Acta Cryst. (2009). E65, o535 [ doi:10.1107/S1600536809004930 ]
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.
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.
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).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
![[Figure 1]](./hb2905fig1thm.gif)
| 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. |
| C6H3ClINO2 | F(000) = 528 |
| Mr = 283.44 | Dx = 2.263 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2157 reflections |
| a = 4.1583 (2) Å | θ = 2.8–28.7° |
| b = 14.5213 (7) Å | µ = 4.12 mm−1 |
| c = 13.7990 (6) Å | T = 296 K |
| β = 93.361 (2)° | Needle, yellow |
| V = 831.81 (7) Å3 | 0.26 × 0.12 × 0.10 mm |
| Z = 4 |
| Bruker Kappa APEXII CCD diffractometer | 2157 independent reflections |
| Radiation source: fine-focus sealed tube | 1684 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| Detector resolution: 7.40 pixels mm-1 | θmax = 28.7°, θmin = 2.8° |
| ω scans | h = −5→3 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −18→19 |
| Tmin = 0.554, Tmax = 0.664 | l = −18→18 |
| 9922 measured reflections |
| 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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.051 | Only H-atom coordinates refined |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0177P)2 + 0.626P] where P = (Fo2 + 2Fc2)/3 |
| 2157 reflections | (Δ/σ)max = 0.002 |
| 128 parameters | Δρmax = 0.66 e Å−3 |
| 0 restraints | Δρmin = −0.60 e Å−3 |
| C6H3ClINO2 | V = 831.81 (7) Å3 |
| Mr = 283.44 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 4.1583 (2) Å | µ = 4.12 mm−1 |
| b = 14.5213 (7) Å | T = 296 K |
| c = 13.7990 (6) Å | 0.26 × 0.12 × 0.10 mm |
| β = 93.361 (2)° |
| Bruker Kappa APEXII CCD diffractometer | 2157 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 1684 reflections with I > 2σ(I) |
| Tmin = 0.554, Tmax = 0.664 | Rint = 0.025 |
| 9922 measured reflections | θmax = 28.7° |
| R[F2 > 2σ(F2)] = 0.023 | Only H-atom coordinates refined |
| wR(F2) = 0.051 | Δρmax = 0.66 e Å−3 |
| S = 1.01 | Δρmin = −0.60 e Å−3 |
| 2157 reflections | Absolute structure: ? |
| 128 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| I1 | −0.08606 (5) | 0.03022 (1) | 0.36564 (1) | 0.0520 (1) | |
| Cl1 | 0.5423 (2) | 0.29672 (6) | 0.03919 (7) | 0.0739 (3) | |
| O1A | 0.1842 (14) | −0.0814 (3) | 0.2012 (4) | 0.0693 (19) | 0.506 (6) |
| O2A | 0.1343 (15) | −0.0393 (3) | 0.0522 (4) | 0.077 (2) | 0.506 (6) |
| N1 | 0.1689 (7) | −0.02093 (18) | 0.14257 (19) | 0.0521 (9) | |
| C1 | 0.2016 (6) | 0.07685 (18) | 0.16917 (19) | 0.0395 (8) | |
| C2 | 0.1064 (6) | 0.10984 (18) | 0.25738 (18) | 0.0394 (8) | |
| C3 | 0.1504 (8) | 0.2032 (2) | 0.2764 (2) | 0.0525 (10) | |
| C4 | 0.2833 (8) | 0.2599 (2) | 0.2098 (3) | 0.0554 (11) | |
| C5 | 0.3754 (7) | 0.2250 (2) | 0.1233 (2) | 0.0487 (9) | |
| C6 | 0.3366 (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) |
| O2B | 0.4074 (16) | −0.0577 (3) | 0.1171 (4) | 0.082 (3) | 0.494 (6) |
| H6 | 0.392 (7) | 0.109 (2) | 0.045 (2) | 0.0552* | |
| H3 | 0.086 (8) | 0.228 (2) | 0.336 (2) | 0.0630* | |
| H4 | 0.325 (8) | 0.321 (2) | 0.223 (2) | 0.0666* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| I1 | 0.0531 (1) | 0.0648 (1) | 0.0392 (1) | 0.0006 (1) | 0.0124 (1) | 0.0053 (1) |
| Cl1 | 0.0847 (6) | 0.0649 (5) | 0.0724 (6) | −0.0142 (5) | 0.0073 (5) | 0.0265 (4) |
| O1A | 0.098 (4) | 0.038 (3) | 0.074 (3) | 0.000 (2) | 0.024 (3) | 0.007 (2) |
| O2A | 0.109 (5) | 0.074 (3) | 0.050 (3) | −0.023 (3) | 0.013 (3) | −0.024 (2) |
| N1 | 0.0660 (16) | 0.0438 (15) | 0.0478 (15) | −0.0018 (12) | 0.0137 (13) | −0.0032 (12) |
| C1 | 0.0427 (13) | 0.0359 (14) | 0.0398 (14) | 0.0018 (11) | 0.0015 (11) | −0.0004 (11) |
| C2 | 0.0406 (13) | 0.0450 (15) | 0.0325 (13) | 0.0061 (11) | 0.0010 (10) | 0.0014 (11) |
| C3 | 0.0650 (18) | 0.0492 (18) | 0.0432 (16) | 0.0097 (14) | 0.0029 (14) | −0.0066 (14) |
| C4 | 0.070 (2) | 0.0375 (16) | 0.058 (2) | 0.0011 (14) | −0.0022 (16) | −0.0001 (15) |
| C5 | 0.0504 (15) | 0.0462 (17) | 0.0490 (17) | −0.0004 (12) | −0.0010 (13) | 0.0131 (14) |
| C6 | 0.0508 (15) | 0.0496 (17) | 0.0382 (15) | 0.0019 (12) | 0.0072 (12) | 0.0004 (13) |
| O1B | 0.096 (4) | 0.057 (3) | 0.066 (3) | −0.027 (3) | 0.027 (3) | −0.012 (2) |
| O2B | 0.100 (5) | 0.055 (3) | 0.095 (5) | 0.019 (3) | 0.037 (4) | −0.017 (3) |
| I1—C2 | 2.086 (3) | C1—C2 | 1.387 (4) |
| Cl1—C5 | 1.734 (3) | C2—C3 | 1.391 (4) |
| O1A—N1 | 1.193 (6) | C3—C4 | 1.374 (5) |
| O1B—N1 | 1.216 (7) | C4—C5 | 1.372 (5) |
| O2A—N1 | 1.275 (6) | C5—C6 | 1.377 (4) |
| O2B—N1 | 1.197 (7) | C3—H3 | 0.95 (3) |
| N1—C1 | 1.471 (4) | C4—H4 | 0.92 (3) |
| C1—C6 | 1.378 (4) | C6—H6 | 0.90 (3) |
| O2B···O1Bi | 2.110 (9) | ||
| O1A—N1—O2A | 120.5 (4) | C2—C3—C4 | 120.8 (3) |
| O1A—N1—C1 | 122.7 (3) | C3—C4—C5 | 120.3 (3) |
| O2A—N1—C1 | 116.7 (3) | Cl1—C5—C4 | 120.2 (2) |
| O1B—N1—C1 | 116.5 (3) | Cl1—C5—C6 | 119.1 (2) |
| O2B—N1—C1 | 116.0 (3) | C4—C5—C6 | 120.6 (3) |
| O1B—N1—O2B | 127.4 (4) | C1—C6—C5 | 118.5 (3) |
| N1—C1—C2 | 121.7 (2) | C2—C3—H3 | 119.5 (18) |
| N1—C1—C6 | 116.0 (2) | C4—C3—H3 | 119.8 (18) |
| C2—C1—C6 | 122.3 (2) | C3—C4—H4 | 121.6 (18) |
| I1—C2—C1 | 125.33 (19) | C5—C4—H4 | 118.0 (18) |
| I1—C2—C3 | 117.19 (19) | C1—C6—H6 | 119.6 (19) |
| C1—C2—C3 | 117.5 (2) | C5—C6—H6 | 121.8 (19) |
| O1A—N1—C1—C2 | −30.2 (5) | C2—C1—C6—C5 | −0.5 (4) |
| O1A—N1—C1—C6 | 148.8 (4) | I1—C2—C3—C4 | 178.4 (2) |
| O2A—N1—C1—C2 | 152.2 (4) | C1—C2—C3—C4 | 0.0 (4) |
| O2A—N1—C1—C6 | −28.8 (5) | C2—C3—C4—C5 | −0.1 (5) |
| N1—C1—C2—I1 | 1.0 (4) | C3—C4—C5—Cl1 | 179.9 (3) |
| N1—C1—C2—C3 | 179.3 (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—C3 | 0.3 (4) | C4—C5—C6—C1 | 0.4 (4) |
| N1—C1—C6—C5 | −179.5 (3) |
| Symmetry codes: (i) x+1, y, z. |
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).
Arshad, M. N., Tahir, M. N., Khan, I. U., Shafiq, M. & Siddiqui, W. A. (2008). Acta Cryst. E64, o2045.
Arshad, M. N., Tahir, M. N., Khan, I. U., Siddiqui, W. A. & Shafiq, M. (2009). Acta Cryst. E65, o230.
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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.
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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.