2,6-Dibromo-4-chloro­aniline

Abstract

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,

• a = 13.3132 (7) Å

• b = 3.9387 (2) Å

• c = 16.5476 (9) Å

• β = 112.318 (2)°

• V = 802.70 (7) ų

• 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[F ² > 2σ(F ²)] = 0.024

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812023331/hb6810Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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

m. p. 352–354 K.

Refinement

The H-atoms were positioned geometrically at C—H = 0.93 and N—H = 0.86 Å, respectively and included in the refinement as riding with U_iso(H) = xU_eq(C, N), where x = 1.2 for all H atoms.

Figures

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.

Crystal data

C6H4Br2ClN	F(000) = 536
Mr = 285.37	Dx = 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

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

Refinement

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(Fo2) + (0.0225P)2 + 0.3103P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
1900 reflections	Δρmax = 0.43 e Å−3
92 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.