5-Bromo-4-iodo-2-methyl­aniline

Abstract

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,

• a = 26.831 (5) Å

• b = 5.3920 (11) Å

• c = 12.217 (2) Å

• β = 98.05 (3)°

• V = 1750.1 (6) ų

• 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[F ² > 2σ(F ²)] = 0.060

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681200921X/aa2048Isup3.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
N2—H2A⋯N1	0.86	2.67	3.300 (15)	131

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H atoms were positioned geometrically and refined as riding, with N—H = 0.86 Å and C—H = 0.93 Å, with U_iso(H) = 1.2U_eq(C, N).

Figures

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).

Crystal data

C7H7BrIN	F(000) = 1152
Mr = 311.94	Dx = 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

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

Refinement

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(Fo2) + (0.0946P)2] where P = (Fo2 + 2Fc2)/3
3177 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.97 e Å−3
0 restraints	Δρmin = −1.03 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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