2-Chloro-4-iodo­aniline

Xu, Y.-H.; Wang, C.; Qu, F.

doi:10.1107/S1600536808036076

organic compounds

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Volume 64| Part 12| December 2008| Page o2300

doi:10.1107/S1600536808036076

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2-Chloro-4-iodoaniline

Yun-Hua Xu,^a ^* Can Wang ^b and Fanqi Qu ^b

^aSchool of Science, Beijing Jiaotong University, Beijing 100044, People's Republic of China, and ^bCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, People's Republic of China
^*Correspondence e-mail: yhxu@bjtu.edu.cn

(Received 30 September 2008; accepted 3 November 2008; online 8 November 2008)

The title dihaloaniline, C₆H₅ClIN, shows no significant hydrogen bonds nor the commonly observed I⋯I interactions in the crystal structure, although an amino group and an I atom are available for such contacts. The crystal structure is stabilized by weak interactions involving the amine functionality as donor group and N or halogen atoms as acceptors.

Related literature

The title compound was first synthesized 90 years ago (Dains et al., 1918 ). For structures of halogenated anilines, see: Cox (2001 ); Dey et al. (2003 ); Dou et al. (1993 ); Fukuyo et al. (1982 ); Goubitz et al. (2001 ); Parkin et al. (2005 ); Sakurai et al. (1963 ).

Experimental

Crystal data

C₆H₅ClIN
M_r = 253.46
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.6277 (2) Å
b = 8.7859 (3) Å
c = 14.9217 (5) Å
V = 737.79 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.61 mm⁻¹
T = 90.0 (2) K
0.22 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.424, T_max = 0.630
5635 measured reflections
1696 independent reflections
1587 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.046
S = 1.14
1696 reflections
89 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.18 e Å⁻³
Δρ_min = −0.76 e Å⁻³
Absolute structure: Flack (1983 ), 681 Friedel pairs
Flack parameter: −0.03 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N1ⁱ	0.82 (3)	2.61 (3)	3.359 (4)	153 (4)
N1—H1N⋯Cl1ⁱⁱ	0.82 (3)	2.94 (4)	3.515 (4)	129 (4)
N1—H2N⋯I1ⁱⁱⁱ	0.81 (3)	3.16 (3)	3.807 (4)	139 (4)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) x+1, y, z; (iii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 2002 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO–SMN (Otwinowski & Minor, 1997); 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: SHELXL97 and local procedures.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036076/bh2201sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808036076/bh2201Isup2.hkl

checkCIF report

Comment top

Although structurally simple and readily available, few crystal structures of dihaloanilines have been measured. A total of 10 structures were found in the 2007 CSD; the refcodes are CAJWEQ, CAJWEQ01 (Goubitz et al., 2001), DCHLAN, DCHLAN01 (Sakurai et al., 1963), KUMTER (Cox, 2001), WEMDAT, WEMDEX, WEMDIB, WEMDOH, WEMDUN (Dou et al., 1993). 2-Chloro-4-iodoaniline, (I), an aniline with two different halogen substituents, was first synthesized 90 years ago (Dains et al., 1918), yet its crystal structure is reported here for the first time.

The asymmetric unit contains one molecule (Fig. 1). The N atom is not coplanar with the aromatic ring; H atoms of the amino group are also out of the halogenated benzene ring, but in the opposite direction to that of the N atom. So, the C(Ar)NH₂ group has a pyramidal shape. This is similar to the structure of aniline at 252 K (Fukuyo et al., 1982), 2-iodoaniline at 100 K (Parkin et al., 2005) and 4-iodoaniline at 203 K (Dey et al., 2003).

Despite the presence of amino, chloro and iodo groups, no classic interactions associated with them, such as hydrogen bonds, Cl···Cl, or I···I contacts were observed in the crystal structure of (I). Instead, weak interactions such as N—H···N, N—H···I, and N—H···Cl are found to provide stability to the crystal (Fig. 2).

Related literature top

The title compound was first synthesized 90 years ago (Dains et al., 1918). For structures of halogenated anilines, see: Cox (2001); Dey et al. (2003); Dou et al. (1993); Fukuyo et al. (1982); Goubitz et al. (2001); Parkin et al. (2005); Sakurai et al. (1963).

Experimental top

The compound was purchased from TCI America Laboratory Chemicals as colorless block crystals suitable for single-crystal X-ray diffraction measurement.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); 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: SHELXL97 (Sheldrick, 2008) and local procedures.

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms).
	Fig. 2. A packing diagram of (I) down the a axis.

2-Chloro-4-iodoaniline top

Crystal data top

C₆H₅ClIN	F(000) = 472
M_r = 253.46	D_x = 2.282 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1019 reflections
a = 5.6277 (2) Å	θ = 1.0–27.5°
b = 8.7859 (3) Å	µ = 4.61 mm⁻¹
c = 14.9217 (5) Å	T = 90 K
V = 737.79 (4) Å³	Rounded block, colourless
Z = 4	0.22 × 0.15 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1696 independent reflections
Radiation source: fine-focus sealed tube	1587 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 18 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
ω scans at fixed χ = 55°	h = −7→7
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −11→11
T_min = 0.424, T_max = 0.630	l = −19→19
5635 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.024	w = 1/[σ²(F_o²) + (0.P)² + 0.4678P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.046	(Δ/σ)_max = 0.001
S = 1.14	Δρ_max = 1.18 e Å⁻³
1696 reflections	Δρ_min = −0.76 e Å⁻³
89 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0021 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 681 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.03 (3)

Crystal data top

C₆H₅ClIN	V = 737.79 (4) Å³
M_r = 253.46	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.6277 (2) Å	µ = 4.61 mm⁻¹
b = 8.7859 (3) Å	T = 90 K
c = 14.9217 (5) Å	0.22 × 0.15 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1696 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	1587 reflections with I > 2σ(I)
T_min = 0.424, T_max = 0.630	R_int = 0.033
5635 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.046	Δρ_max = 1.18 e Å⁻³
S = 1.14	Δρ_min = −0.76 e Å⁻³
1696 reflections	Absolute structure: Flack (1983), 681 Friedel pairs
89 parameters	Absolute structure parameter: −0.03 (3)
1 restraint

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

	x	y	z	U_iso*/U_eq
I1	0.48590 (4)	0.17882 (2)	0.730162 (15)	0.01928 (9)
Cl1	0.46148 (17)	0.51349 (10)	0.40305 (6)	0.0194 (2)
N1	0.9067 (6)	0.6647 (5)	0.4646 (2)	0.0188 (8)
H1N	1.048 (5)	0.679 (5)	0.474 (3)	0.028*
H2N	0.882 (7)	0.656 (5)	0.411 (2)	0.028*
C1	0.6370 (6)	0.3328 (4)	0.6386 (2)	0.0133 (7)
C2	0.5194 (7)	0.3639 (3)	0.5594 (2)	0.0138 (7)
H2	0.3764	0.3121	0.5448	0.017*
C3	0.6128 (6)	0.4711 (4)	0.5018 (2)	0.0145 (8)
C4	0.8253 (6)	0.5480 (4)	0.5199 (3)	0.0152 (8)
C5	0.9422 (6)	0.5117 (4)	0.5999 (2)	0.0166 (8)
H5	1.0875	0.5611	0.6142	0.020*
C6	0.8494 (7)	0.4049 (4)	0.6588 (3)	0.0163 (8)
H6	0.9312	0.3812	0.7127	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02354 (13)	0.01764 (13)	0.01666 (14)	−0.00271 (12)	0.00379 (13)	0.00106 (9)
Cl1	0.0189 (5)	0.0231 (4)	0.0163 (4)	0.0003 (4)	−0.0036 (4)	−0.0007 (3)
N1	0.0163 (16)	0.0192 (18)	0.0208 (18)	−0.0046 (15)	0.0035 (15)	0.0025 (15)
C1	0.0136 (16)	0.0101 (17)	0.0161 (19)	0.0001 (15)	0.0027 (15)	−0.0029 (16)
C2	0.0142 (18)	0.0107 (15)	0.0165 (17)	0.0005 (16)	0.003 (2)	−0.0046 (13)
C3	0.0134 (18)	0.0133 (17)	0.0169 (19)	0.0020 (16)	−0.0006 (16)	−0.0017 (16)
C4	0.0121 (18)	0.0129 (18)	0.020 (2)	0.0043 (15)	0.0034 (16)	−0.0031 (17)
C5	0.0096 (18)	0.0154 (17)	0.025 (2)	0.0007 (14)	0.0002 (16)	−0.0053 (15)
C6	0.0172 (19)	0.0182 (19)	0.0133 (18)	0.0019 (16)	−0.0003 (16)	−0.0034 (16)

Geometric parameters (Å, º) top

I1—C1	2.103 (4)	C2—C3	1.379 (5)
Cl1—C3	1.742 (4)	C2—H2	0.9500
N1—C4	1.394 (5)	C3—C4	1.400 (5)
N1—H1N	0.82 (3)	C4—C5	1.400 (5)
N1—H2N	0.81 (3)	C5—C6	1.387 (5)
C1—C2	1.382 (5)	C5—H5	0.9500
C1—C6	1.386 (5)	C6—H6	0.9500

C4—N1—H1N	110 (3)	C4—C3—Cl1	118.6 (3)
C4—N1—H2N	117 (3)	N1—C4—C5	121.2 (3)
H1N—N1—H2N	110 (5)	N1—C4—C3	121.4 (3)
C2—C1—C6	120.6 (3)	C5—C4—C3	117.2 (3)
C2—C1—I1	119.3 (3)	C6—C5—C4	121.1 (3)
C6—C1—I1	120.1 (3)	C6—C5—H5	119.4
C3—C2—C1	119.0 (3)	C4—C5—H5	119.4
C3—C2—H2	120.5	C1—C6—C5	119.7 (3)
C1—C2—H2	120.5	C1—C6—H6	120.1
C2—C3—C4	122.3 (3)	C5—C6—H6	120.1
C2—C3—Cl1	119.1 (3)

C6—C1—C2—C3	−1.9 (5)	Cl1—C3—C4—C5	179.8 (3)
I1—C1—C2—C3	176.5 (2)	N1—C4—C5—C6	174.2 (3)
C1—C2—C3—C4	1.2 (5)	C3—C4—C5—C6	−0.5 (5)
C1—C2—C3—Cl1	−178.6 (3)	C2—C1—C6—C5	1.5 (5)
C2—C3—C4—N1	−174.7 (3)	I1—C1—C6—C5	−176.9 (2)
Cl1—C3—C4—N1	5.1 (5)	C4—C5—C6—C1	−0.3 (5)
C2—C3—C4—C5	0.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N1ⁱ	0.82 (3)	2.61 (3)	3.359 (4)	153 (4)
N1—H1N···Cl1ⁱⁱ	0.82 (3)	2.94 (4)	3.515 (4)	129 (4)
N1—H2N···I1ⁱⁱⁱ	0.81 (3)	3.16 (3)	3.807 (4)	139 (4)

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x+1, y, z; (iii) −x+3/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₆H₅ClIN
M_r	253.46
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	90
a, b, c (Å)	5.6277 (2), 8.7859 (3), 14.9217 (5)
V (Å³)	737.79 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.61
Crystal size (mm)	0.22 × 0.15 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.424, 0.630
No. of measured, independent and observed [I > 2σ(I)] reflections	5635, 1696, 1587
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.046, 1.14
No. of reflections	1696
No. of parameters	89
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.18, −0.76
Absolute structure	Flack (1983), 681 Friedel pairs
Absolute structure parameter	−0.03 (3)

Computer programs: COLLECT (Nonius, 2002), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and local procedures.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N1ⁱ	0.82 (3)	2.61 (3)	3.359 (4)	153 (4)
N1—H1N···Cl1ⁱⁱ	0.82 (3)	2.94 (4)	3.515 (4)	129 (4)
N1—H2N···I1ⁱⁱⁱ	0.81 (3)	3.16 (3)	3.807 (4)	139 (4)

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x+1, y, z; (iii) −x+3/2, −y+1, z−1/2.

Acknowledgements

Y-HX thanks Dr Sihui Long for helpful discussions and invaluable suggestions.

References

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