2,6-Di­bromo-4-methyl­aniline

Brihi, O.; Medjani, M.; Bougueria, H.; Djedouani, A.; Francois, M.; Fleutot, S.; Boudjada, A.

doi:10.1107/S2414314622005776

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 6| June 2022| x220577

https://doi.org/10.1107/S2414314622005776

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2,6-Dibromo-4-methylaniline

Ouarda Brihi,^a ^* Meriem Medjani,^b Hassiba Bougueria,^c Amel Djedouani,^d Michelle Francois,^e Solenne Fleutot ^e and Ali Boudjada ^a

^aLaboratoire de Cristallographie, Département de Physique, Université Frères Mentouri-Constantine 1, 25000 Constantine, Algeria, ^bLaboratoire de Cristallographie, Département de Physique, Université Mentouri-Constantine 1, 25000 Constantine, Algeria, ^cUnité de Recherche de Chimie de l'envirenement et Moléculaire Structurale (CHEMS), Département de Chimie, Faculté des Sciences Exactes, Université de Constantine 1, 25000 Constantine, Algeria, ^dLaboratoire de Physicochimie Analytique et de Cristallochimie de Matériaux Organo-métalique et Biomoléculaire, 25000 Constantine, Algeria, and ^eInstitut Jean Lamour UMR, 7198 Parc de Saurup CS 14234, F 54042 Nancy, France
^*Correspondence e-mail: ouardabrihi@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 January 2022; accepted 28 May 2022; online 7 June 2022)

In the title compound, C₇H₇Br₂N, the C—C—C bond angles of the benzene ring are notably distorted and two short intamolecular N—H⋯Br contacts occur. In the crystal, the molecules are linked by N—H⋯N hydrogen bonds to generate C(2) chains propagating in the [100] direction.

Keywords: aniline; crystal structure; N—H⋯N hydrogen bonds.

CCDC reference: 2175519

Structure description

The solid-state structure of the title compound, C₇H₇Br₂N, was established by single-crystal X-ray diffraction analysis at 200 K and the molecular structure is illustrated in Fig. 1. The bromine atoms are slightly displaced from the mean plane of C1–C4/C6/C7 benzene ring, by 0.032 (1) and 0.065 (1) Å for Br1 and Br2, respectively. This can also be quantified by the C4—C3—C2—Br1 and C4—C6—C7—Br2 torsion angles, which are 179.7 (3) and −178.5 (3)°, respectively. The bond angles in the benzene ring are notably distorted from the ideal value of 120° with C7—C1—C2 = 115.1 (4), C1—C2—C3 = 122.8 (4) and C1—C7—C6 = 123.0 (4)°. The amine group lying between the bromine atoms results in two short intramolecular N—H⋯Br contacts (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br1	0.86	2.65	3.077 (4)	112
N1—H1B⋯Br2	0.86	2.64	3.072 (4)	113
N1—H1B⋯N1ⁱ	0.86	2.38	3.120 (7)	144
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 1
The molecular structure of the title compound showing displacement ellipsoids at the 50% probability level.

In the crystal, the molecules are linked by weak N1—H1B⋯N1 hydrogen bonds (Table 1) with N⋯N = 3.120 (7) Å to generate [100] C(2) chains with adjacent molecules related by the 2₁ screw axis. A similar hydrogen bond was observed in diaminomesithylene (Brihi et al., 2016 ). The packing is illustrated in Fig. 2, which shows the topology of the chain is a zigzag, with an angle of inclination of the benzene ring to the a axis of 53.73 (14)°.

Figure 2
Views along the (a) b and (b) c axes of the crystal packing of the title compound with hydrogen bonds shown as dotted lines.

Synthesis and crystallization

The title compound is commercially available (Lancaster Synthesis). It was purified by recrystallization from a solution of 80% ethanol and 20% distilled water. The colorless single crystals obtained are in the form of needles, which grow along the a axis.

Refinement

Crystal data, data collection and structure refinement details of the compound are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₇Br₂N
M_r	264.96
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	200
a, b, c (Å)	4.3773 (7), 13.585 (2), 14.057 (3)
V (Å³)	835.9 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	9.62
Crystal size (mm)	0.12 × 0.05 × 0.04

Data collection
Diffractometer	Bruker APEXII QUAZAR CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.396, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7550, 1715, 1422
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.072, 0.91
No. of reflections	1715
No. of parameters	92
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.38
Absolute structure	Flack (1983 )
Absolute structure parameter	0.02 (2)
Computer programs: APEX2 and SAINT (Bruker, 2016), SIR92 (Altomare et al., 1994 ), SHELXL2013 (Sheldrick, 2015 ), ORTEP for Windows and WinGX publication routines (Farrugia, 2012 ).

Structural data

CCDC reference: 2175519

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622005776/hb4398sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622005776/hb4398Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622005776/hb4398Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: ORTEP for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).

2,6-Dibromo-4-methylaniline top

Crystal data top

C₇H₇Br₂N	F(000) = 504
M_r = 264.96	D_x = 2.105 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7750 reflections
a = 4.3773 (7) Å	θ = 2.1–26.4°
b = 13.585 (2) Å	µ = 9.62 mm⁻¹
c = 14.057 (3) Å	T = 200 K
V = 835.9 (2) Å³	Needle, colorless
Z = 4	0.12 × 0.05 × 0.04 mm

Data collection top

Bruker APEXII QUAZAR CCD diffractometer	1715 independent reflections
Radiation source: ImuS	1422 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 8.02 pixels mm^-1	θ_max = 26.4°, θ_min = 2.1°
f\ and ω scans	h = −5→5
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −15→16
T_min = 0.396, T_max = 0.746	l = −17→17
7550 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)] = 0.030	H-atom parameters not refined
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0409P)²] where P = (F_o² + 2F_c²)/3
S = 0.91	(Δ/σ)_max = 0.001
1715 reflections	Δρ_max = 0.36 e Å⁻³
92 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Absolute structure: Flack (1983)
0 constraints	Absolute structure parameter: 0.02 (2)
Primary atom site location: structure-invariant direct methods

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 esds 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 > 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	0.69454 (12)	0.51851 (3)	0.40790 (4)	0.0449 (2)
Br2	0.49325 (11)	0.11063 (3)	0.35184 (3)	0.0374 (2)
N1	0.4343 (8)	0.3124 (3)	0.4488 (2)	0.0340 (14)
C1	0.6072 (9)	0.3165 (3)	0.3674 (3)	0.0255 (14)
C2	0.7481 (9)	0.4015 (3)	0.3360 (3)	0.0277 (14)
C3	0.9295 (10)	0.4045 (3)	0.2553 (3)	0.0323 (17)
C4	0.9781 (10)	0.3217 (3)	0.2004 (3)	0.0313 (14)
C5	1.1658 (11)	0.3259 (3)	0.1108 (3)	0.0447 (17)
C6	0.8409 (10)	0.2336 (3)	0.2315 (3)	0.0317 (14)
C7	0.6636 (10)	0.2322 (3)	0.3118 (3)	0.0280 (12)
H1	1.33755	0.28238	0.11654	0.0669*
H1A	0.40957	0.36443	0.48284	0.0407*
H1B	0.35064	0.25790	0.46576	0.0407*
H2	1.02080	0.46361	0.23780	0.0388*
H3	0.87095	0.17585	0.19722	0.0378*
H4	1.23699	0.39194	0.10090	0.0669*
H5	1.04240	0.30603	0.05765	0.0669*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0576 (3)	0.0274 (2)	0.0497 (3)	−0.0005 (2)	0.0057 (3)	−0.0016 (2)
Br2	0.0373 (3)	0.0279 (2)	0.0471 (3)	−0.0053 (2)	−0.0027 (3)	0.0002 (2)
N1	0.038 (3)	0.031 (2)	0.033 (2)	−0.0013 (18)	0.0070 (18)	0.0005 (17)
C1	0.0174 (19)	0.028 (2)	0.031 (3)	0.0015 (17)	−0.0052 (19)	0.007 (2)
C2	0.023 (2)	0.027 (2)	0.033 (3)	0.0023 (18)	−0.0039 (19)	0.0002 (19)
C3	0.027 (3)	0.029 (3)	0.041 (3)	0.0011 (19)	0.001 (2)	0.006 (2)
C4	0.021 (2)	0.041 (3)	0.032 (2)	0.005 (2)	0.000 (2)	0.007 (2)
C5	0.036 (3)	0.057 (3)	0.041 (3)	0.009 (3)	0.005 (3)	0.008 (3)
C6	0.030 (2)	0.038 (3)	0.027 (2)	0.004 (2)	−0.004 (2)	−0.002 (2)
C7	0.024 (2)	0.028 (2)	0.032 (2)	0.001 (2)	−0.006 (2)	−0.0010 (19)

Geometric parameters (Å, º) top

Br1—C2	1.898 (4)	C4—C5	1.505 (6)
Br2—C7	1.898 (4)	C4—C6	1.409 (6)
N1—C1	1.373 (5)	C6—C7	1.370 (6)
N1—H1A	0.8600	C3—H2	0.9300
N1—H1B	0.8600	C5—H1	0.9600
C1—C7	1.408 (6)	C5—H4	0.9600
C1—C2	1.382 (6)	C5—H5	0.9600
C2—C3	1.385 (6)	C6—H3	0.9300
C3—C4	1.381 (6)

C1—N1—H1B	120.00	Br2—C7—C1	118.3 (3)
H1A—N1—H1B	120.00	Br2—C7—C6	118.6 (3)
C1—N1—H1A	120.00	C1—C7—C6	123.0 (4)
C2—C1—C7	115.1 (4)	C2—C3—H2	119.00
N1—C1—C7	121.8 (4)	C4—C3—H2	119.00
N1—C1—C2	123.1 (4)	C4—C5—H1	110.00
Br1—C2—C1	118.3 (3)	C4—C5—H4	110.00
Br1—C2—C3	118.8 (3)	C4—C5—H5	109.00
C1—C2—C3	122.8 (4)	H1—C5—H4	109.00
C2—C3—C4	121.5 (4)	H1—C5—H5	109.00
C5—C4—C6	121.7 (4)	H4—C5—H5	109.00
C3—C4—C5	121.4 (4)	C4—C6—H3	120.00
C3—C4—C6	116.9 (4)	C7—C6—H3	120.00
C4—C6—C7	120.6 (4)

N1—C1—C2—Br1	−1.0 (5)	Br1—C2—C3—C4	179.7 (3)
N1—C1—C2—C3	178.1 (4)	C1—C2—C3—C4	0.6 (7)
C7—C1—C2—Br1	−178.5 (3)	C2—C3—C4—C5	177.7 (4)
C7—C1—C2—C3	0.6 (6)	C2—C3—C4—C6	−1.5 (6)
N1—C1—C7—Br2	0.1 (6)	C3—C4—C6—C7	1.2 (6)
N1—C1—C7—C6	−178.5 (4)	C5—C4—C6—C7	−178.1 (4)
C2—C1—C7—Br2	177.6 (3)	C4—C6—C7—Br2	−178.5 (3)
C2—C1—C7—C6	−1.0 (6)	C4—C6—C7—C1	0.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.86	2.65	3.077 (4)	112
N1—H1B···Br2	0.86	2.64	3.072 (4)	113
N1—H1B···N1ⁱ	0.86	2.38	3.120 (7)	144

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

Acknowledgements

This work was supported by the Laboratoire de Cristallographie, Département de Physique, Université Mentouri-Constantine, Algérie and Institut Jean Lamour UMR 7198, Parc de Saurupt, CS 14234 F 54042 Nancy, France.

References

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