4-Bromo-2-chloro­aniline

Wei, Z.-B.; Liu, Z.-H.; Ye, J.-L.; Zhang, H.-K.

doi:10.1107/S1600536809054944

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o250

doi:10.1107/S1600536809054944

Open

access

4-Bromo-2-chloroaniline

Zan-Bin Wei,^a Zhi-Hong Liu,^a Jian-Liang Ye ^a ^* and Hong-Kui Zhang ^a

^aThe Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, People's Republic of China
^*Correspondence e-mail: yejl@xmu.edu.cn

(Received 17 December 2009; accepted 21 December 2009; online 24 December 2009)

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 ). For related structures, see: Cox (2001 ); Parkin et al. (2005 ); Ng (2005 ); Ferguson et al. (1998 ). For the synthesis, see: Ault & Kraig (1966 ).

Experimental

Crystal data

C₆H₅BrClN
M_r = 206.47
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.033
wR(F²) = 0.081
S = 0.99
1710 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.48 e Å⁻³
Absolute structure: Flack (1983 ), 511 Friedel pairs
Flack parameter: 0.035 (15)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Br1ⁱ	0.86	3.04	3.719 (3)	137
N1—H1A⋯N1ⁱⁱ	0.86	2.34	3.172 (4)	164
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

4-Bromo-2-chloroaniline top

Crystal data top

C₆H₅BrClN	F(000) = 424
M_r = 206.47	D_x = 1.965 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1199 reflections
a = 10.965 (4) Å	θ = 2.3–29.8°
b = 15.814 (6) Å	µ = 6.17 mm⁻¹
c = 4.0232 (15) Å	T = 298 K
V = 697.7 (4) Å³	Needle, colourless
Z = 4	0.7 × 0.19 × 0.15 mm

Data collection top

Bruker SMART CCD diffractometer	1710 independent reflections
Radiation source: fine-focus sealed tube	1333 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scan	θ_max = 29.8°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
T_min = 0.254, T_max = 0.396	k = −20→21
5799 measured reflections	l = −5→5

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0374P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.081	(Δ/σ)_max = 0.008
S = 0.99	Δρ_max = 0.33 e Å⁻³
1710 reflections	Δρ_min = −0.48 e Å⁻³
83 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.246 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 511 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.035 (15)

Crystal data top

C₆H₅BrClN	V = 697.7 (4) Å³
M_r = 206.47	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 10.965 (4) Å	µ = 6.17 mm⁻¹
b = 15.814 (6) Å	T = 298 K
c = 4.0232 (15) Å	0.7 × 0.19 × 0.15 mm

Data collection top

Bruker SMART CCD diffractometer	1710 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1333 reflections with I > 2σ(I)
T_min = 0.254, T_max = 0.396	R_int = 0.044
5799 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.081	Δρ_max = 0.33 e Å⁻³
S = 0.99	Δρ_min = −0.48 e Å⁻³
1710 reflections	Absolute structure: Flack (1983), 511 Friedel pairs
83 parameters	Absolute structure parameter: 0.035 (15)
0 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.28337 (3)	0.74386 (2)	0.51936 (10)	0.0646 (2)
Cl1	0.42519 (8)	0.41363 (5)	0.4648 (3)	0.0588 (3)
C1	0.3957 (3)	0.65802 (18)	0.6258 (8)	0.0432 (7)
C2	0.4999 (3)	0.6770 (2)	0.7973 (9)	0.0494 (8)
H2A	0.5151	0.7322	0.8656	0.059*
C3	0.5812 (3)	0.6145 (2)	0.8673 (9)	0.0456 (8)
H3A	0.6518	0.6276	0.9846	0.055*
C4	0.5613 (3)	0.5320 (2)	0.7681 (8)	0.0428 (8)
C5	0.4548 (3)	0.51544 (19)	0.5957 (8)	0.0395 (7)
C6	0.3728 (2)	0.57746 (17)	0.5249 (7)	0.0431 (7)
H6A	0.3018	0.5649	0.4087	0.052*
N1	0.6464 (2)	0.47087 (18)	0.8346 (8)	0.0565 (8)
H1A	0.7124	0.4838	0.9383	0.068*
H1B	0.6338	0.4196	0.7726	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0770 (3)	0.0451 (2)	0.0717 (3)	0.01789 (15)	−0.0064 (2)	0.0025 (2)
Cl1	0.0638 (5)	0.0349 (4)	0.0776 (6)	−0.0034 (3)	−0.0023 (5)	−0.0047 (5)
C1	0.0509 (17)	0.0347 (16)	0.0438 (16)	0.0061 (14)	0.0043 (14)	0.0027 (13)
C2	0.0582 (18)	0.0357 (18)	0.054 (2)	−0.0081 (15)	0.0075 (16)	−0.0027 (15)
C3	0.0368 (15)	0.0481 (19)	0.0520 (18)	−0.0064 (14)	−0.0002 (14)	−0.0008 (15)
C4	0.0399 (16)	0.0430 (18)	0.0455 (18)	0.0005 (14)	0.0086 (14)	0.0040 (13)
C5	0.0416 (15)	0.0344 (15)	0.0424 (16)	−0.0028 (12)	0.0053 (13)	0.0012 (12)
C6	0.0424 (14)	0.0406 (15)	0.0461 (16)	−0.0022 (12)	−0.0007 (16)	0.0016 (16)
N1	0.0434 (15)	0.0500 (17)	0.076 (2)	0.0101 (13)	−0.0015 (15)	0.0006 (15)

Geometric parameters (Å, º) top

Br1—C1	1.883 (3)	C3—H3A	0.9300
Cl1—C5	1.725 (3)	C4—N1	1.369 (4)
C1—C6	1.361 (4)	C4—C5	1.383 (4)
C1—C2	1.368 (5)	C5—C6	1.361 (4)
C2—C3	1.361 (5)	C6—H6A	0.9300
C2—H2A	0.9300	N1—H1A	0.8600
C3—C4	1.382 (4)	N1—H1B	0.8600

C6—C1—C2	120.7 (3)	C3—C4—C5	117.1 (3)
C6—C1—Br1	119.1 (2)	C6—C5—C4	121.8 (3)
C2—C1—Br1	120.2 (2)	C6—C5—Cl1	119.0 (2)
C3—C2—C1	119.4 (3)	C4—C5—Cl1	119.2 (2)
C3—C2—H2A	120.3	C1—C6—C5	119.4 (3)
C1—C2—H2A	120.3	C1—C6—H6A	120.3
C2—C3—C4	121.6 (3)	C5—C6—H6A	120.3
C2—C3—H3A	119.2	C4—N1—H1A	120.0
C4—C3—H3A	119.2	C4—N1—H1B	120.0
N1—C4—C3	120.2 (3)	H1A—N1—H1B	120.0
N1—C4—C5	122.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Br1ⁱ	0.86	3.04	3.719 (3)	137
N1—H1A···N1ⁱⁱ	0.86	2.34	3.172 (4)	164

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

Experimental details

Crystal data
Chemical formula	C₆H₅BrClN
M_r	206.47
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	10.965 (4), 15.814 (6), 4.0232 (15)
V (Å³)	697.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.17
Crystal size (mm)	0.7 × 0.19 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.254, 0.396
No. of measured, independent and observed [I > 2σ(I)] reflections	5799, 1710, 1333
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.698

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.081, 0.99
No. of reflections	1710
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.48
Absolute structure	Flack (1983), 511 Friedel pairs
Absolute structure parameter	0.035 (15)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Br1ⁱ	0.86	3.04	3.719 (3)	137
N1—H1A···N1ⁱⁱ	0.86	2.34	3.172 (4)	164

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

Acknowledgements

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

References

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