4-Bromo-N-(4-bromo-phen-yl)aniline.

In the title compound, C(12)H(9)Br(2)N, the dihedral angle between the benzene rings is 47.32 (5)°, whereas the pitch angles, or the angles between the mean plane of each aryl group 'propeller blade' and the plane defined by the aryl bridging C-N-C angle, are 18.1 (2) and 31.7 (2)°. No inter-molecular N-H hydrogen bonding is present in the crystal; however, there is a short inter-molecular Br⋯Br contact of 3.568 (1) Å.

Related literature

The title compound is an amine analogue of brominated diphenyl ether flame retardant materials commonly used in household items. For information on environmental and health concerns related to brominated flame retardants, see: de Wit (2002) ▶; Lunder et al. (2010 ▶). For the synthesis of the title compound, see: Crounse & Raiford (1945 ▶); Galatis & Megaloikonomos (1934 ▶); He et al. (2008 ▶). For related structures, see: Eriksson et al. (2004 ▶); Plieth & Ruban (1961 ▶); Li et al. (2010 ▶). For the van der Waals radius of Br and inter­molecular Br⋯Br contacts, see: Bondi (1964 ▶); Medlycott et al. (2007 ▶). For a description of the pitch angle, see: Lim & Tanski (2007 ▶).

Experimental

Crystal data

C12H9Br2N

M = 327.02

Monoclinic,

a = 5.9993 (12) Å

b = 13.032 (3) Å

c = 14.228 (3) Å

β = 96.967 (3)°

V = 1104.2 (4) Å3

Z = 4

Mo Kα radiation

μ = 7.30 mm−1

T = 125 K

0.30 × 0.30 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2007 ▶) T min = 0.218, T max = 0.370

17275 measured reflections

3373 independent reflections

2786 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.064

S = 1.02

3373 reflections

139 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.94 e Å−3

Δρmin = −0.45 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100715X/si2339sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100715X/si2339Isup2.hkl

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

C12H9Br2N	F(000) = 632
Mr = 327.02	Dx = 1.967 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8371 reflections
a = 5.9993 (12) Å	θ = 2.9–30.4°
b = 13.032 (3) Å	µ = 7.30 mm−1
c = 14.228 (3) Å	T = 125 K
β = 96.967 (3)°	Plate, colourless
V = 1104.2 (4) Å3	0.30 × 0.30 × 0.17 mm
Z = 4

Bruker APEXII CCD diffractometer	3373 independent reflections
Radiation source: fine-focus sealed tube	2786 reflections with I > 2σ(I)
graphite	Rint = 0.038
φ and ω scans	θmax = 30.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker 2007)	h = −8→8
Tmin = 0.218, Tmax = 0.370	k = −18→18
17275 measured reflections	l = −20→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0365P)2] where P = (Fo2 + 2Fc2)/3
3373 reflections	(Δ/σ)max = 0.001
139 parameters	Δρmax = 0.94 e Å−3
1 restraint	Δρmin = −0.45 e Å−3

Experimental. A suitable crystal was mounted in a nylon loop with Paratone-N cryoprotectant oil and data was collected on a Bruker APEX 2 CCD platform diffractometer. The structure was solved using direct methods and standard difference map techniques, and was refined by full-matrix least-squares procedures on F2 with SHELXTL Version 6.14 (Sheldrick, 2008).

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.

	x	y	z	Uiso*/Ueq
Br1	0.35642 (4)	0.125752 (16)	0.143618 (15)	0.02649 (7)
Br2	−0.19656 (3)	0.946875 (15)	0.134200 (15)	0.02372 (7)
N	0.4407 (3)	0.58823 (13)	0.10486 (13)	0.0224 (4)
H1	0.566 (3)	0.6043 (18)	0.0893 (16)	0.027*
C1	0.3790 (3)	0.27103 (16)	0.13498 (13)	0.0200 (4)
C2	0.5839 (3)	0.31866 (15)	0.16241 (14)	0.0229 (4)
H2A	0.7114	0.2793	0.1865	0.027*
C3	0.5998 (3)	0.42427 (15)	0.15413 (14)	0.0215 (4)
H3A	0.7391	0.4573	0.1733	0.026*
C4	0.4131 (3)	0.48316 (15)	0.11792 (13)	0.0186 (4)
C5	0.2092 (3)	0.43296 (15)	0.09209 (14)	0.0204 (4)
H5A	0.0806	0.4719	0.0685	0.025*
C6	0.1911 (3)	0.32763 (15)	0.10030 (14)	0.0209 (4)
H6A	0.0514	0.2944	0.0824	0.025*
C7	0.2844 (3)	0.66694 (15)	0.10980 (14)	0.0188 (4)
C8	0.0933 (3)	0.65683 (15)	0.15638 (14)	0.0192 (4)
H8A	0.0621	0.5931	0.1845	0.023*
C9	−0.0513 (3)	0.73940 (15)	0.16173 (13)	0.0194 (4)
H9A	−0.1822	0.7318	0.1925	0.023*
C10	−0.0044 (3)	0.83266 (14)	0.12218 (14)	0.0191 (4)
C11	0.1859 (3)	0.84517 (15)	0.07631 (14)	0.0208 (4)
H11A	0.2179	0.9096	0.0497	0.025*
C12	0.3281 (3)	0.76224 (15)	0.06992 (13)	0.0202 (4)
H12A	0.4572	0.7701	0.0380	0.024*

	U11	U22	U33	U12	U13	U23
Br1	0.03250 (12)	0.01599 (11)	0.03174 (12)	0.00176 (8)	0.00695 (9)	−0.00159 (8)
Br2	0.02408 (11)	0.01647 (10)	0.03091 (12)	0.00214 (7)	0.00456 (8)	−0.00193 (7)
N	0.0179 (8)	0.0174 (8)	0.0330 (10)	0.0004 (7)	0.0076 (7)	0.0013 (7)
C1	0.0219 (9)	0.0166 (9)	0.0217 (9)	0.0016 (7)	0.0039 (7)	−0.0020 (7)
C2	0.0197 (9)	0.0232 (10)	0.0253 (10)	0.0046 (8)	0.0008 (8)	0.0007 (8)
C3	0.0144 (9)	0.0215 (10)	0.0283 (10)	−0.0001 (7)	0.0012 (7)	−0.0016 (8)
C4	0.0203 (9)	0.0182 (9)	0.0180 (9)	−0.0002 (7)	0.0051 (7)	−0.0009 (7)
C5	0.0184 (9)	0.0210 (10)	0.0212 (9)	0.0031 (7)	−0.0006 (7)	−0.0014 (7)
C6	0.0189 (9)	0.0225 (10)	0.0211 (9)	−0.0008 (7)	0.0020 (7)	−0.0033 (7)
C7	0.0192 (9)	0.0167 (9)	0.0205 (9)	−0.0008 (7)	0.0019 (7)	0.0001 (7)
C8	0.0204 (9)	0.0155 (9)	0.0219 (9)	−0.0030 (7)	0.0038 (7)	0.0002 (7)
C9	0.0176 (9)	0.0207 (10)	0.0206 (9)	−0.0031 (7)	0.0049 (7)	−0.0008 (7)
C10	0.0192 (9)	0.0150 (9)	0.0227 (9)	0.0017 (7)	0.0005 (7)	−0.0019 (7)
C11	0.0239 (10)	0.0156 (9)	0.0232 (10)	−0.0042 (7)	0.0038 (8)	0.0009 (7)
C12	0.0193 (9)	0.0210 (9)	0.0210 (9)	−0.0027 (7)	0.0049 (7)	−0.0007 (7)

Br1—C1	1.903 (2)	C5—H5A	0.9500
Br2—C10	1.9031 (19)	C6—H6A	0.9500
N—C4	1.394 (3)	C7—C8	1.399 (3)
N—C7	1.397 (3)	C7—C12	1.403 (3)
N—H1	0.835 (16)	C8—C9	1.390 (3)
C1—C6	1.387 (3)	C8—H8A	0.9500
C1—C2	1.390 (3)	C9—C10	1.383 (3)
C2—C3	1.386 (3)	C9—H9A	0.9500
C2—H2A	0.9500	C10—C11	1.391 (3)
C3—C4	1.403 (3)	C11—C12	1.387 (3)
C3—H3A	0.9500	C11—H11A	0.9500
C4—C5	1.397 (3)	C12—H12A	0.9500
C5—C6	1.383 (3)
C4—N—C7	128.53 (17)	C1—C6—H6A	120.4
C4—N—H1	114.0 (17)	N—C7—C8	123.26 (17)
C7—N—H1	117.4 (17)	N—C7—C12	118.05 (17)
C6—C1—C2	121.03 (19)	C8—C7—C12	118.62 (18)
C6—C1—Br1	119.41 (15)	C9—C8—C7	120.40 (18)
C2—C1—Br1	119.56 (15)	C9—C8—H8A	119.8
C3—C2—C1	119.14 (18)	C7—C8—H8A	119.8
C3—C2—H2A	120.4	C10—C9—C8	119.93 (18)
C1—C2—H2A	120.4	C10—C9—H9A	120.0
C2—C3—C4	120.97 (18)	C8—C9—H9A	120.0
C2—C3—H3A	119.5	C9—C10—C11	120.87 (18)
C4—C3—H3A	119.5	C9—C10—Br2	119.70 (15)
N—C4—C5	122.64 (18)	C11—C10—Br2	119.40 (14)
N—C4—C3	118.93 (17)	C12—C11—C10	119.05 (18)
C5—C4—C3	118.36 (18)	C12—C11—H11A	120.5
C6—C5—C4	121.20 (18)	C10—C11—H11A	120.5
C6—C5—H5A	119.4	C11—C12—C7	121.13 (18)
C4—C5—H5A	119.4	C11—C12—H12A	119.4
C5—C6—C1	119.28 (19)	C7—C12—H12A	119.4
C5—C6—H6A	120.4
C6—C1—C2—C3	−0.5 (3)	C4—N—C7—C8	20.0 (3)
Br1—C1—C2—C3	178.75 (15)	C4—N—C7—C12	−163.25 (19)
C1—C2—C3—C4	−0.5 (3)	N—C7—C8—C9	177.59 (18)
C7—N—C4—C5	33.3 (3)	C12—C7—C8—C9	0.8 (3)
C7—N—C4—C3	−149.9 (2)	C7—C8—C9—C10	−1.1 (3)
C2—C3—C4—N	−175.67 (18)	C8—C9—C10—C11	0.4 (3)
C2—C3—C4—C5	1.3 (3)	C8—C9—C10—Br2	−177.49 (14)
N—C4—C5—C6	175.75 (18)	C9—C10—C11—C12	0.5 (3)
C3—C4—C5—C6	−1.1 (3)	Br2—C10—C11—C12	178.40 (15)
C4—C5—C6—C1	0.1 (3)	C10—C11—C12—C7	−0.8 (3)
C2—C1—C6—C5	0.7 (3)	N—C7—C12—C11	−176.84 (18)
Br1—C1—C6—C5	−178.55 (14)	C8—C7—C12—C11	0.1 (3)