organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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2-Chloro-5-nitro­aniline

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[Heinisch, G., Huber, E., Matuszczak, B., Maurer, A. & Prillinge, U. (1997). Arch. Pharm. 330, 29-34.]); Wang et al. (2000[Wang, Y., Wu, Y. & Tian, H. (2000). Dyes Pigm. 44, 93-100.]); Yosuke et al. (2003[Yosuke, M., Takako, U. & Tetsuo, M. (2003). Book of Abstracts, Congress of Heterocyclic Chemistry, Tokyo, Japan, Vol. 33, pp. 114-115.]); Zou et al. (1997[Zou, R., Drach, J. C. & Townsend, L. B. (1997). J. Med. Chem. 40, 811-818.]). For a related structure, see: Zhang et al. (2004[Zhang, Y., Feng, T.-Y. & Li, S.-Y. (2004). Acta Cryst. E60, o2501-o2502.]). For bond-length data, see: Allen et al. (1987[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.]). For synthesis, see: Suwanprasop et al. (2003[Suwanprasop, S., Suksorn, S., Nhujak, T., Roengsumran, S. & Petsom, A. (2003). Ind. Eng. Chem. Res. 42, 5054-5059.]).

[Scheme 1]

Experimental

Crystal data
  • C6H5ClN2O2

  • Mr = 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[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.847, Tmax = 0.871

  • 5108 measured reflections

  • 1300 independent reflections

  • 1266 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Stoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-RED (Stoe & Cie, 2001[Stoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany.]); data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 C6H5ClN2O2: C, 41.76; H, 2.92; N, 16.23%; found: C, 41.71; H, 2.97; N, 16.16%

Refinement top

H atoms (for NH2) were located in a difference synthesis and refined isotropically. The remaining H atoms were positioned geometrically, with C—H = 0.95 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

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
[Figure 1] 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
C6H5ClN2O2F(000) = 352
Mr = 172.57Dx = 1.648 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7189 reflections
a = 13.6233 (10) Åθ = 3.4–25.9°
b = 3.7445 (3) ŵ = 0.49 mm1
c = 13.6420 (9) ÅT = 173 K
β = 91.768 (5)°Block, orange
V = 695.58 (9) Å30.35 × 0.34 × 0.29 mm
Z = 4
Data collection top
Stoe IPDSII two-circle
diffractometer
1300 independent reflections
Radiation source: fine-focus sealed tube1266 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ω scansθmax = 25.5°, θmin = 3.4°
Absorption correction: multi-scan
(MULABS; Blessing, 1995)
h = 1614
Tmin = 0.847, Tmax = 0.871k = 44
5108 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.061 w = 1/[σ2(Fo2) + (0.0448P)2 + 0.0466P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
1300 reflectionsΔρmax = 0.20 e Å3
110 parametersΔρmin = 0.21 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.034 (4)
Crystal data top
C6H5ClN2O2V = 695.58 (9) Å3
Mr = 172.57Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.6233 (10) ŵ = 0.49 mm1
b = 3.7445 (3) ÅT = 173 K
c = 13.6420 (9) Å0.35 × 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)
Tmin = 0.847, Tmax = 0.871Rint = 0.034
5108 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.20 e Å3
1300 reflectionsΔρmin = 0.21 e Å3
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
xyzUiso*/Ueq
Cl10.91913 (3)0.59906 (8)0.62642 (3)0.02963 (14)
O10.50548 (9)0.8247 (4)0.37207 (9)0.0385 (3)
O20.60383 (10)1.0787 (4)0.27322 (9)0.0475 (4)
N10.58750 (10)0.9201 (3)0.34951 (9)0.0258 (3)
N20.70761 (10)0.4832 (4)0.66629 (9)0.0255 (3)
H2B0.7582 (18)0.367 (5)0.6920 (18)0.043 (6)*
H2A0.6514 (17)0.384 (4)0.6685 (15)0.029 (5)*
C10.82203 (10)0.6968 (3)0.54548 (10)0.0215 (3)
C20.72634 (11)0.6173 (3)0.57428 (10)0.0203 (3)
C30.64960 (10)0.6935 (3)0.50720 (10)0.0206 (3)
H30.58360.64270.52300.025*
C40.67060 (10)0.8434 (3)0.41772 (10)0.0206 (3)
C50.76477 (11)0.9244 (3)0.38893 (11)0.0231 (3)
H50.77641.02850.32690.028*
C60.84118 (11)0.8461 (4)0.45509 (11)0.0248 (3)
H60.90700.89520.43830.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0223 (2)0.03330 (19)0.0329 (2)0.00210 (13)0.00586 (12)0.00076 (14)
O10.0221 (6)0.0617 (7)0.0315 (6)0.0054 (5)0.0011 (4)0.0122 (5)
O20.0374 (7)0.0750 (10)0.0298 (6)0.0099 (6)0.0040 (5)0.0271 (6)
N10.0252 (7)0.0302 (6)0.0218 (6)0.0012 (5)0.0000 (5)0.0029 (5)
N20.0266 (7)0.0291 (6)0.0206 (6)0.0039 (6)0.0011 (5)0.0041 (5)
C10.0215 (7)0.0184 (5)0.0245 (7)0.0006 (5)0.0014 (5)0.0047 (5)
C20.0246 (7)0.0181 (6)0.0182 (7)0.0004 (5)0.0014 (5)0.0026 (4)
C30.0204 (6)0.0216 (6)0.0201 (6)0.0019 (5)0.0034 (5)0.0021 (5)
C40.0222 (7)0.0196 (6)0.0198 (6)0.0001 (5)0.0006 (5)0.0015 (5)
C50.0257 (7)0.0235 (6)0.0203 (7)0.0021 (5)0.0060 (6)0.0007 (5)
C60.0199 (7)0.0247 (6)0.0301 (7)0.0009 (5)0.0054 (5)0.0027 (5)
Geometric parameters (Å, º) top
N1—O11.2216 (19)C2—C31.397 (2)
N1—O21.2245 (18)C3—C41.382 (2)
N2—H2B0.88 (3)C3—H30.9500
N2—H2A0.85 (2)C4—C51.387 (2)
C1—C61.386 (2)C4—N11.4713 (18)
C1—C21.405 (2)C5—C61.388 (2)
C1—Cl11.7357 (14)C5—H50.9500
C2—N21.3830 (18)C6—H60.9500
O1—N1—O2123.19 (14)C4—C3—C2119.37 (12)
O1—N1—C4118.40 (12)C4—C3—H3120.3
O2—N1—C4118.41 (13)C2—C3—H3120.3
C2—N2—H2B112.2 (15)C3—C4—C5123.90 (13)
C2—N2—H2A112.4 (14)C3—C4—N1117.51 (12)
H2B—N2—H2A117.7 (18)C5—C4—N1118.59 (13)
C6—C1—C2122.42 (13)C4—C5—C6116.84 (13)
C6—C1—Cl1119.36 (11)C4—C5—H5121.6
C2—C1—Cl1118.22 (11)C6—C5—H5121.6
N2—C2—C3120.88 (13)C1—C6—C5120.38 (13)
N2—C2—C1121.98 (13)C1—C6—H6119.8
C3—C2—C1117.09 (13)C5—C6—H6119.8
C6—C1—C2—N2177.05 (13)N1—C4—C5—C6179.64 (12)
Cl1—C1—C2—N23.57 (17)C2—C1—C6—C50.2 (2)
C6—C1—C2—C30.33 (19)Cl1—C1—C6—C5179.57 (10)
Cl1—C1—C2—C3179.04 (9)C4—C5—C6—C10.5 (2)
N2—C2—C3—C4176.87 (12)C3—C4—N1—O15.21 (19)
C1—C2—C3—C40.55 (19)C5—C4—N1—O1174.73 (13)
C2—C3—C4—C50.2 (2)C3—C4—N1—O2174.29 (13)
C2—C3—C4—N1179.82 (12)C5—C4—N1—O25.8 (2)
C3—C4—C5—C60.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.85 (2)2.33 (2)3.1521 (18)163.2 (19)
N2—H2B···N2ii0.88 (3)2.44 (2)3.1452 (19)137.4 (18)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+3/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC6H5ClN2O2
Mr172.57
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)13.6233 (10), 3.7445 (3), 13.6420 (9)
β (°) 91.768 (5)
V3)695.58 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.35 × 0.34 × 0.29
Data collection
DiffractometerStoe IPDSII two-circle
diffractometer
Absorption correctionMulti-scan
(MULABS; Blessing, 1995)
Tmin, Tmax0.847, 0.871
No. of measured, independent and
observed [I > 2σ(I)] reflections
5108, 1300, 1266
Rint0.034
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.061, 1.06
No. of reflections1300
No. of parameters110
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2A···O1i0.85 (2)2.33 (2)3.1521 (18)163.2 (19)
N2—H2B···N2ii0.88 (3)2.44 (2)3.1452 (19)137.4 (18)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+3/2, y1/2, z+3/2.
 

References

First citationAllen, 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
First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHeinisch, G., Huber, E., Matuszczak, B., Maurer, A. & Prillinge, U. (1997). Arch. Pharm. 330, 29–34.  CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationSuwanprasop, S., Suksorn, S., Nhujak, T., Roengsumran, S. & Petsom, A. (2003). Ind. Eng. Chem. Res. 42, 5054–5059.  Web of Science CrossRef CAS Google Scholar
First citationWang, Y., Wu, Y. & Tian, H. (2000). Dyes Pigm. 44, 93–100.  Web of Science CrossRef CAS Google Scholar
First citationYosuke, M., Takako, U. & Tetsuo, M. (2003). Book of Abstracts, Congress of Heterocyclic Chemistry, Tokyo, Japan, Vol. 33, pp. 114–115.  Google Scholar
First citationZhang, Y., Feng, T.-Y. & Li, S.-Y. (2004). Acta Cryst. E60, o2501–o2502.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationZou, 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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