2-Chloro-5-nitro­aniline

Saeed, A.; Ashraf, Z.; Batool, M.; Bolte, M.

doi:10.1107/S160053680901945X

organic compounds

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Volume 65| Part 6| June 2009| Page o1417

doi:10.1107/S160053680901945X

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2-Chloro-5-nitroaniline

Aamer Saeed,^a ^* Zaman Ashraf,^b Mahira Batool ^a and Michael Bolte ^c

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bRiphah Institute of Pharmaceutical Sciences, Islamabad, Pakistan, and ^cInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 19 May 2009; accepted 22 May 2009; online 29 May 2009)

The molecule of the title compound, C₆H₅ClN₂O₂, is close to being planar (rms deviation = 0.032 Å for all non-H atoms), with a maximum deviation of −0.107 (3) Å for an O atom. In the crystal structure, intermolecular N—H⋯O and N—H⋯N interactions link the molecules into a three-dimensional network.

Related literature

For applications of substituted nitrobenzene and aniline derivatives, see: Heinisch et al. (1997 ); Wang et al. (2000 ); Yosuke et al. (2003 ); Zou et al. (1997 ). For a related structure, see: Zhang et al. (2004 ). For bond-length data, see: Allen et al. (1987 ). For synthesis, see: Suwanprasop et al. (2003 ).

Experimental

Crystal data

C₆H₅ClN₂O₂
M_r = 172.57
Monoclinic, P 2₁ /n
a = 13.6233 (10) Å
b = 3.7445 (3) Å
c = 13.6420 (9) Å
β = 91.768 (5)°
V = 695.58 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 173 K
0.35 × 0.34 × 0.29 mm

Data collection

Stoe IPDSII two-circle diffractometer
Absorption correction: multi-scan (MULABS; Blessing, 1995 ) T_min = 0.847, T_max = 0.871
5108 measured reflections
1300 independent reflections
1266 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.061
S = 1.06
1300 reflections
110 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.85 (2)	2.33 (2)	3.1521 (18)	163.2 (19)
N2—H2B⋯N2ⁱⁱ	0.88 (3)	2.44 (2)	3.1452 (19)	137.4 (18)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-RED (Stoe & Cie, 2001); data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901945X/hk2694sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901945X/hk2694Isup2.hkl

checkCIF report

Comment top

Substituted nitrobenzene and aniline derivatives are valuable as intermediates towards a variety of dye and pigments, heterocycles, pesticides, rubber chemicals and agricultural products, and are useful as textile printing agents, nickel stripping agents and polymerization catalysts. Thus, then title compound is an important intermediate or starting point in the syntheses of alkyl derivatives of 2-aminobenzenethiols substituted by chloro and nitro groups (Wang et al., 2000), donor-bridge-acceptor' triad compounds containing the aromatic sulfur bridges (Yosuke et al., 2003), pyridazinobenzodiazepin-5-ones as non-nucleoside HIV Reverse Transcriptase Inhibitors (Heinisch et al., 1997) and 2-chloro-5,6-dihalo-D-ribofuranosylbenzimidazoles as potential agents for human cytomegalovirus infections (Zou et al., 1997). We report herein the crystal structure of the title compound, as a key starting point towards many heterocycles.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges, and may be compared with the corresponding values in N-tert-butyl-4-chloro-5-methyl-2-nitroaniline (Zhang et al., 2004). Ring A (C1–C6) is, of course, planar. Atoms Cl1, O1, O2, N1 and N2 are 0.019 (3), 0.104 (3), -0.107 (3), 0.003 (3) and -0.066 (3) Å away from the ring plane, respectively. So, the molecule is nearly planar.

In the crystal structure, intermolecular N—H···O and N—H···N hydrogen bonds (Table 1) link the molecules into a network, in which they may be effective in the stabilization of the structure.

Related literature top

For applications of substituted nitrobenzene and aniline derivatives, see: Heinisch et al. (1997); Wang et al. (2000); Yosuke et al. (2003); Zou et al. (1997). For a related structure, see: Zhang et al. (2004). For bond-length data, see: Allen et al. (1987). For synthesis, see: Suwanprasop et al. (2003).

Experimental top

The title compound was prepared by nitration and selective reduction of 4-nitroaniline according to the literature method (Suwanprasop et al., 2003). Recrystallization from methanol afforded the title compound. Anal. calcd. for C₆H₅Cl_N2_O2: C, 41.76; H, 2.92; N, 16.23%; found: C, 41.71; H, 2.97; N, 16.16%

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-RED (Stoe & Cie, 2001); data reduction: X-RED (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

2-Chloro-5-nitroaniline top

Crystal data top

C₆H₅ClN₂O₂	F(000) = 352
M_r = 172.57	D_x = 1.648 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7189 reflections
a = 13.6233 (10) Å	θ = 3.4–25.9°
b = 3.7445 (3) Å	µ = 0.49 mm⁻¹
c = 13.6420 (9) Å	T = 173 K
β = 91.768 (5)°	Block, orange
V = 695.58 (9) Å³	0.35 × 0.34 × 0.29 mm
Z = 4

Data collection top

Stoe IPDSII two-circle diffractometer	1300 independent reflections
Radiation source: fine-focus sealed tube	1266 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 25.5°, θ_min = 3.4°
Absorption correction: multi-scan (MULABS; Blessing, 1995)	h = −16→14
T_min = 0.847, T_max = 0.871	k = −4→4
5108 measured reflections	l = −16→16

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)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.061	w = 1/[σ²(F_o²) + (0.0448P)² + 0.0466P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1300 reflections	Δρ_max = 0.20 e Å⁻³
110 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (4)

Crystal data top

C₆H₅ClN₂O₂	V = 695.58 (9) Å³
M_r = 172.57	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.6233 (10) Å	µ = 0.49 mm⁻¹
b = 3.7445 (3) Å	T = 173 K
c = 13.6420 (9) Å	0.35 × 0.34 × 0.29 mm
β = 91.768 (5)°

Data collection top

Stoe IPDSII two-circle diffractometer	1300 independent reflections
Absorption correction: multi-scan (MULABS; Blessing, 1995)	1266 reflections with I > 2σ(I)
T_min = 0.847, T_max = 0.871	R_int = 0.034
5108 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.20 e Å⁻³
1300 reflections	Δρ_min = −0.21 e Å⁻³
110 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.

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	0.91913 (3)	0.59906 (8)	0.62642 (3)	0.02963 (14)
O1	0.50548 (9)	0.8247 (4)	0.37207 (9)	0.0385 (3)
O2	0.60383 (10)	1.0787 (4)	0.27322 (9)	0.0475 (4)
N1	0.58750 (10)	0.9201 (3)	0.34951 (9)	0.0258 (3)
N2	0.70761 (10)	0.4832 (4)	0.66629 (9)	0.0255 (3)
H2B	0.7582 (18)	0.367 (5)	0.6920 (18)	0.043 (6)*
H2A	0.6514 (17)	0.384 (4)	0.6685 (15)	0.029 (5)*
C1	0.82203 (10)	0.6968 (3)	0.54548 (10)	0.0215 (3)
C2	0.72634 (11)	0.6173 (3)	0.57428 (10)	0.0203 (3)
C3	0.64960 (10)	0.6935 (3)	0.50720 (10)	0.0206 (3)
H3	0.5836	0.6427	0.5230	0.025*
C4	0.67060 (10)	0.8434 (3)	0.41772 (10)	0.0206 (3)
C5	0.76477 (11)	0.9244 (3)	0.38893 (11)	0.0231 (3)
H5	0.7764	1.0285	0.3269	0.028*
C6	0.84118 (11)	0.8461 (4)	0.45509 (11)	0.0248 (3)
H6	0.9070	0.8952	0.4383	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0223 (2)	0.03330 (19)	0.0329 (2)	0.00210 (13)	−0.00586 (12)	−0.00076 (14)
O1	0.0221 (6)	0.0617 (7)	0.0315 (6)	−0.0054 (5)	−0.0011 (4)	0.0122 (5)
O2	0.0374 (7)	0.0750 (10)	0.0298 (6)	−0.0099 (6)	−0.0040 (5)	0.0271 (6)
N1	0.0252 (7)	0.0302 (6)	0.0218 (6)	−0.0012 (5)	0.0000 (5)	0.0029 (5)
N2	0.0266 (7)	0.0291 (6)	0.0206 (6)	−0.0039 (6)	−0.0011 (5)	0.0041 (5)
C1	0.0215 (7)	0.0184 (5)	0.0245 (7)	0.0006 (5)	−0.0014 (5)	−0.0047 (5)
C2	0.0246 (7)	0.0181 (6)	0.0182 (7)	−0.0004 (5)	0.0014 (5)	−0.0026 (4)
C3	0.0204 (6)	0.0216 (6)	0.0201 (6)	−0.0019 (5)	0.0034 (5)	−0.0021 (5)
C4	0.0222 (7)	0.0196 (6)	0.0198 (6)	0.0001 (5)	0.0006 (5)	−0.0015 (5)
C5	0.0257 (7)	0.0235 (6)	0.0203 (7)	−0.0021 (5)	0.0060 (6)	−0.0007 (5)
C6	0.0199 (7)	0.0247 (6)	0.0301 (7)	−0.0009 (5)	0.0054 (5)	−0.0027 (5)

Geometric parameters (Å, º) top

N1—O1	1.2216 (19)	C2—C3	1.397 (2)
N1—O2	1.2245 (18)	C3—C4	1.382 (2)
N2—H2B	0.88 (3)	C3—H3	0.9500
N2—H2A	0.85 (2)	C4—C5	1.387 (2)
C1—C6	1.386 (2)	C4—N1	1.4713 (18)
C1—C2	1.405 (2)	C5—C6	1.388 (2)
C1—Cl1	1.7357 (14)	C5—H5	0.9500
C2—N2	1.3830 (18)	C6—H6	0.9500

O1—N1—O2	123.19 (14)	C4—C3—C2	119.37 (12)
O1—N1—C4	118.40 (12)	C4—C3—H3	120.3
O2—N1—C4	118.41 (13)	C2—C3—H3	120.3
C2—N2—H2B	112.2 (15)	C3—C4—C5	123.90 (13)
C2—N2—H2A	112.4 (14)	C3—C4—N1	117.51 (12)
H2B—N2—H2A	117.7 (18)	C5—C4—N1	118.59 (13)
C6—C1—C2	122.42 (13)	C4—C5—C6	116.84 (13)
C6—C1—Cl1	119.36 (11)	C4—C5—H5	121.6
C2—C1—Cl1	118.22 (11)	C6—C5—H5	121.6
N2—C2—C3	120.88 (13)	C1—C6—C5	120.38 (13)
N2—C2—C1	121.98 (13)	C1—C6—H6	119.8
C3—C2—C1	117.09 (13)	C5—C6—H6	119.8

C6—C1—C2—N2	−177.05 (13)	N1—C4—C5—C6	−179.64 (12)
Cl1—C1—C2—N2	3.57 (17)	C2—C1—C6—C5	0.2 (2)
C6—C1—C2—C3	0.33 (19)	Cl1—C1—C6—C5	179.57 (10)
Cl1—C1—C2—C3	−179.04 (9)	C4—C5—C6—C1	−0.5 (2)
N2—C2—C3—C4	176.87 (12)	C3—C4—N1—O1	−5.21 (19)
C1—C2—C3—C4	−0.55 (19)	C5—C4—N1—O1	174.73 (13)
C2—C3—C4—C5	0.2 (2)	C3—C4—N1—O2	174.29 (13)
C2—C3—C4—N1	−179.82 (12)	C5—C4—N1—O2	−5.8 (2)
C3—C4—C5—C6	0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.85 (2)	2.33 (2)	3.1521 (18)	163.2 (19)
N2—H2B···N2ⁱⁱ	0.88 (3)	2.44 (2)	3.1452 (19)	137.4 (18)

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

Experimental details

Crystal data
Chemical formula	C₆H₅ClN₂O₂
M_r	172.57
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	13.6233 (10), 3.7445 (3), 13.6420 (9)
β (°)	91.768 (5)
V (Å³)	695.58 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.35 × 0.34 × 0.29

Data collection
Diffractometer	Stoe IPDSII two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Blessing, 1995)
T_min, T_max	0.847, 0.871
No. of measured, independent and observed [I > 2σ(I)] reflections	5108, 1300, 1266
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.06
No. of reflections	1300
No. of parameters	110
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.21

Computer programs: X-AREA (Stoe & Cie, 2001), X-RED (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.85 (2)	2.33 (2)	3.1521 (18)	163.2 (19)
N2—H2B···N2ⁱⁱ	0.88 (3)	2.44 (2)	3.1452 (19)	137.4 (18)

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Heinisch, G., Huber, E., Matuszczak, B., Maurer, A. & Prillinge, U. (1997). Arch. Pharm. 330, 29–34. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
Suwanprasop, S., Suksorn, S., Nhujak, T., Roengsumran, S. & Petsom, A. (2003). Ind. Eng. Chem. Res. 42, 5054–5059. Web of Science CrossRef CAS Google Scholar
Wang, Y., Wu, Y. & Tian, H. (2000). Dyes Pigm. 44, 93–100. Web of Science CrossRef CAS Google Scholar
Yosuke, M., Takako, U. & Tetsuo, M. (2003). Book of Abstracts, Congress of Heterocyclic Chemistry, Tokyo, Japan, Vol. 33, pp. 114–115. Google Scholar
Zhang, Y., Feng, T.-Y. & Li, S.-Y. (2004). Acta Cryst. E60, o2501–o2502. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zou, R., Drach, J. C. & Townsend, L. B. (1997). J. Med. Chem. 40, 811–818. CrossRef CAS PubMed Web of Science Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1417

doi:10.1107/S160053680901945X

Open

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