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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o535.
Published online 2009 February 18. doi:  10.1107/S1600536809004930
PMCID: PMC2968683

4-Chloro-1-iodo-2-nitro­benzene

Abstract

In the mol­ecule of the title compound, C6H3ClINO2, the nitro group is disordered over two sites with occupancies of 0.506 (6) and 0.494 (6). The dihedral angles between the benzene ring and the two disordered components of the nitro group are 29.0 (2) and 51.0 (3)°. The disordering avoids short O(...)O inter­molecular contacts in the crystal.

Related literature

For background, see: Arshad et al. (2008 [triangle], 2009 [triangle]). For related structures, see: Meriles et al. (1999 [triangle]).

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Object name is e-65-0o535-scheme1.jpg

Experimental

Crystal data

  • C6H3ClINO2
  • M r = 283.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o535-efi1.jpg
  • a = 4.1583 (2) Å
  • b = 14.5213 (7) Å
  • c = 13.7990 (6) Å
  • β = 93.361 (2)°
  • V = 831.81 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 4.12 mm−1
  • T = 296 K
  • 0.26 × 0.12 × 0.10 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.554, T max = 0.664
  • 9922 measured reflections
  • 2157 independent reflections
  • 1684 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.051
  • S = 1.02
  • 2157 reflections
  • 128 parameters
  • Only H-atom coordinates refined
  • Δρmax = 0.66 e Å−3
  • Δρmin = −0.60 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809004930/hb2905sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809004930/hb2905Isup2.hkl

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

Acknowledgments

MNA greatfully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing him with a Scholaship under the Indigenous PhD Program (PIN 042–120607-PS2–183).

supplementary crystallographic information

Comment

The title compound (I), (Fig 1), has been prepared as an intermediate for the synthesis of sulfonamides (Arshad et al., 2009) and benzothiazines (Arshad et al., 2008). The crystal structures of p-chlorobromobenzene and p-chloroiodobenzene (Meriles et al., 1999) have been published.

In (I), the iodo and chloro moiety is in plane with the benzene ring. The nitro group is disordered over two sites with nearly equal occupancy ratio of 0.506 (6):0.494 (6). The behaviour of nitro groups is very different from each other. The distance between the symmetry related O-atoms of nitro groups have nearly equal value of 2.110 (9) Å. One group [O1B···O2B (x - 1, y, z)] interact in trans form while the other [O2A···O2A (-x, -y, -z)] remains in cis form. The dihedral angle between the benzene ring and two nitro groups is 29.03 (23)° and 51.03 (31)°, respectively. The dihedral angle between the disordered nitro groups is 79.76 (37)°. There does not exist any classical H-bond or any kind of π-interaction.

Experimental

4-Chloro-2-nitroaniline (2 g, 0.0116 mol) was dissolved in conc. HCl (10 ml) in a flask. The mixture was put in ice to attain 273-78 K. NaNO2 (0.96 g, 0.14 mol) was added in the solution under stirring. After 5 minutes the solution of KI (2.17 g, 0.0134 mol) was added and stirred for 10 minutes at the same temperature i.e 273-278 K. Then ice was removed and allowed to stirr till the room temperature was attained. After this mixture was heated to remove the nitrogen and reduce the volume. The resulting mixture was cooled in ice overnight. The obtained precipitate was filtered and washed with distilled water. The dried filterate was recrystalized in dicloromethane and methanol to obtain crystals of (I) as yellow needles.

Refinement

The O atoms of the nitro group are disordered over two sets of sites in a 0.506 (6):0.496 (6) ratio. The H atoms were located in a difference map and their positions were refined with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
View of the molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level. H-atoms are shown by spheres of arbitrary radius.

Crystal data

C6H3ClINO2F(000) = 528
Mr = 283.44Dx = 2.263 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2157 reflections
a = 4.1583 (2) Åθ = 2.8–28.7°
b = 14.5213 (7) ŵ = 4.12 mm1
c = 13.7990 (6) ÅT = 296 K
β = 93.361 (2)°Needle, yellow
V = 831.81 (7) Å30.26 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer2157 independent reflections
Radiation source: fine-focus sealed tube1684 reflections with I > 2σ(I)
graphiteRint = 0.025
Detector resolution: 7.40 pixels mm-1θmax = 28.7°, θmin = 2.8°
ω scansh = −5→3
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −18→19
Tmin = 0.554, Tmax = 0.664l = −18→18
9922 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051Only H-atom coordinates refined
S = 1.01w = 1/[σ2(Fo2) + (0.0177P)2 + 0.626P] where P = (Fo2 + 2Fc2)/3
2157 reflections(Δ/σ)max = 0.002
128 parametersΔρmax = 0.66 e Å3
0 restraintsΔρmin = −0.60 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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)

xyzUiso*/UeqOcc. (<1)
I1−0.08606 (5)0.03022 (1)0.36564 (1)0.0520 (1)
Cl10.5423 (2)0.29672 (6)0.03919 (7)0.0739 (3)
O1A0.1842 (14)−0.0814 (3)0.2012 (4)0.0693 (19)0.506 (6)
O2A0.1343 (15)−0.0393 (3)0.0522 (4)0.077 (2)0.506 (6)
N10.1689 (7)−0.02093 (18)0.14257 (19)0.0521 (9)
C10.2016 (6)0.07685 (18)0.16917 (19)0.0395 (8)
C20.1064 (6)0.10984 (18)0.25738 (18)0.0394 (8)
C30.1504 (8)0.2032 (2)0.2764 (2)0.0525 (10)
C40.2833 (8)0.2599 (2)0.2098 (3)0.0554 (11)
C50.3754 (7)0.2250 (2)0.1233 (2)0.0487 (9)
C60.3366 (7)0.1329 (2)0.1020 (2)0.0460 (9)
O1B−0.0923 (15)−0.0561 (3)0.1528 (4)0.0721 (19)0.494 (6)
O2B0.4074 (16)−0.0577 (3)0.1171 (4)0.082 (3)0.494 (6)
H60.392 (7)0.109 (2)0.045 (2)0.0552*
H30.086 (8)0.228 (2)0.336 (2)0.0630*
H40.325 (8)0.321 (2)0.223 (2)0.0666*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.0531 (1)0.0648 (1)0.0392 (1)0.0006 (1)0.0124 (1)0.0053 (1)
Cl10.0847 (6)0.0649 (5)0.0724 (6)−0.0142 (5)0.0073 (5)0.0265 (4)
O1A0.098 (4)0.038 (3)0.074 (3)0.000 (2)0.024 (3)0.007 (2)
O2A0.109 (5)0.074 (3)0.050 (3)−0.023 (3)0.013 (3)−0.024 (2)
N10.0660 (16)0.0438 (15)0.0478 (15)−0.0018 (12)0.0137 (13)−0.0032 (12)
C10.0427 (13)0.0359 (14)0.0398 (14)0.0018 (11)0.0015 (11)−0.0004 (11)
C20.0406 (13)0.0450 (15)0.0325 (13)0.0061 (11)0.0010 (10)0.0014 (11)
C30.0650 (18)0.0492 (18)0.0432 (16)0.0097 (14)0.0029 (14)−0.0066 (14)
C40.070 (2)0.0375 (16)0.058 (2)0.0011 (14)−0.0022 (16)−0.0001 (15)
C50.0504 (15)0.0462 (17)0.0490 (17)−0.0004 (12)−0.0010 (13)0.0131 (14)
C60.0508 (15)0.0496 (17)0.0382 (15)0.0019 (12)0.0072 (12)0.0004 (13)
O1B0.096 (4)0.057 (3)0.066 (3)−0.027 (3)0.027 (3)−0.012 (2)
O2B0.100 (5)0.055 (3)0.095 (5)0.019 (3)0.037 (4)−0.017 (3)

Geometric parameters (Å, °)

I1—C22.086 (3)C1—C21.387 (4)
Cl1—C51.734 (3)C2—C31.391 (4)
O1A—N11.193 (6)C3—C41.374 (5)
O1B—N11.216 (7)C4—C51.372 (5)
O2A—N11.275 (6)C5—C61.377 (4)
O2B—N11.197 (7)C3—H30.95 (3)
N1—C11.471 (4)C4—H40.92 (3)
C1—C61.378 (4)C6—H60.90 (3)
O2B···O1Bi2.110 (9)
O1A—N1—O2A120.5 (4)C2—C3—C4120.8 (3)
O1A—N1—C1122.7 (3)C3—C4—C5120.3 (3)
O2A—N1—C1116.7 (3)Cl1—C5—C4120.2 (2)
O1B—N1—C1116.5 (3)Cl1—C5—C6119.1 (2)
O2B—N1—C1116.0 (3)C4—C5—C6120.6 (3)
O1B—N1—O2B127.4 (4)C1—C6—C5118.5 (3)
N1—C1—C2121.7 (2)C2—C3—H3119.5 (18)
N1—C1—C6116.0 (2)C4—C3—H3119.8 (18)
C2—C1—C6122.3 (2)C3—C4—H4121.6 (18)
I1—C2—C1125.33 (19)C5—C4—H4118.0 (18)
I1—C2—C3117.19 (19)C1—C6—H6119.6 (19)
C1—C2—C3117.5 (2)C5—C6—H6121.8 (19)
O1A—N1—C1—C2−30.2 (5)C2—C1—C6—C5−0.5 (4)
O1A—N1—C1—C6148.8 (4)I1—C2—C3—C4178.4 (2)
O2A—N1—C1—C2152.2 (4)C1—C2—C3—C40.0 (4)
O2A—N1—C1—C6−28.8 (5)C2—C3—C4—C5−0.1 (5)
N1—C1—C2—I11.0 (4)C3—C4—C5—Cl1179.9 (3)
N1—C1—C2—C3179.3 (3)C3—C4—C5—C6−0.1 (5)
C6—C1—C2—I1−177.9 (2)Cl1—C5—C6—C1−179.5 (2)
C6—C1—C2—C30.3 (4)C4—C5—C6—C10.4 (4)
N1—C1—C6—C5−179.5 (3)

Symmetry codes: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2905).

References

  • Arshad, M. N., Tahir, M. N., Khan, I. U., Shafiq, M. & Siddiqui, W. A. (2008). Acta Cryst. E64, o2045. [PMC free article] [PubMed]
  • Arshad, M. N., Tahir, M. N., Khan, I. U., Siddiqui, W. A. & Shafiq, M. (2009). Acta Cryst. E65, o230. [PMC free article] [PubMed]
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Meriles, C. A., de Almeida Santos, R. H., do Prado Gambardella, M. T., Ellena, J., Mascarenhas, Y. P. & Brunetti, A. H. (1999). J. Mol. Struct.513, 245–250.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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