2,6-Dibromo-4-chloro­aniline

Ali, U.S.; Siddiqui, W.A.; Ashraf, A.; Tahir, M.N.

doi:10.1107/S1600536812023331

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1904

doi:10.1107/S1600536812023331

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2,6-Dibromo-4-chloroaniline

Umar Sharif Ali,^a Waseeq Ahmad Siddiqui,^a Adnan Ashraf ^a and M. Nawaz Tahir ^b ^*

^aUniversity of Sargodha, Department of Chemistry, Sargodha, Pakistan, and ^bUniversity of Sargodha, Department of Physics, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 21 May 2012; accepted 21 May 2012; online 26 May 2012)

The title compound, C₆H₄Br₂ClN, is almost planar (r.m.s. deviation = 0.024 Å) and two intramolecular N—H⋯Br hydrogen bonds generate S(5) rings. In the crystal, N—H⋯Br hydrogen bonds link the molecules into chains propagating in [010].

Related literature

For related structures, see: Schlemper & Konnert (1967 ): Takazawa et al. (1989 ). For the synthesis, see: Harrison et al. (1981 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₆H₄Br₂ClN
M_r = 285.37
Monoclinic, P 2₁ /n
a = 13.3132 (7) Å
b = 3.9387 (2) Å
c = 16.5476 (9) Å
β = 112.318 (2)°
V = 802.70 (7) Å³
Z = 4
Mo Kα radiation
μ = 10.35 mm⁻¹
T = 296 K
0.35 × 0.15 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.170, T_max = 0.292
6640 measured reflections
1900 independent reflections
1429 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.056
S = 1.02
1900 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br2	0.86	2.64	3.067 (2)	112
N1—H1A⋯Br2ⁱ	0.86	2.91	3.380 (3)	117
N1—H1B⋯Br1	0.86	2.67	3.099 (3)	112
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812023331/hb6810sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023331/hb6810Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812023331/hb6810Isup3.cml

checkCIF report

Comment top

The title compound (I), (Fig. 1) has been synthesized as a pre-cursor. The crystal structures of 4-chloroaniline (Takazawa et al., 1989), 2,4, 6-tribromoaniline (Schlemper & Konnert, 1967) have been published which are related to (I).

The molecule as a whole is almost planar with r. m. s. deviation of 0.0242 Å. In (I), there exist intramolecular H-bonding of N—H···Br type to form two S(5) rings (Bernstein et al., 1995). The molecules are connected along the b-axis due to H-bondings of N—H···Br type (Table 1, Fig. 2). There does not exist any kind of π-interaction.

Related literature top

For related structures, see: Schlemper & Konnert (1967): Takazawa et al. (1989). For the synthesis, see: Harrison et al. (1981). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound has been synthesized from the 4-chloroaniline using the method of Harrison, et al., 1981.

m. p. 352–354 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The partial packing (PLATON; Spek, 2009), which shows that molecules form C(2) chains extending along [0 1 0] direction.

2,6-Dibromo-4-chloroaniline top

Crystal data top

C₆H₄Br₂ClN	F(000) = 536
M_r = 285.37	D_x = 2.361 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1429 reflections
a = 13.3132 (7) Å	θ = 2.5–27.9°
b = 3.9387 (2) Å	µ = 10.35 mm⁻¹
c = 16.5476 (9) Å	T = 296 K
β = 112.318 (2)°	Needle, dark brown
V = 802.70 (7) Å³	0.35 × 0.15 × 0.12 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	1900 independent reflections
Radiation source: fine-focus sealed tube	1429 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 7.60 pixels mm^-1	θ_max = 27.9°, θ_min = 2.5°
ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −3→5
T_min = 0.170, T_max = 0.292	l = −21→21
6640 measured reflections

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)] = 0.024	H-atom parameters constrained
wR(F²) = 0.056	w = 1/[σ²(F_o²) + (0.0225P)² + 0.3103P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
1900 reflections	Δρ_max = 0.43 e Å⁻³
92 parameters	Δρ_min = −0.36 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: 0.0048 (5)

Crystal data top

C₆H₄Br₂ClN	V = 802.70 (7) Å³
M_r = 285.37	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.3132 (7) Å	µ = 10.35 mm⁻¹
b = 3.9387 (2) Å	T = 296 K
c = 16.5476 (9) Å	0.35 × 0.15 × 0.12 mm
β = 112.318 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1900 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1429 reflections with I > 2σ(I)
T_min = 0.170, T_max = 0.292	R_int = 0.028
6640 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.056	H-atom parameters constrained
S = 1.02	Δρ_max = 0.43 e Å⁻³
1900 reflections	Δρ_min = −0.36 e Å⁻³
92 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
Br1	0.43969 (2)	0.63712 (8)	0.36884 (2)	0.0452 (1)
Br2	0.63382 (2)	0.13268 (8)	0.14100 (2)	0.0465 (1)
Cl1	0.21601 (6)	0.6350 (2)	0.01323 (5)	0.0528 (3)
N1	0.61671 (18)	0.3035 (7)	0.31614 (15)	0.0447 (8)
C1	0.5233 (2)	0.3766 (6)	0.24594 (17)	0.0310 (8)
C2	0.4327 (2)	0.5295 (7)	0.25508 (16)	0.0312 (8)
C3	0.3397 (2)	0.6082 (7)	0.18522 (17)	0.0333 (8)
C4	0.3335 (2)	0.5335 (7)	0.10201 (18)	0.0351 (8)
C5	0.4205 (2)	0.3896 (7)	0.08856 (17)	0.0355 (8)
C6	0.5129 (2)	0.3157 (6)	0.15999 (17)	0.0301 (8)
H1A	0.67145	0.21719	0.30798	0.0537*
H1B	0.62055	0.34404	0.36830	0.0537*
H3	0.28153	0.71053	0.19381	0.0399*
H5	0.41666	0.34358	0.03233	0.0426*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0471 (2)	0.0548 (2)	0.0351 (2)	−0.0064 (1)	0.0173 (1)	−0.0081 (1)
Br2	0.0434 (2)	0.0423 (2)	0.0610 (2)	0.0059 (1)	0.0281 (2)	−0.0024 (2)
Cl1	0.0439 (4)	0.0637 (6)	0.0373 (4)	0.0116 (4)	0.0002 (3)	0.0030 (4)
N1	0.0297 (12)	0.0628 (18)	0.0369 (13)	0.0035 (12)	0.0072 (10)	0.0046 (12)
C1	0.0284 (13)	0.0255 (14)	0.0371 (13)	−0.0050 (12)	0.0103 (11)	0.0035 (12)
C2	0.0352 (14)	0.0284 (15)	0.0312 (13)	−0.0071 (12)	0.0141 (12)	−0.0026 (11)
C3	0.0294 (13)	0.0317 (16)	0.0384 (14)	0.0017 (12)	0.0125 (12)	0.0000 (12)
C4	0.0332 (14)	0.0315 (16)	0.0333 (14)	0.0024 (12)	0.0043 (12)	0.0020 (12)
C5	0.0412 (15)	0.0334 (16)	0.0320 (13)	−0.0017 (13)	0.0141 (12)	−0.0033 (12)
C6	0.0299 (13)	0.0229 (15)	0.0391 (14)	0.0004 (11)	0.0150 (11)	0.0009 (12)

Geometric parameters (Å, º) top

Br1—C2	1.897 (3)	C1—C2	1.407 (4)
Br2—C6	1.896 (3)	C2—C3	1.371 (4)
Cl1—C4	1.738 (3)	C3—C4	1.380 (4)
N1—C1	1.372 (4)	C4—C5	1.381 (4)
N1—H1B	0.8600	C5—C6	1.375 (4)
N1—H1A	0.8600	C3—H3	0.9300
C1—C6	1.396 (4)	C5—H5	0.9300

C1—N1—H1B	120.00	Cl1—C4—C3	119.2 (2)
H1A—N1—H1B	120.00	Cl1—C4—C5	119.9 (2)
C1—N1—H1A	120.00	C4—C5—C6	118.7 (2)
C2—C1—C6	115.2 (2)	Br2—C6—C1	118.2 (2)
N1—C1—C6	122.3 (3)	Br2—C6—C5	118.5 (2)
N1—C1—C2	122.5 (2)	C1—C6—C5	123.3 (3)
Br1—C2—C1	118.78 (19)	C2—C3—H3	120.00
Br1—C2—C3	118.3 (2)	C4—C3—H3	120.00
C1—C2—C3	122.9 (2)	C4—C5—H5	121.00
C2—C3—C4	119.1 (3)	C6—C5—H5	121.00
C3—C4—C5	120.8 (3)

N1—C1—C2—Br1	−0.3 (4)	Br1—C2—C3—C4	179.6 (2)
N1—C1—C2—C3	179.0 (3)	C1—C2—C3—C4	0.4 (4)
C6—C1—C2—Br1	−178.01 (19)	C2—C3—C4—Cl1	−179.7 (2)
C6—C1—C2—C3	1.2 (4)	C2—C3—C4—C5	−1.7 (4)
N1—C1—C6—Br2	−1.1 (3)	Cl1—C4—C5—C6	179.2 (2)
N1—C1—C6—C5	−179.4 (3)	C3—C4—C5—C6	1.3 (4)
C2—C1—C6—Br2	176.68 (19)	C4—C5—C6—Br2	−177.9 (2)
C2—C1—C6—C5	−1.6 (4)	C4—C5—C6—C1	0.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br2	0.86	2.64	3.067 (2)	112
N1—H1A···Br2ⁱ	0.86	2.91	3.380 (3)	117
N1—H1B···Br1	0.86	2.67	3.099 (3)	112

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

Experimental details

Crystal data
Chemical formula	C₆H₄Br₂ClN
M_r	285.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	13.3132 (7), 3.9387 (2), 16.5476 (9)
β (°)	112.318 (2)
V (Å³)	802.70 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.35
Crystal size (mm)	0.35 × 0.15 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.170, 0.292
No. of measured, independent and observed [I > 2σ(I)] reflections	6640, 1900, 1429
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.056, 1.02
No. of reflections	1900
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.36

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br2	0.86	2.64	3.067 (2)	112
N1—H1A···Br2ⁱ	0.86	2.91	3.380 (3)	117
N1—H1B···Br1	0.86	2.67	3.099 (3)	112

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

Acknowledgements

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

References

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