4-Bromo-2,6-dimethyl­aniline

Liu, R.; Li, Y.-H.; Luo, W.; Liu, S.; Zhu, H.-J.

doi:10.1107/S1600536807064641

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o220

https://doi.org/10.1107/S1600536807064641

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4-Bromo-2,6-dimethylaniline

Rui Liu,^a Yu-Hao Li,^a Wei Luo,^a Shan Liu ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 29 November 2007; accepted 30 November 2007; online 6 December 2007)

The asymmetric unit of the title compound, C₈H₁₀BrN, contains two independent molecules. The Br, N and methyl group C atoms lie in the benzene ring planes. In the crystal structure, N—H⋯N hydrogen bonds link the molecules.

Related literature

For general background, see: Heravi et al. (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₁₀BrN
M_r = 200.07
Monoclinic, P 2₁ /c
a = 20.141 (4) Å
b = 5.150 (1) Å
c = 17.300 (4) Å
β = 111.53 (3)°
V = 1669.3 (7) Å³
Z = 8
Mo Kα radiation
μ = 4.85 mm⁻¹
T = 294 (2) K
0.40 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.211, T_max = 0.379
3392 measured reflections
3268 independent reflections
1523 reflections with I > 2σ(I)
R_int = 0.040
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.166
S = 1.06
3268 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.86	2.50	3.279 (10)	151
N2—H2E⋯N1ⁱⁱ	0.86	2.50	3.287 (10)	152
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Bruker, 2000 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807064641/hk2405sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807064641/hk2405Isup2.hkl

checkCIF report

Comment top

The title compound, (I), contains amino and halogen groups, which can react with different groups to prepare various function organic compounds. It is a kind of aromatic organic intermediate that can be used for many fields such as aromatic conductive polymers and organometallic chemistry (Heravi et al., 2005). We herein report its crystal structure.

The asymmetric unit of (I) contains two independent molecules (Fig. 1), in which the bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987). The Br, N and C atoms of the methyl groups lie in the benzene ring planes.

In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 2) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Heravi et al. (2005). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared by the literature method (Heravi et al., 2005). The crystals were obtained by dissolving (I) (0.5 g) in hexane (20 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Structure description top

In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 2) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

For general background, see: Heravi et al. (2005). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius,1985); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

4-Bromo-2,6-dimethylaniline top

Crystal data top

C₈H₁₀BrN	F(000) = 800
M_r = 200.07	D_x = 1.592 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 321 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 20.141 (4) Å	Cell parameters from 25 reflections
b = 5.150 (1) Å	θ = 10–13°
c = 17.300 (4) Å	µ = 4.85 mm⁻¹
β = 111.53 (3)°	T = 294 K
V = 1669.3 (7) Å³	Needle, colorless
Z = 8	0.40 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1523 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.040
Graphite monochromator	θ_max = 26.0°, θ_min = 1.1°
ω/2θ scans	h = −24→23
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
T_min = 0.211, T_max = 0.379	l = 0→21
3392 measured reflections	3 standard reflections every 120 min
3268 independent reflections	intensity decay: none

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)] = 0.064	H-atom parameters constrained
wR(F²) = 0.166	w = 1/[σ²(F_o²) + (0.050P)² + 0.6P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
3268 reflections	Δρ_max = 0.24 e Å⁻³
183 parameters	Δρ_min = −0.25 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₈H₁₀BrN	V = 1669.3 (7) Å³
M_r = 200.07	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 20.141 (4) Å	µ = 4.85 mm⁻¹
b = 5.150 (1) Å	T = 294 K
c = 17.300 (4) Å	0.40 × 0.20 × 0.20 mm
β = 111.53 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1523 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.040
T_min = 0.211, T_max = 0.379	3 standard reflections every 120 min
3392 measured reflections	intensity decay: none
3268 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	183 parameters
wR(F²) = 0.166	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
3268 reflections	Δρ_min = −0.25 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.08550 (5)	0.9358 (3)	0.10030 (5)	0.1246 (5)
Br2	0.43509 (5)	0.5936 (2)	0.34568 (6)	0.1157 (4)
N1	0.1751 (3)	1.3344 (13)	0.4526 (4)	0.100 (2)
H1A	0.2092	1.4455	0.4708	0.120*
H1B	0.1557	1.2726	0.4854	0.120*
N2	0.7343 (3)	0.1666 (14)	0.4436 (4)	0.102 (2)
H2D	0.7635	0.2300	0.4226	0.123*
H2E	0.7482	0.0463	0.4805	0.123*
C1	0.2375 (4)	1.5677 (16)	0.3431 (5)	0.103 (3)
H1C	0.2540	1.6065	0.2989	0.154*
H1D	0.2771	1.5124	0.3912	0.154*
H1E	0.2165	1.7202	0.3565	0.154*
C2	0.0684 (4)	0.9407 (18)	0.4006 (5)	0.103 (3)
H2A	0.0354	0.8059	0.3727	0.154*
H2B	0.0437	1.0737	0.4183	0.154*
H2C	0.1056	0.8692	0.4482	0.154*
C3	0.1002 (4)	1.0549 (18)	0.3425 (5)	0.086 (2)
C4	0.0812 (4)	0.9643 (17)	0.2630 (5)	0.090 (2)
H4A	0.0475	0.8324	0.2448	0.108*
C5	0.1113 (4)	1.066 (2)	0.2090 (5)	0.095 (2)
C6	0.1609 (4)	1.2610 (17)	0.2362 (4)	0.086 (2)
H6A	0.1803	1.3325	0.1998	0.103*
C7	0.1822 (4)	1.3524 (15)	0.3159 (5)	0.079 (2)
C8	0.1512 (4)	1.2540 (18)	0.3696 (5)	0.086 (2)
C9	0.6901 (4)	0.5486 (19)	0.3171 (5)	0.108 (3)
H9A	0.7332	0.6128	0.3586	0.163*
H9B	0.6673	0.6858	0.2790	0.163*
H9C	0.7013	0.4084	0.2874	0.163*
C10	0.6417 (4)	−0.0549 (16)	0.5187 (5)	0.101 (3)
H10A	0.6562	−0.2025	0.4948	0.152*
H10B	0.6024	−0.1023	0.5346	0.152*
H10C	0.6810	0.0023	0.5669	0.152*
C11	0.6190 (4)	0.1636 (15)	0.4553 (5)	0.083 (2)
C12	0.5507 (4)	0.2581 (19)	0.4319 (5)	0.093 (2)
H12A	0.5193	0.1906	0.4550	0.112*
C13	0.5290 (4)	0.4543 (18)	0.3736 (5)	0.089 (2)
C14	0.5726 (4)	0.5468 (19)	0.3354 (5)	0.097 (3)
H14A	0.5561	0.6727	0.2942	0.116*
C15	0.6406 (5)	0.4529 (17)	0.3581 (5)	0.087 (2)
C16	0.6641 (4)	0.2596 (18)	0.4174 (5)	0.087 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1232 (8)	0.1683 (11)	0.0770 (6)	−0.0228 (7)	0.0304 (5)	−0.0229 (6)
Br2	0.0927 (6)	0.1499 (9)	0.0949 (7)	0.0165 (6)	0.0231 (5)	0.0050 (7)
N1	0.096 (4)	0.113 (6)	0.087 (5)	−0.010 (4)	0.029 (4)	−0.010 (4)
N2	0.092 (4)	0.116 (6)	0.095 (5)	0.001 (4)	0.028 (4)	−0.003 (4)
C1	0.098 (6)	0.088 (6)	0.117 (7)	−0.006 (5)	0.033 (5)	−0.009 (6)
C2	0.093 (5)	0.119 (7)	0.094 (6)	−0.004 (5)	0.032 (5)	0.013 (6)
C3	0.077 (4)	0.106 (6)	0.070 (5)	0.002 (5)	0.023 (4)	0.006 (5)
C4	0.084 (5)	0.091 (6)	0.085 (5)	0.005 (4)	0.020 (4)	−0.002 (5)
C5	0.092 (5)	0.126 (7)	0.063 (4)	−0.007 (5)	0.024 (4)	0.002 (5)
C6	0.086 (5)	0.105 (6)	0.065 (5)	−0.007 (5)	0.026 (4)	0.008 (5)
C7	0.073 (4)	0.085 (5)	0.074 (4)	−0.003 (4)	0.021 (3)	0.005 (4)
C8	0.082 (4)	0.095 (5)	0.073 (4)	0.007 (4)	0.020 (4)	0.002 (4)
C9	0.105 (6)	0.136 (8)	0.083 (5)	0.006 (6)	0.033 (5)	0.000 (6)
C10	0.109 (6)	0.091 (6)	0.092 (6)	−0.002 (5)	0.023 (5)	−0.008 (5)
C11	0.080 (5)	0.078 (6)	0.076 (5)	−0.009 (4)	0.009 (4)	−0.008 (4)
C12	0.084 (5)	0.109 (7)	0.077 (5)	−0.003 (5)	0.019 (4)	0.002 (5)
C13	0.090 (5)	0.104 (7)	0.062 (4)	0.014 (5)	0.013 (4)	−0.013 (5)
C14	0.095 (6)	0.120 (7)	0.071 (5)	0.001 (5)	0.025 (4)	0.006 (5)
C15	0.094 (5)	0.095 (6)	0.071 (5)	−0.009 (5)	0.029 (4)	−0.010 (5)
C16	0.079 (5)	0.104 (6)	0.075 (5)	−0.009 (5)	0.023 (4)	−0.014 (5)

Geometric parameters (Å, º) top

Br1—C5	1.880 (8)	Br2—C13	1.913 (8)
N1—C8	1.399 (9)	N2—C16	1.403 (9)
N1—H1A	0.8600	N2—H2D	0.8600
N1—H1B	0.8600	N2—H2E	0.8600
C1—C7	1.520 (10)	C9—C15	1.503 (11)
C1—H1C	0.9600	C9—H9A	0.9600
C1—H1D	0.9600	C9—H9B	0.9600
C1—H1E	0.9600	C9—H9C	0.9600
C2—C3	1.497 (10)	C10—C11	1.520 (10)
C2—H2A	0.9600	C10—H10A	0.9600
C2—H2B	0.9600	C10—H10B	0.9600
C2—H2C	0.9600	C10—H10C	0.9600
C3—C4	1.367 (10)	C11—C12	1.373 (10)
C3—C8	1.405 (11)	C11—C16	1.391 (10)
C4—C5	1.390 (11)	C12—C13	1.380 (11)
C4—H4A	0.9300	C12—H12A	0.9300
C5—C6	1.374 (11)	C13—C14	1.363 (11)
C6—C7	1.369 (10)	C14—C15	1.368 (10)
C6—H6A	0.9300	C14—H14A	0.9300
C7—C8	1.390 (10)	C15—C16	1.382 (11)

C8—N1—H1A	120.0	C16—N2—H2D	120.0
C8—N1—H1B	120.0	C16—N2—H2E	120.0
H1A—N1—H1B	120.0	H2D—N2—H2E	120.0
C7—C1—H1C	109.5	C15—C9—H9A	109.5
C7—C1—H1D	109.5	C15—C9—H9B	109.5
H1C—C1—H1D	109.5	H9A—C9—H9B	109.5
C7—C1—H1E	109.5	C15—C9—H9C	109.5
H1C—C1—H1E	109.5	H9A—C9—H9C	109.5
H1D—C1—H1E	109.5	H9B—C9—H9C	109.5
C3—C2—H2A	109.5	C11—C10—H10A	109.5
C3—C2—H2B	109.5	C11—C10—H10B	109.5
H2A—C2—H2B	109.5	H10A—C10—H10B	109.5
C3—C2—H2C	109.5	C11—C10—H10C	109.5
H2A—C2—H2C	109.5	H10A—C10—H10C	109.5
H2B—C2—H2C	109.5	H10B—C10—H10C	109.5
C4—C3—C8	119.0 (7)	C12—C11—C16	119.4 (8)
C4—C3—C2	120.7 (8)	C12—C11—C10	118.6 (8)
C8—C3—C2	120.3 (7)	C16—C11—C10	121.8 (8)
C3—C4—C5	121.2 (8)	C11—C12—C13	119.3 (8)
C3—C4—H4A	119.4	C11—C12—H12A	120.4
C5—C4—H4A	119.4	C13—C12—H12A	120.4
C6—C5—C4	119.1 (8)	C14—C13—C12	121.5 (8)
C6—C5—Br1	120.2 (6)	C14—C13—Br2	119.9 (7)
C4—C5—Br1	120.7 (7)	C12—C13—Br2	118.5 (7)
C7—C6—C5	121.1 (7)	C13—C14—C15	119.5 (8)
C7—C6—H6A	119.5	C13—C14—H14A	120.3
C5—C6—H6A	119.5	C15—C14—H14A	120.3
C6—C7—C8	119.8 (7)	C14—C15—C16	120.1 (8)
C6—C7—C1	119.1 (7)	C14—C15—C9	121.1 (8)
C8—C7—C1	121.1 (7)	C16—C15—C9	118.8 (8)
C7—C8—N1	120.6 (8)	C15—C16—C11	120.1 (8)
C7—C8—C3	119.7 (7)	C15—C16—N2	121.0 (8)
N1—C8—C3	119.5 (7)	C11—C16—N2	118.9 (8)

C8—C3—C4—C5	0.0 (12)	C16—C11—C12—C13	−2.7 (12)
C2—C3—C4—C5	−178.9 (8)	C10—C11—C12—C13	−179.3 (7)
C3—C4—C5—C6	−0.2 (13)	C11—C12—C13—C14	3.7 (13)
C3—C4—C5—Br1	179.1 (6)	C11—C12—C13—Br2	−177.2 (6)
C4—C5—C6—C7	1.6 (13)	C12—C13—C14—C15	−3.4 (13)
Br1—C5—C6—C7	−177.8 (6)	Br2—C13—C14—C15	177.5 (6)
C5—C6—C7—C8	−2.6 (12)	C13—C14—C15—C16	2.2 (13)
C5—C6—C7—C1	179.6 (8)	C13—C14—C15—C9	179.6 (8)
C6—C7—C8—N1	176.4 (7)	C14—C15—C16—C11	−1.2 (12)
C1—C7—C8—N1	−5.9 (12)	C9—C15—C16—C11	−178.7 (7)
C6—C7—C8—C3	2.3 (12)	C14—C15—C16—N2	−177.9 (7)
C1—C7—C8—C3	−180.0 (7)	C9—C15—C16—N2	4.6 (12)
C4—C3—C8—C7	−1.0 (12)	C12—C11—C16—C15	1.5 (12)
C2—C3—C8—C7	177.8 (7)	C10—C11—C16—C15	178.0 (7)
C4—C3—C8—N1	−175.1 (7)	C12—C11—C16—N2	178.2 (7)
C2—C3—C8—N1	3.7 (12)	C10—C11—C16—N2	−5.3 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.50	3.279 (10)	151
N2—H2E···N1ⁱⁱ	0.86	2.50	3.287 (10)	152

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀BrN
M_r	200.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	20.141 (4), 5.150 (1), 17.300 (4)
β (°)	111.53 (3)
V (Å³)	1669.3 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.85
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.211, 0.379
No. of measured, independent and observed [I > 2σ(I)] reflections	3392, 3268, 1523
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.166, 1.06
No. of reflections	3268
No. of parameters	183
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius,1985), CAD-4 Software, XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXTL (Bruker, 2000).

Selected geometric parameters (Å, º) top

Br1—C5	1.880 (8)	Br2—C13	1.913 (8)
N1—C8	1.399 (9)	N2—C16	1.403 (9)

C6—C5—Br1	120.2 (6)	C14—C13—Br2	119.9 (7)
C4—C5—Br1	120.7 (7)	C12—C13—Br2	118.5 (7)
C7—C8—N1	120.6 (8)	C15—C16—N2	121.0 (8)
N1—C8—C3	119.5 (7)	C11—C16—N2	118.9 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.86	2.50	3.279 (10)	151.00
N2—H2E···N1ⁱⁱ	0.86	2.50	3.287 (10)	152.00

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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