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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2300.
Published online 2008 November 8. doi:  10.1107/S1600536808036076
PMCID: PMC2959873

2-Chloro-4-iodo­aniline

Abstract

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 [triangle]). For structures of halogenated anilines, see: Cox (2001 [triangle]); Dey et al. (2003 [triangle]); Dou et al. (1993 [triangle]); Fukuyo et al. (1982 [triangle]); Goubitz et al. (2001 [triangle]); Parkin et al. (2005 [triangle]); Sakurai et al. (1963 [triangle]).

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Object name is e-64-o2300-scheme1.jpg

Experimental

Crystal data

  • C6H5ClIN
  • M r = 253.46
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2300-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.024
  • wR(F 2) = 0.046
  • S = 1.14
  • 1696 reflections
  • 89 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.18 e Å−3
  • Δρmin = −0.76 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 681 Friedel pairs
  • Flack parameter: −0.03 (3)

Data collection: COLLECT (Nonius, 2002 [triangle]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO–SMN (Otwinowski & Minor, 1997 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97 and local procedures.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

Refinement

H atoms were found in a difference map and those on the aromatic ring subsequently placed in idealized positions with C—H distances of 0.95 Å and isotropic displacement parameters equal to 1.2Ueq of the carrier C atom. Amine H atoms H1N and H2N were refined freely but were restrained to converge to the same N—H bond lengths, with a standard deviation of 0.02 Å. Isotropic displacement parameters for H1N and H2N were computed as 1.5Ueq(N1)

Figures

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.

Crystal data

C6H5ClINF000 = 472
Mr = 253.46Dx = 2.282 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1019 reflections
a = 5.6277 (2) Åθ = 1.0–27.5º
b = 8.7859 (3) ŵ = 4.61 mm1
c = 14.9217 (5) ÅT = 90.0 (2) K
V = 737.79 (4) Å3Rounded block, colourless
Z = 40.22 × 0.15 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer1696 independent reflections
Radiation source: fine-focus sealed tube1587 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
Detector resolution: 18 pixels mm-1θmax = 27.5º
T = 90.0(2) Kθmin = 2.7º
ω scans at fixed χ = 55°h = −7→7
Absorption correction: multi-scan(SCALEPACK; Otwinowski & Minor, 1997)k = −11→11
Tmin = 0.424, Tmax = 0.630l = −19→19
5635 measured reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.024  w = 1/[σ2(Fo2) + (0.P)2 + 0.4678P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.046(Δ/σ)max = 0.001
S = 1.14Δρmax = 1.18 e Å3
1696 reflectionsΔρmin = −0.76 e Å3
89 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0021 (3)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 681 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.03 (3)

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

xyzUiso*/Ueq
I10.48590 (4)0.17882 (2)0.730162 (15)0.01928 (9)
Cl10.46148 (17)0.51349 (10)0.40305 (6)0.0194 (2)
N10.9067 (6)0.6647 (5)0.4646 (2)0.0188 (8)
H1N1.048 (5)0.679 (5)0.474 (3)0.028*
H2N0.882 (7)0.656 (5)0.411 (2)0.028*
C10.6370 (6)0.3328 (4)0.6386 (2)0.0133 (7)
C20.5194 (7)0.3639 (3)0.5594 (2)0.0138 (7)
H20.37640.31210.54480.017*
C30.6128 (6)0.4711 (4)0.5018 (2)0.0145 (8)
C40.8253 (6)0.5480 (4)0.5199 (3)0.0152 (8)
C50.9422 (6)0.5117 (4)0.5999 (2)0.0166 (8)
H51.08750.56110.61420.020*
C60.8494 (7)0.4049 (4)0.6588 (3)0.0163 (8)
H60.93120.38120.71270.020*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.02354 (13)0.01764 (13)0.01666 (14)−0.00271 (12)0.00379 (13)0.00106 (9)
Cl10.0189 (5)0.0231 (4)0.0163 (4)0.0003 (4)−0.0036 (4)−0.0007 (3)
N10.0163 (16)0.0192 (18)0.0208 (18)−0.0046 (15)0.0035 (15)0.0025 (15)
C10.0136 (16)0.0101 (17)0.0161 (19)0.0001 (15)0.0027 (15)−0.0029 (16)
C20.0142 (18)0.0107 (15)0.0165 (17)0.0005 (16)0.003 (2)−0.0046 (13)
C30.0134 (18)0.0133 (17)0.0169 (19)0.0020 (16)−0.0006 (16)−0.0017 (16)
C40.0121 (18)0.0129 (18)0.020 (2)0.0043 (15)0.0034 (16)−0.0031 (17)
C50.0096 (18)0.0154 (17)0.025 (2)0.0007 (14)0.0002 (16)−0.0053 (15)
C60.0172 (19)0.0182 (19)0.0133 (18)0.0019 (16)−0.0003 (16)−0.0034 (16)

Geometric parameters (Å, °)

I1—C12.103 (4)C2—C31.379 (5)
Cl1—C31.742 (4)C2—H20.9500
N1—C41.394 (5)C3—C41.400 (5)
N1—H1N0.82 (3)C4—C51.400 (5)
N1—H2N0.81 (3)C5—C61.387 (5)
C1—C21.382 (5)C5—H50.9500
C1—C61.386 (5)C6—H60.9500
C4—N1—H1N110 (3)C4—C3—Cl1118.6 (3)
C4—N1—H2N117 (3)N1—C4—C5121.2 (3)
H1N—N1—H2N110 (5)N1—C4—C3121.4 (3)
C2—C1—C6120.6 (3)C5—C4—C3117.2 (3)
C2—C1—I1119.3 (3)C6—C5—C4121.1 (3)
C6—C1—I1120.1 (3)C6—C5—H5119.4
C3—C2—C1119.0 (3)C4—C5—H5119.4
C3—C2—H2120.5C1—C6—C5119.7 (3)
C1—C2—H2120.5C1—C6—H6120.1
C2—C3—C4122.3 (3)C5—C6—H6120.1
C2—C3—Cl1119.1 (3)
C6—C1—C2—C3−1.9 (5)Cl1—C3—C4—C5179.8 (3)
I1—C1—C2—C3176.5 (2)N1—C4—C5—C6174.2 (3)
C1—C2—C3—C41.2 (5)C3—C4—C5—C6−0.5 (5)
C1—C2—C3—Cl1−178.6 (3)C2—C1—C6—C51.5 (5)
C2—C3—C4—N1−174.7 (3)I1—C1—C6—C5−176.9 (2)
Cl1—C3—C4—N15.1 (5)C4—C5—C6—C1−0.3 (5)
C2—C3—C4—C50.0 (5)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···N1i0.82 (3)2.61 (3)3.359 (4)153 (4)
N1—H1N···Cl1ii0.82 (3)2.94 (4)3.515 (4)129 (4)
N1—H2N···I1iii0.81 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2201).

References

  • Cox, P. J. (2001). Acta Cryst. E57, o1203–o1205.
  • Dains, F. B., Vaughan, T. H. & Janney, W. M. (1918). J. Am. Chem. Soc.40, 930–936.
  • Dey, A., Jetti, R. K. R., Boese, R. & Desiraju, G. R. (2003). CrystEngComm, 5, 248–252.
  • Dou, S. Q., Weiden, N. & Weiss, A. (1993). Acta Chim. Hung.130, 497–522.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Fukuyo, M., Hirotsu, K. & Higuchi, T. (1982). Acta Cryst. B38, 640–643.
  • Goubitz, K., Sonneveld, E. J. & Schenk, H. (2001). Z. Kristallogr.216, 176–181.
  • Nonius (2002). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Parkin, A., Spanswick, C. K., Pulham, C. R. & Wilson, C. C. (2005). Acta Cryst. E61, o1087–o1089.
  • Sakurai, T., Sundaralingam, M. & Jeffrey, G. A. (1963). Acta Cryst.16, 354–363.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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