6	1.494 (4)
O1—N2	1.184 (3)	C5—H5A	0.9300
O2—N2	1.203 (3)	C6—H6A	0.9600
O3—N4	1.206 (4)	C6—H6B	0.9600
O4—N4	1.213 (4)	C6—H6C	0.9600
N1—C1	1.306 (3)	C7—C8	1.376 (4)
N1—C5	1.335 (4)	C8—C9	1.372 (4)
N2—C2	1.469 (3)	C9—C10	1.376 (4)
N3—C7	1.310 (4)	C9—H9A	0.9300
N3—C11	1.338 (4)	C10—C11	1.368 (4)
N4—C8	1.471 (4)	C10—C12	1.502 (4)
C1—C2	1.372 (3)	C11—H11A	0.9300
C2—C3	1.369 (4)	C12—H12A	0.9600
C3—C4	1.373 (4)	C12—H12B	0.9600
C3—H3B	0.9300	C12—H12C	0.9600

C1—N1—C5	117.3 (2)	H6A—C6—H6B	109.5
O1—N2—O2	125.2 (3)	C4—C6—H6C	109.5
O1—N2—C2	116.6 (3)	H6A—C6—H6C	109.5
O2—N2—C2	118.0 (2)	H6B—C6—H6C	109.5
C7—N3—C11	117.3 (2)	N3—C7—C8	122.1 (3)
O3—N4—O4	124.7 (3)	N3—C7—Cl2	114.8 (2)
O3—N4—C8	116.9 (3)	C8—C7—Cl2	123.1 (2)
O4—N4—C8	118.4 (3)	C9—C8—C7	119.6 (3)
N1—C1—C2	122.1 (3)	C9—C8—N4	117.2 (3)
N1—C1—Cl1	116.2 (2)	C7—C8—N4	123.2 (3)
C2—C1—Cl1	121.7 (2)	C8—C9—C10	119.5 (3)
C3—C2—C1	120.1 (2)	C8—C9—H9A	120.2
C3—C2—N2	118.2 (2)	C10—C9—H9A	120.2
C1—C2—N2	121.6 (2)	C11—C10—C9	116.1 (3)
C2—C3—C4	119.2 (2)	C11—C10—C12	121.5 (3)
C2—C3—H3B	120.4	C9—C10—C12	122.4 (3)
C4—C3—H3B	120.4	N3—C11—C10	125.3 (3)
C3—C4—C5	116.1 (3)	N3—C11—H11A	117.3
C3—C4—C6	122.2 (3)	C10—C11—H11A	117.3
C5—C4—C6	121.7 (3)	C10—C12—H12A	109.5
N1—C5—C4	125.1 (3)	C10—C12—H12B	109.5
N1—C5—H5A	117.5	H12A—C12—H12B	109.5
C4—C5—H5A	117.5	C10—C12—H12C	109.5
C4—C6—H6A	109.5	H12A—C12—H12C	109.5
C4—C6—H6B	109.5	H12B—C12—H12C	109.5

C5—N1—C1—C2	2.0 (4)	C11—N3—C7—C8	−0.2 (4)
C5—N1—C1—Cl1	179.2 (2)	C11—N3—C7—Cl2	−178.1 (2)
N1—C1—C2—C3	−0.9 (4)	N3—C7—C8—C9	−1.7 (4)
Cl1—C1—C2—C3	−177.95 (19)	Cl2—C7—C8—C9	176.00 (19)
N1—C1—C2—N2	179.7 (2)	N3—C7—C8—N4	178.3 (3)
Cl1—C1—C2—N2	2.7 (3)	Cl2—C7—C8—N4	−4.0 (4)
O1—N2—C2—C3	55.0 (4)	O3—N4—C8—C9	−34.7 (4)
O2—N2—C2—C3	−120.8 (3)	O4—N4—C8—C9	143.8 (3)
O1—N2—C2—C1	−125.7 (3)	O3—N4—C8—C7	145.3 (3)
O2—N2—C2—C1	58.5 (4)	O4—N4—C8—C7	−36.2 (4)
C1—C2—C3—C4	−1.5 (4)	C7—C8—C9—C10	1.5 (4)
N2—C2—C3—C4	177.8 (2)	N4—C8—C9—C10	−178.5 (2)
C2—C3—C4—C5	2.6 (4)	C8—C9—C10—C11	0.6 (4)
C2—C3—C4—C6	−176.9 (2)	C8—C9—C10—C12	−179.3 (2)
C1—N1—C5—C4	−0.8 (4)	C7—N3—C11—C10	2.5 (5)
C3—C4—C5—N1	−1.6 (4)	C9—C10—C11—N3	−2.7 (5)
C6—C4—C5—N1	177.9 (3)	C12—C10—C11—N3	177.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O2ⁱ	0.93	2.51	3.243 (4)	136

Symmetry code: (i) −x+1, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₅ClN₂O₂
M_r	172.57
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	298
a, b, c (Å)	21.435 (6), 8.151 (2), 8.494 (2)
V (Å³)	1484.0 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.38 × 0.24 × 0.21

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7071, 2134, 1749
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.093, 1.06
No. of reflections	2134
No. of parameters	201
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.13
Absolute structure	Flack (1983), 139 Friedel pairs
Absolute structure parameter	−0.08 (8)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O2ⁱ	0.93	2.51	3.243 (4)	135.6

Symmetry code: (i) −x+1, −y+1, z−1/2.

References

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Volume 67| Part 11| November 2011| Page o3134

doi:10.1107/S160053681104400X

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