5-Bromo-4-iodo-2-methyl­aniline

Liu, Y.-J.; Dai, D.-S.

doi:10.1107/S160053681200921X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1001

doi:10.1107/S160053681200921X

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5-Bromo-4-iodo-2-methylaniline

Yan-Ju Liu ^a ^* and Da-Shun Dai ^b

^aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China, and ^bHenan Hospital of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
^*Correspondence e-mail: liuyanju886@163.com

(Received 17 January 2012; accepted 1 March 2012; online 10 March 2012)

The asymmetric unit of the title compound, C₇H₇BrIN, contains two independent molecules, which are linked by weak N—H⋯N hydroden-bonding interactions between the amino groups.

Related literature

For the synthetic procedure, see: Lee et al. (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₇BrIN
M_r = 311.94
Monoclinic, P 2₁ /c
a = 26.831 (5) Å
b = 5.3920 (11) Å
c = 12.217 (2) Å
β = 98.05 (3)°
V = 1750.1 (6) Å³
Z = 8
Mo Kα radiation
μ = 8.15 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.292, T_max = 0.496
3177 measured reflections
3177 independent reflections
2057 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.163
S = 1.01
3177 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −1.03 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1	0.86	2.67	3.300 (15)	131

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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.

Supporting information

Crystal structure: contains datablocks I, LYJ. DOI: 10.1107/S160053681200921X/aa2048sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200921X/aa2048Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200921X/aa2048Isup3.cml

checkCIF report

Comment top

The tittle compound, 5-bromo-4-iodo-2-methylaniline is an important intermediate, which can be utilized to synthesize highly fluorescent solid-state asymmetric spirosilabifluorene derivatives (Lee et al., 2005). And we report here the crystal structure of the title compound (I), see Fig. 1.

The asymmetric unit contains two title molecules of 5-bromo-4-iodo-2-methylaniline. Weak hydroden bonding interactions link them together with N···N distance 3.300 (14) Å. The bromo, iodo and amino substituents lie in the mean plane of the phenyl rings, with mean deviation of 0.0040 (1) Å from the plane (C2—C7), and 0.0120 (1) Å from the plane (C9—C14). The bond lengths and angles are within normal ranges (Allen et al., 1987).

Related literature top

For the synthetic procedure, see: Lee et al. (2005). F for bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by a method reported in literature (Lee et al., 2005). The crystals were obtained by dissolving (I) (0.5 g) in methanol (50 ml) and evaporating the solvent slowly at room temperature for about 10 d.

Structure description top

For the synthetic procedure, see: Lee et al. (2005). F for bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I).

5-Bromo-4-iodo-2-methylaniline top

Crystal data top

C₇H₇BrIN	F(000) = 1152
M_r = 311.94	D_x = 2.368 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 26.831 (5) Å	θ = 9–13°
b = 5.3920 (11) Å	µ = 8.15 mm⁻¹
c = 12.217 (2) Å	T = 293 K
β = 98.05 (3)°	Block, colourless
V = 1750.1 (6) Å³	0.20 × 0.10 × 0.10 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	2057 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 1.5°
ω/2θ scans	h = −32→31
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
T_min = 0.292, T_max = 0.496	l = 0→14
3177 measured reflections	3 standard reflections every 200 reflections
3177 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0946P)²] where P = (F_o² + 2F_c²)/3
3177 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.97 e Å⁻³
0 restraints	Δρ_min = −1.03 e Å⁻³

Crystal data top

C₇H₇BrIN	V = 1750.1 (6) Å³
M_r = 311.94	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 26.831 (5) Å	µ = 8.15 mm⁻¹
b = 5.3920 (11) Å	T = 293 K
c = 12.217 (2) Å	0.20 × 0.10 × 0.10 mm
β = 98.05 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2057 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.292, T_max = 0.496	3 standard reflections every 200 reflections
3177 measured reflections	intensity decay: 1%
3177 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.01	Δρ_max = 0.97 e Å⁻³
3177 reflections	Δρ_min = −1.03 e Å⁻³
183 parameters

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
I1	0.05030 (3)	−0.37033 (14)	0.72451 (7)	0.0542 (3)
Br1	0.18159 (5)	−0.3594 (2)	0.82076 (10)	0.0583 (4)
N1	0.2022 (4)	0.3506 (17)	0.5418 (9)	0.058 (3)
H1A	0.2337	0.3468	0.5679	0.069*
H1B	0.1914	0.4538	0.4902	0.069*
C1	0.0968 (5)	0.373 (2)	0.4509 (9)	0.053 (3)
H1C	0.1125	0.3476	0.3859	0.080*
H1D	0.1026	0.5404	0.4765	0.080*
H1E	0.0612	0.3447	0.4336	0.080*
C2	0.1187 (4)	0.1958 (19)	0.5397 (9)	0.041 (3)
C3	0.1691 (4)	0.191 (2)	0.5825 (9)	0.043 (3)
C4	0.1864 (4)	0.025 (2)	0.6653 (10)	0.049 (3)
H4A	0.2204	0.0251	0.6940	0.059*
C5	0.1542 (4)	−0.1415 (19)	0.7070 (9)	0.042 (3)
C6	0.1033 (4)	−0.1352 (17)	0.6651 (8)	0.036 (2)
C7	0.0864 (4)	0.030 (2)	0.5818 (9)	0.044 (3)
H7A	0.0524	0.0309	0.5530	0.052*
I2	0.45125 (3)	−0.34995 (15)	0.68253 (7)	0.0534 (3)
Br2	0.31999 (5)	−0.3860 (2)	0.68824 (9)	0.0502 (3)
N2	0.2915 (4)	0.2963 (19)	0.3831 (9)	0.060 (3)
H2A	0.2599	0.2726	0.3840	0.072*
H2B	0.3014	0.4056	0.3395	0.072*
C8	0.3973 (6)	0.385 (2)	0.3750 (11)	0.067 (4)
H8A	0.3858	0.5453	0.3943	0.100*
H8B	0.3841	0.3482	0.2996	0.100*
H8C	0.4334	0.3837	0.3836	0.100*
C9	0.3795 (4)	0.1937 (19)	0.4488 (9)	0.044 (3)
C10	0.4119 (5)	0.039 (2)	0.5159 (9)	0.048 (3)
H10A	0.4463	0.0539	0.5135	0.057*
C11	0.3960 (4)	−0.137 (2)	0.5865 (8)	0.041 (3)
C12	0.3454 (4)	−0.1580 (18)	0.5898 (8)	0.038 (2)
C13	0.3108 (4)	−0.019 (2)	0.5224 (8)	0.040 (3)
H13A	0.2765	−0.0421	0.5237	0.048*
C14	0.3270 (4)	0.157 (2)	0.4527 (9)	0.043 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0587 (5)	0.0456 (5)	0.0631 (6)	−0.0017 (4)	0.0249 (4)	0.0019 (4)
Br1	0.0684 (8)	0.0578 (8)	0.0482 (8)	0.0159 (6)	0.0067 (6)	0.0058 (6)
N1	0.050 (6)	0.065 (7)	0.061 (7)	−0.002 (5)	0.015 (5)	0.007 (6)
C1	0.073 (8)	0.045 (7)	0.043 (7)	−0.002 (6)	0.013 (6)	−0.003 (6)
C2	0.053 (7)	0.037 (6)	0.033 (6)	0.004 (5)	0.012 (5)	−0.006 (5)
C3	0.050 (7)	0.050 (7)	0.034 (6)	0.002 (6)	0.020 (5)	−0.006 (5)
C4	0.046 (7)	0.050 (7)	0.053 (7)	0.008 (6)	0.013 (6)	−0.017 (6)
C5	0.050 (6)	0.030 (6)	0.046 (6)	0.011 (5)	0.008 (5)	−0.004 (5)
C6	0.046 (6)	0.025 (5)	0.038 (6)	−0.001 (5)	0.012 (5)	−0.008 (5)
C7	0.050 (7)	0.041 (6)	0.039 (6)	0.008 (5)	0.003 (5)	−0.010 (5)
I2	0.0509 (5)	0.0515 (5)	0.0565 (5)	0.0043 (4)	0.0028 (4)	−0.0006 (4)
Br2	0.0534 (7)	0.0530 (8)	0.0453 (7)	−0.0088 (6)	0.0104 (5)	0.0087 (6)
N2	0.052 (6)	0.063 (7)	0.061 (7)	−0.006 (5)	0.002 (5)	0.024 (6)
C8	0.082 (10)	0.056 (9)	0.064 (9)	−0.014 (7)	0.019 (7)	0.008 (7)
C9	0.064 (8)	0.032 (6)	0.039 (6)	−0.001 (5)	0.020 (6)	0.002 (5)
C10	0.060 (7)	0.052 (7)	0.033 (6)	−0.002 (6)	0.009 (5)	−0.016 (6)
C11	0.046 (6)	0.051 (7)	0.028 (5)	−0.002 (5)	0.016 (5)	0.003 (5)
C12	0.053 (6)	0.036 (6)	0.028 (5)	−0.006 (5)	0.015 (5)	−0.005 (5)
C13	0.050 (7)	0.046 (7)	0.025 (5)	0.000 (5)	0.012 (5)	0.007 (5)
C14	0.050 (6)	0.040 (6)	0.042 (6)	0.007 (5)	0.012 (5)	−0.005 (5)

Geometric parameters (Å, º) top

I1—C6	2.108 (10)	I2—C11	2.098 (11)
Br1—C5	1.889 (11)	Br2—C12	1.911 (10)
N1—C3	1.378 (14)	N2—C14	1.405 (14)
N1—H1A	0.8600	N2—H2A	0.8600
N1—H1B	0.8600	N2—H2B	0.8600
C1—C2	1.503 (15)	C8—C9	1.490 (14)
C1—H1C	0.9600	C8—H8A	0.9600
C1—H1D	0.9600	C8—H8B	0.9600
C1—H1E	0.9600	C8—H8C	0.9600
C2—C3	1.381 (15)	C9—C10	1.388 (15)
C2—C7	1.392 (15)	C9—C14	1.430 (15)
C3—C4	1.381 (16)	C10—C11	1.391 (15)
C4—C5	1.393 (16)	C10—H10A	0.9300
C4—H4A	0.9300	C11—C12	1.369 (15)
C5—C6	1.390 (14)	C12—C13	1.375 (15)
C6—C7	1.380 (14)	C13—C14	1.383 (15)
C7—H7A	0.9300	C13—H13A	0.9300

C3—N1—H1A	120.0	C14—N2—H2A	120.0
C3—N1—H1B	120.0	C14—N2—H2B	120.0
H1A—N1—H1B	120.0	H2A—N2—H2B	120.0
C2—C1—H1C	109.5	C9—C8—H8A	109.5
C2—C1—H1D	109.5	C9—C8—H8B	109.5
H1C—C1—H1D	109.5	H8A—C8—H8B	109.5
C2—C1—H1E	109.5	C9—C8—H8C	109.5
H1C—C1—H1E	109.5	H8A—C8—H8C	109.5
H1D—C1—H1E	109.5	H8B—C8—H8C	109.5
C3—C2—C7	118.5 (10)	C10—C9—C14	115.8 (10)
C3—C2—C1	123.2 (11)	C10—C9—C8	123.1 (12)
C7—C2—C1	118.3 (10)	C14—C9—C8	121.1 (11)
N1—C3—C4	120.1 (11)	C9—C10—C11	123.7 (11)
N1—C3—C2	120.0 (11)	C9—C10—H10A	118.1
C4—C3—C2	119.9 (11)	C11—C10—H10A	118.1
C3—C4—C5	121.7 (11)	C12—C11—C10	117.8 (10)
C3—C4—H4A	119.2	C12—C11—I2	124.5 (8)
C5—C4—H4A	119.2	C10—C11—I2	117.7 (8)
C6—C5—C4	118.5 (10)	C11—C12—C13	121.9 (10)
C6—C5—Br1	123.2 (8)	C11—C12—Br2	120.8 (8)
C4—C5—Br1	118.3 (9)	C13—C12—Br2	117.3 (8)
C7—C6—C5	119.5 (10)	C12—C13—C14	119.8 (10)
C7—C6—I1	118.3 (8)	C12—C13—H13A	120.1
C5—C6—I1	122.2 (8)	C14—C13—H13A	120.1
C6—C7—C2	122.0 (10)	C13—C14—N2	119.5 (11)
C6—C7—H7A	119.0	C13—C14—C9	120.9 (10)
C2—C7—H7A	119.0	N2—C14—C9	119.6 (10)

C7—C2—C3—N1	179.2 (10)	C14—C9—C10—C11	−2.2 (16)
C1—C2—C3—N1	−1.6 (16)	C8—C9—C10—C11	178.9 (11)
C7—C2—C3—C4	−0.2 (16)	C9—C10—C11—C12	−0.1 (16)
C1—C2—C3—C4	179.0 (10)	C9—C10—C11—I2	−179.3 (8)
N1—C3—C4—C5	−178.8 (10)	C10—C11—C12—C13	2.9 (16)
C2—C3—C4—C5	0.6 (16)	I2—C11—C12—C13	−178.0 (8)
C3—C4—C5—C6	−1.4 (16)	C10—C11—C12—Br2	−177.6 (8)
C3—C4—C5—Br1	−179.7 (8)	I2—C11—C12—Br2	1.4 (13)
C4—C5—C6—C7	1.7 (15)	C11—C12—C13—C14	−3.2 (16)
Br1—C5—C6—C7	180.0 (7)	Br2—C12—C13—C14	177.4 (8)
C4—C5—C6—I1	−178.1 (7)	C12—C13—C14—N2	179.2 (10)
Br1—C5—C6—I1	0.1 (12)	C12—C13—C14—C9	0.6 (16)
C5—C6—C7—C2	−1.4 (15)	C10—C9—C14—C13	1.9 (15)
I1—C6—C7—C2	178.5 (8)	C8—C9—C14—C13	−179.1 (11)
C3—C2—C7—C6	0.6 (16)	C10—C9—C14—N2	−176.6 (10)
C1—C2—C7—C6	−178.6 (9)	C8—C9—C14—N2	2.3 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1	0.86	2.67	3.300 (15)	131

Experimental details

Crystal data
Chemical formula	C₇H₇BrIN
M_r	311.94
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	26.831 (5), 5.3920 (11), 12.217 (2)
β (°)	98.05 (3)
V (Å³)	1750.1 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	8.15
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.292, 0.496
No. of measured, independent and observed [I > 2σ(I)] reflections	3177, 3177, 2057
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.163, 1.01
No. of reflections	3177
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.97, −1.03

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1	0.86	2.67	3.300 (15)	131

Acknowledgements

This work was supported by the Doctoral Research Fund of Henan Chinese Medicine (BSJJ2009–38) and the Science and Technology Department of Henan Province (102102310321).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
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