4-Iodo-2-methyl­aniline

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

doi:10.1107/S1600536808004145

organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o591

doi:10.1107/S1600536808004145

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4-Iodo-2-methylaniline

Wei Luo,^a Rui Liu,^a Yu-Hao Li,^a Wei Chen ^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 17 January 2008; accepted 10 February 2008; online 15 February 2008)

In the molecule of the title compound, C₇H₈IN, the methyl C, I and N atoms lie in the benzene ring plane. In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the molecules in a stacked arrangement along the a axis.

Related literature

For related literature, see: Kajigaeshi et al. (1988 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₇H₈IN
M_r = 233.04
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.5910 (11) Å
b = 8.9410 (18) Å
c = 15.674 (3) Å
V = 783.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.00 mm⁻¹
T = 294 (2) 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 = 0.487, T_max = 0.670
917 measured reflections
917 independent reflections
737 reflections with I > 2σ(I)
R_int = 0.012
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.151
S = 1.04
917 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.96 e Å⁻³
Absolute structure: Flack (1983 ), with no Friedel pairs
Flack parameter: −0.29 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0B⋯Nⁱ	0.86	2.54	3.397 (15)	174
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

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: PLATON-10M (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004145/hk2418sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004145/hk2418Isup2.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 polymer, organometallic chemistry etc. (Kajigaeshi et al., 1988). We report herein its crystal structure.

In the molecule of (I), (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The atoms I, N and C7 lie in the benzene ring plane.

In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 1) link the molecules stacked along the a axis, (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For related literature, see: Kajigaeshi et al. (1988). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared by the literature method (Kajigaeshi et al., 1988). Crystals suitable for X-ray analysis were obtained by dissolving (I) (0.5 g) in hexane (20 ml) and evaporating the solvent slowly at room temperature for about 7 d.

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: PLATON10M (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.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

4-Iodo-2-methylaniline top

Crystal data top

C₇H₈IN	D_x = 1.976 Mg m⁻³
M_r = 233.04	Melting point: 360 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 5.5910 (11) Å	θ = 10–14°
b = 8.9410 (18) Å	µ = 4.00 mm⁻¹
c = 15.674 (3) Å	T = 294 K
V = 783.5 (3) Å³	Block, purple
Z = 4	0.20 × 0.10 × 0.10 mm
F(000) = 440

Data collection top

Enraf–Nonius CAD-4 diffractometer	737 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.012
Graphite monochromator	θ_max = 26.0°, θ_min = 2.6°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.487, T_max = 0.670	l = 0→19
917 measured reflections	3 standard reflections every 120 min
917 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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.1P)² + 1.P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
917 reflections	Δρ_max = 0.51 e Å⁻³
82 parameters	Δρ_min = −0.96 e Å⁻³
0 restraints	Absolute structure: Flack (1983), with no Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.29 (13)

Crystal data top

C₇H₈IN	V = 783.5 (3) Å³
M_r = 233.04	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.5910 (11) Å	µ = 4.00 mm⁻¹
b = 8.9410 (18) Å	T = 294 K
c = 15.674 (3) Å	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	737 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.012
T_min = 0.487, T_max = 0.670	3 standard reflections every 120 min
917 measured reflections	intensity decay: none
917 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.151	Δρ_max = 0.51 e Å⁻³
S = 1.04	Δρ_min = −0.96 e Å⁻³
917 reflections	Absolute structure: Flack (1983), with no Friedel pairs
82 parameters	Absolute structure parameter: −0.29 (13)
0 restraints

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
I	0.01067 (18)	0.20097 (9)	0.23728 (5)	0.0696 (4)
N	0.407 (2)	0.6567 (10)	−0.0309 (8)	0.063 (3)
H0A	0.3335	0.6711	−0.0784	0.076*
H0B	0.5326	0.7081	−0.0188	0.076*
C1	0.1534 (18)	0.3484 (11)	0.1464 (7)	0.044 (2)
C2	0.360 (2)	0.4273 (12)	0.1643 (8)	0.053 (3)
H2A	0.4425	0.4137	0.2152	0.063*
C3	0.439 (2)	0.5276 (13)	0.1030 (7)	0.054 (3)
H3A	0.5772	0.5825	0.1139	0.064*
C4	0.322 (2)	0.5491 (11)	0.0269 (7)	0.042 (2)
C5	0.122 (2)	0.4658 (11)	0.0088 (7)	0.045 (2)
C6	0.028 (2)	0.3671 (11)	0.0701 (7)	0.051 (3)
H6A	−0.1143	0.3158	0.0601	0.062*
C7	−0.011 (2)	0.4852 (13)	−0.0736 (7)	0.059 (3)
H7A	−0.1480	0.4207	−0.0741	0.089*
H7B	0.0924	0.4599	−0.1204	0.089*
H7C	−0.0615	0.5873	−0.0791	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I	0.0908 (7)	0.0662 (5)	0.0517 (5)	−0.0067 (5)	0.0050 (5)	0.0104 (3)
N	0.061 (6)	0.051 (5)	0.078 (7)	−0.004 (5)	0.007 (6)	0.012 (5)
C1	0.048 (6)	0.044 (5)	0.038 (5)	0.002 (5)	0.011 (5)	−0.001 (4)
C2	0.056 (7)	0.052 (6)	0.050 (6)	−0.005 (5)	−0.005 (6)	−0.005 (5)
C3	0.041 (6)	0.055 (7)	0.064 (7)	−0.001 (5)	0.001 (5)	−0.010 (6)
C4	0.040 (6)	0.043 (6)	0.043 (5)	0.006 (4)	0.009 (5)	−0.002 (4)
C5	0.058 (7)	0.036 (5)	0.040 (5)	0.005 (5)	0.002 (5)	0.001 (4)
C6	0.056 (7)	0.044 (5)	0.054 (6)	−0.005 (6)	−0.001 (6)	−0.006 (4)
C7	0.063 (7)	0.065 (6)	0.050 (5)	0.013 (9)	−0.009 (8)	−0.006 (5)

Geometric parameters (Å, º) top

I—C1	2.099 (10)	C4—C5	1.374 (16)
N—H0A	0.8600	C4—N	1.403 (13)
N—H0B	0.8600	C5—C6	1.408 (15)
C1—C2	1.383 (15)	C6—H6A	0.9300
C1—C6	1.397 (15)	C7—C5	1.500 (15)
C2—C3	1.386 (16)	C7—H7A	0.9600
C2—H2A	0.9300	C7—H7B	0.9600
C3—C4	1.375 (16)	C7—H7C	0.9600
C3—H3A	0.9300

C4—N—H0A	120.0	C3—C4—N	119.7 (11)
C4—N—H0B	120.0	C4—C5—C6	120.3 (10)
H0A—N—H0B	120.0	C4—C5—C7	121.2 (10)
C2—C1—C6	122.2 (10)	C6—C5—C7	118.3 (11)
C2—C1—I	120.0 (8)	C1—C6—C5	118.1 (10)
C6—C1—I	117.7 (8)	C1—C6—H6A	121.0
C1—C2—C3	117.2 (10)	C5—C6—H6A	121.0
C1—C2—H2A	121.4	C5—C7—H7A	109.5
C3—C2—H2A	121.4	C5—C7—H7B	109.5
C4—C3—C2	122.7 (10)	H7A—C7—H7B	109.5
C4—C3—H3A	118.6	C5—C7—H7C	109.5
C2—C3—H3A	118.6	H7A—C7—H7C	109.5
C5—C4—C3	119.4 (10)	H7B—C7—H7C	109.5
C5—C4—N	120.9 (11)

C6—C1—C2—C3	0.2 (16)	C3—C4—C5—C6	4.6 (16)
I—C1—C2—C3	−177.3 (8)	N—C4—C5—C6	−174.8 (9)
C2—C1—C6—C5	2.5 (16)	C3—C4—C5—C7	−179.8 (10)
I—C1—C6—C5	180.0 (7)	N—C4—C5—C7	0.8 (15)
C1—C2—C3—C4	−0.5 (17)	C4—C5—C6—C1	−4.9 (16)
C2—C3—C4—C5	−1.8 (17)	C7—C5—C6—C1	179.4 (10)
C2—C3—C4—N	177.5 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0B···Nⁱ	0.86	2.54	3.397 (15)	174

Symmetry code: (i) x+1/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	C₇H₈IN
M_r	233.04
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	294
a, b, c (Å)	5.5910 (11), 8.9410 (18), 15.674 (3)
V (Å³)	783.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.00
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.487, 0.670
No. of measured, independent and observed [I > 2σ(I)] reflections	917, 917, 737
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.151, 1.04
No. of reflections	917
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.96
Absolute structure	Flack (1983), with no Friedel pairs
Absolute structure parameter	−0.29 (13)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON10M (Spek, 2003), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0B···Nⁱ	0.86	2.54	3.397 (15)	174.00

Symmetry code: (i) x+1/2, −y+3/2, −z.

Acknowledgements

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

References

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