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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): o250.
Published online 2009 December 24. doi:  10.1107/S1600536809054944
PMCID: PMC2980141

4-Bromo-2-chloro­aniline

Abstract

The title compound, C6H5BrClN, is almost planar (r.m.s. deviation = 0.018 Å). In the crystal, mol­ecules are linked by inter­molecular N—H(...)N and weak N—H(...)Br hydrogen bonds, generating sheets.

Related literature

For background to halogentaed aromatic compounds, see: Katritzky et al. (1994 [triangle]). For related structures, see: Cox (2001 [triangle]); Parkin et al. (2005 [triangle]); Ng (2005 [triangle]); Ferguson et al. (1998 [triangle]). For the synthesis, see: Ault & Kraig (1966 [triangle]).

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Object name is e-66-0o250-scheme1.jpg

Experimental

Crystal data

  • C6H5BrClN
  • M r = 206.47
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o250-efi1.jpg
  • a = 10.965 (4) Å
  • b = 15.814 (6) Å
  • c = 4.0232 (15) Å
  • V = 697.7 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.17 mm−1
  • T = 298 K
  • 0.7 × 0.19 × 0.15 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.254, T max = 0.396
  • 5799 measured reflections
  • 1710 independent reflections
  • 1333 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.081
  • S = 0.99
  • 1710 reflections
  • 83 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.48 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 511 Friedel pairs
  • Flack parameter: 0.035 (15)

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809054944/hb5285sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054944/hb5285Isup2.hkl

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

Acknowledgments

The authors thank the Natural Science Foundation of China (No. 20602028) and the NFFTBS (No. J0630429) for financial support.

supplementary crystallographic information

Comment

Halogenated aromatic compounds is an important class of intermediates for the synthesis of bio-active substances such as antibacterial, antioxidizing, antiviral agents (e.g. Katritzky et al., 1994). Despite their simple structures, the X-ray structures of halogenated aniline compounds periodically were reported, such as 2,5-dichloroaniline (Cox, 2001), 2-iodoaniline (Parkin et al., 2005) and 5-chloro-2-nitroaniline (Ng, 2005). We now report the title compound, (I).

The packing of molecules in the crystal structure is stabilized and linked into a two-dimensional texture by intermolecular N—H···N and N—H···Br hydrogen bonds. The N···N distance is 3.172 (4) Å in hydrogen bond N—H···N, which are similar to that observed in 2,4-dibromo-6- chloroaniline (Ferguson et al., 1998), 3.150 (11) Å and 2-iodoaniline (Parkin et al., 2005), 3.161 (14) Å.

Experimental

The tiltle compound was prepared according to a previously reported method (Ault & Kraig, 1966). Colourless needles of (I) were obtained by slow evaporation of a petroleum ether solution.

Refinement

The hydrogen atoms were positioned geometrically, with C—H = 0.93, 0.98, 0.97 and 0.96 Å for phenyl, methine, methylene and methyl H atoms, respectively, and were included in the refinement in the riding model approximation. The displacement parameters of methyl H atoms were set to 1.5Ueq(C), while those of other H atoms were set to 1.2Ueq(C). In the absence of significant anomalous scattering effects, Friedel pairs were merged.

Figures

Fig. 1.
The molecular structure of (I) showing 50% probability displacement ellipsoids.
Fig. 2.
The packing of (I), viewed down the c axis. N—H···N and N—H···Br hydrogen bond interactions are shown as dashed lines.

Crystal data

C6H5BrClNF(000) = 424
Mr = 206.47Dx = 1.965 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1199 reflections
a = 10.965 (4) Åθ = 2.3–29.8°
b = 15.814 (6) ŵ = 6.17 mm1
c = 4.0232 (15) ÅT = 298 K
V = 697.7 (4) Å3Needle, colourless
Z = 40.7 × 0.19 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer1710 independent reflections
Radiation source: fine-focus sealed tube1333 reflections with I > 2σ(I)
graphiteRint = 0.044
[var phi] and ω scanθmax = 29.8°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −14→14
Tmin = 0.254, Tmax = 0.396k = −20→21
5799 measured reflectionsl = −5→5

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033w = 1/[σ2(Fo2) + (0.0374P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.081(Δ/σ)max = 0.008
S = 0.99Δρmax = 0.33 e Å3
1710 reflectionsΔρmin = −0.48 e Å3
83 parametersExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.246 (8)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 511 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.035 (15)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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)

xyzUiso*/Ueq
Br10.28337 (3)0.74386 (2)0.51936 (10)0.0646 (2)
Cl10.42519 (8)0.41363 (5)0.4648 (3)0.0588 (3)
C10.3957 (3)0.65802 (18)0.6258 (8)0.0432 (7)
C20.4999 (3)0.6770 (2)0.7973 (9)0.0494 (8)
H2A0.51510.73220.86560.059*
C30.5812 (3)0.6145 (2)0.8673 (9)0.0456 (8)
H3A0.65180.62760.98460.055*
C40.5613 (3)0.5320 (2)0.7681 (8)0.0428 (8)
C50.4548 (3)0.51544 (19)0.5957 (8)0.0395 (7)
C60.3728 (2)0.57746 (17)0.5249 (7)0.0431 (7)
H6A0.30180.56490.40870.052*
N10.6464 (2)0.47087 (18)0.8346 (8)0.0565 (8)
H1A0.71240.48380.93830.068*
H1B0.63380.41960.77260.068*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0770 (3)0.0451 (2)0.0717 (3)0.01789 (15)−0.0064 (2)0.0025 (2)
Cl10.0638 (5)0.0349 (4)0.0776 (6)−0.0034 (3)−0.0023 (5)−0.0047 (5)
C10.0509 (17)0.0347 (16)0.0438 (16)0.0061 (14)0.0043 (14)0.0027 (13)
C20.0582 (18)0.0357 (18)0.054 (2)−0.0081 (15)0.0075 (16)−0.0027 (15)
C30.0368 (15)0.0481 (19)0.0520 (18)−0.0064 (14)−0.0002 (14)−0.0008 (15)
C40.0399 (16)0.0430 (18)0.0455 (18)0.0005 (14)0.0086 (14)0.0040 (13)
C50.0416 (15)0.0344 (15)0.0424 (16)−0.0028 (12)0.0053 (13)0.0012 (12)
C60.0424 (14)0.0406 (15)0.0461 (16)−0.0022 (12)−0.0007 (16)0.0016 (16)
N10.0434 (15)0.0500 (17)0.076 (2)0.0101 (13)−0.0015 (15)0.0006 (15)

Geometric parameters (Å, °)

Br1—C11.883 (3)C3—H3A0.9300
Cl1—C51.725 (3)C4—N11.369 (4)
C1—C61.361 (4)C4—C51.383 (4)
C1—C21.368 (5)C5—C61.361 (4)
C2—C31.361 (5)C6—H6A0.9300
C2—H2A0.9300N1—H1A0.8600
C3—C41.382 (4)N1—H1B0.8600
C6—C1—C2120.7 (3)C3—C4—C5117.1 (3)
C6—C1—Br1119.1 (2)C6—C5—C4121.8 (3)
C2—C1—Br1120.2 (2)C6—C5—Cl1119.0 (2)
C3—C2—C1119.4 (3)C4—C5—Cl1119.2 (2)
C3—C2—H2A120.3C1—C6—C5119.4 (3)
C1—C2—H2A120.3C1—C6—H6A120.3
C2—C3—C4121.6 (3)C5—C6—H6A120.3
C2—C3—H3A119.2C4—N1—H1A120.0
C4—C3—H3A119.2C4—N1—H1B120.0
N1—C4—C3120.2 (3)H1A—N1—H1B120.0
N1—C4—C5122.7 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···Br1i0.863.043.719 (3)137
N1—H1A···N1ii0.862.343.172 (4)164

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5285).

References

  • Ault, A. & Kraig, R. (1966). J. Chem. Educ.43, 213–214.
  • Bruker (2001). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cox, P. J. (2001). Acta Cryst. E57, o1203–o1205.
  • Ferguson, G., Low, J. N., Penner, G. H. & Wardell, J. L. (1998). Acta Cryst. C54, 1974–1977.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Katritzky, A. R., Li, J., Stevens, C. V. & Ager, D. (1994). J. Org. Prep. Proced. Int., 26, 439–444.
  • Ng, S. W. (2005). Acta Cryst. E61, o2299–o2300.
  • Parkin, A., Spanswick, C. K., Pulham, C. R. & Wilson, C. C. (2005). Acta Cryst. E61, o1087–o1089.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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