organic compounds
2,4-Dichloro-1-iodo-6-nitrobenzene
aThe University of Iowa, Department of Occupational and Environmental Health, UI Research Park, Iowa City, IA 52242-5000, USA, and bUniversity of Kentucky, Department of Chemistry, Lexington, KY 40506-0055, USA
*Correspondence e-mail: hans-joachim-lehmler@uiowa.edu
In the 6H2Cl2INO2, there are weak C—H⋯Cl interactions and I⋯O [3.387 (4) Å] close contacts. These interactions form sheets in the ac plane, with the closest contact between adjacent planes occurring between inversion-related nitro O atoms [3.025 (8) Å]. The molecule possesses mirror symmetry, with the halogen, N and C atoms all lying in the mirror plane. Hence, the dihedral angle between the benzene ring and the nitro group is 90°.
of the title compound, CCCDC reference: 997807
Related literature
For crystal structures of similar substituted nitrobenzenes, see: Li et al. (2012); Tahir et al. (2009). For information about polychlorinated biphenyls (PCBs) and their synthesis, see: Joshi et al. (2011); Lehmler et al. (2010); Lehmler & Robertson (2001). For the synthesis of the title compound, see: Sohn et al. (2003).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2006); cell SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008a); molecular graphics: XP in SHELXTL (Sheldrick, 2008a); software used to prepare material for publication: SHELXTL and CIFFIX (Parkin, 2013).
Supporting information
CCDC reference: 997807
10.1107/S1600536814008733/lh5698sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814008733/lh5698Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814008733/lh5698Isup3.cml
The title compound was synthesized from 2,4-dichloro-6-nitroaniline by sequential diazotization and iodonization with NaNO2–HCl–KI system (Sohn et al., 2003). Crystals of the title compound suitable for
analysis were obtained by slow evaporation of a solution of the title compound in hexane-ethyl acetate (10:1).H atoms were found in difference Fourier maps, but subsequently included in the
using riding models, with constrained distances set to 0.95Å (Csp2H). Uiso(H) values were set to 1.2Ueq of the attached atom.Data collection: APEX2 (Bruker, 2006); cell
SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008a); molecular graphics: XP in SHELXTL (Sheldrick, 2008a); software used to prepare material for publication: SHELXTL (Sheldrick, 2008a) and CIFFIX (Parkin, 2013).Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. Symmetry code: (A) x, -y+1/2, z. |
C6H2Cl2INO2 | Dx = 2.430 Mg m−3 |
Mr = 317.89 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Pnma | Cell parameters from 6956 reflections |
a = 8.7760 (5) Å | θ = 5.9–67.7° |
b = 6.8989 (4) Å | µ = 34.30 mm−1 |
c = 14.3518 (8) Å | T = 90 K |
V = 868.93 (9) Å3 | Rounded block, pale yellow |
Z = 4 | 0.13 × 0.10 × 0.04 mm |
F(000) = 592 |
Bruker X8 Proteum diffractometer | 862 independent reflections |
Radiation source: fine-focus rotating anode | 827 reflections with I > 2σ(I) |
Detector resolution: 5.6 pixels mm-1 | Rint = 0.082 |
ϕ and ω scans | θmax = 68.0°, θmin = 5.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | h = −10→7 |
Tmin = 0.052, Tmax = 0.216 | k = −8→8 |
9625 measured reflections | l = −13→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0668P)2 + 0.2013P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.001 |
862 reflections | Δρmax = 0.67 e Å−3 |
71 parameters | Δρmin = −0.68 e Å−3 |
0 restraints | Extinction correction: SHELXL2013 (Sheldrick, 2008a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0021 (4) |
C6H2Cl2INO2 | V = 868.93 (9) Å3 |
Mr = 317.89 | Z = 4 |
Orthorhombic, Pnma | Cu Kα radiation |
a = 8.7760 (5) Å | µ = 34.30 mm−1 |
b = 6.8989 (4) Å | T = 90 K |
c = 14.3518 (8) Å | 0.13 × 0.10 × 0.04 mm |
Bruker X8 Proteum diffractometer | 862 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | 827 reflections with I > 2σ(I) |
Tmin = 0.052, Tmax = 0.216 | Rint = 0.082 |
9625 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.67 e Å−3 |
862 reflections | Δρmin = −0.68 e Å−3 |
71 parameters |
Experimental. Diffraction data were collected with the crystal at 90 K, which is standard practice in this laboratory for the majority of flash-cooled crystals. A correction for radiation damage was included in the SADABS (Sheldrick, 2008b) run. This seems to have resulted in all the atomic displacement parameter ellipsoids looking more spherical than usual. |
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. |
x | y | z | Uiso*/Ueq | ||
I1 | 0.10397 (4) | 0.2500 | 0.70325 (2) | 0.0776 (3) | |
Cl1 | −0.18714 (15) | 0.2500 | 0.54761 (10) | 0.0783 (4) | |
Cl2 | 0.16156 (18) | 0.2500 | 0.24439 (10) | 0.0807 (4) | |
N1 | 0.4037 (5) | 0.2500 | 0.5700 (4) | 0.0797 (14) | |
O1 | 0.4576 (4) | 0.4066 (6) | 0.5918 (2) | 0.0946 (9) | |
C1 | 0.1230 (7) | 0.2500 | 0.5590 (5) | 0.0739 (13) | |
C2 | −0.0053 (7) | 0.2500 | 0.5003 (5) | 0.0753 (13) | |
C3 | 0.0065 (7) | 0.2500 | 0.4060 (4) | 0.0754 (13) | |
H3 | −0.0828 | 0.2500 | 0.3686 | 0.090* | |
C4 | 0.1510 (8) | 0.2500 | 0.3637 (5) | 0.0740 (13) | |
C5 | 0.2811 (7) | 0.2500 | 0.4179 (5) | 0.0765 (13) | |
H5 | 0.3796 | 0.2500 | 0.3904 | 0.092* | |
C6 | 0.2624 (7) | 0.2500 | 0.5133 (4) | 0.0757 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0812 (4) | 0.0798 (4) | 0.0718 (4) | 0.000 | 0.00182 (13) | 0.000 |
Cl1 | 0.0753 (8) | 0.0786 (8) | 0.0810 (8) | 0.000 | 0.0026 (6) | 0.000 |
Cl2 | 0.0828 (9) | 0.0878 (9) | 0.0715 (8) | 0.000 | 0.0000 (6) | 0.000 |
N1 | 0.079 (3) | 0.091 (4) | 0.070 (3) | 0.000 | 0.003 (2) | 0.000 |
O1 | 0.0929 (19) | 0.097 (2) | 0.0936 (18) | −0.0143 (17) | −0.0113 (16) | −0.0056 (17) |
C1 | 0.081 (3) | 0.071 (3) | 0.069 (3) | 0.000 | −0.001 (2) | 0.000 |
C2 | 0.074 (3) | 0.067 (3) | 0.084 (3) | 0.000 | 0.002 (3) | 0.000 |
C3 | 0.084 (3) | 0.065 (3) | 0.077 (3) | 0.000 | −0.004 (3) | 0.000 |
C4 | 0.079 (3) | 0.069 (3) | 0.074 (3) | 0.000 | −0.004 (3) | 0.000 |
C5 | 0.076 (3) | 0.073 (3) | 0.081 (3) | 0.000 | 0.005 (3) | 0.000 |
C6 | 0.076 (3) | 0.073 (3) | 0.078 (3) | 0.000 | −0.003 (3) | 0.000 |
I1—C1 | 2.077 (7) | C1—C2 | 1.406 (9) |
Cl1—C2 | 1.734 (7) | C2—C3 | 1.358 (9) |
Cl2—C4 | 1.715 (7) | C3—C4 | 1.406 (10) |
N1—O1 | 1.220 (4) | C3—H3 | 0.9500 |
N1—O1i | 1.220 (4) | C4—C5 | 1.381 (9) |
N1—C6 | 1.484 (8) | C5—C6 | 1.379 (9) |
C1—C6 | 1.388 (9) | C5—H5 | 0.9500 |
O1—N1—O1i | 124.6 (6) | C4—C3—H3 | 120.0 |
O1—N1—C6 | 117.7 (3) | C5—C4—C3 | 120.2 (6) |
O1i—N1—C6 | 117.7 (3) | C5—C4—Cl2 | 121.1 (5) |
C6—C1—C2 | 114.9 (6) | C3—C4—Cl2 | 118.7 (5) |
C6—C1—I1 | 122.9 (5) | C6—C5—C4 | 117.4 (6) |
C2—C1—I1 | 122.2 (5) | C6—C5—H5 | 121.3 |
C3—C2—C1 | 122.4 (6) | C4—C5—H5 | 121.3 |
C3—C2—Cl1 | 117.4 (5) | C5—C6—C1 | 125.1 (6) |
C1—C2—Cl1 | 120.2 (5) | C5—C6—N1 | 116.5 (5) |
C2—C3—C4 | 119.9 (6) | C1—C6—N1 | 118.4 (5) |
C2—C3—H3 | 120.0 | ||
C6—C1—C2—C3 | 0.000 (2) | C4—C5—C6—C1 | 0.000 (2) |
I1—C1—C2—C3 | 180.000 (1) | C4—C5—C6—N1 | 180.000 (1) |
C6—C1—C2—Cl1 | 180.000 (1) | C2—C1—C6—C5 | 0.000 (2) |
I1—C1—C2—Cl1 | 0.000 (1) | I1—C1—C6—C5 | 180.000 (1) |
C1—C2—C3—C4 | 0.000 (2) | C2—C1—C6—N1 | 180.000 (1) |
Cl1—C2—C3—C4 | 180.000 (1) | I1—C1—C6—N1 | 0.000 (2) |
C2—C3—C4—C5 | 0.000 (2) | O1—N1—C6—C5 | 90.0 (5) |
C2—C3—C4—Cl2 | 180.000 (1) | O1i—N1—C6—C5 | −90.0 (5) |
C3—C4—C5—C6 | 0.000 (1) | O1—N1—C6—C1 | −90.0 (5) |
Cl2—C4—C5—C6 | 180.000 (1) | O1i—N1—C6—C1 | 90.0 (5) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl2ii | 0.95 | 2.77 | 3.718 (7) | 179 |
Symmetry code: (ii) x−1/2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl2i | 0.95 | 2.77 | 3.718 (7) | 179 |
Symmetry code: (i) x−1/2, y, −z+1/2. |
Acknowledgements
This work was supported by grants ES05605, ES013661 and ES017425 from the National Institute of Environmental Health Sciences, National Institutes of Health (NIEHS/NIH).
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound was synthesized as a precursor for the preparation of chiral polychlorinated biphenyl (PCB) derivatives (Lehmler et al., 2010) using the Suzuki-coupling reaction (Joshi et al., 2011; Lehmler & Robertson, 2001). There are C3—H3···Cl2 (x - 0.5, y, 0.5 - z) interactions [C3···Cl2 = 3.718 (7) Å] that link the molecules into flat ribbons along the a axis. Between adjacent ribbons there are close contacts between iodine atoms and the nitro group O atoms, with I···O distances of 3.387 (4) Å. Each iodine atom is the same distance from both oxygen atoms because they are equivalent by virtue of the mirror plane. The linking of adjacent ribbons in the crystal structure give sheets in the ac plane (since the mirror plane is perpendicular to b). The closest contact between adjacent planes occurs between inversion (1 - x, 1 - y, 1 - z) related nitro O atoms [3.025 (8) Å]. The distance between layers is simply half the b axis length. Viewed along the b axis, molecules appear to stack in an alternating fashion about a 21 screw (-x, 0.5 + y,-z), which places Cl1 of one molecule directly over the benzene ring of its screw-related counterpart.
As a result of the symmetrical interaction between the iodines and both nitro group O atoms, the molecular structure of the title compound displayed a 90° dihedral angle between the plane of the nitro group and the plane of the benzene ring (which lies on the mirror plane). Only a few solid state structures of structurally related molecules with a 1-iodo-2-nitrobenzene moiety have been reported previously. The molecular structures of 4-chloro-1-iodo-2-nitrobenzene, a structurally related halogenated nitrobenzene with one iodo substituent ortho to the nitro group, display smaller dihedral angles between benzene ring and nitro group [51.0 (3)° and 29.0 (2)°] in the solid state (Tahir et al., 2009). In contrast, 2,4-diiodo-3-nitroanisole, a nitrobenzene with two iodo substituents ortho to the nitro group, displayed dihedral angle of 88.0 (3)° (Li et al., 2012), probably due to the steric demand of the two ortho iodo substituents. These differences demonstrate that packing effects can make significant contributions to the molecular structure (i.e. the dihedral angle between benzene ring and nitro group) in the solid state.