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 ▶, 2009 ▶). For related structures, see: Meriles et al. (1999 ▶).

Experimental

Crystal data

• C₆H₃ClINO₂

• M _r = 283.44

• Monoclinic,

• a = 4.1583 (2) Å

• b = 14.5213 (7) Å

• c = 13.7990 (6) Å

• β = 93.361 (2)°

• V = 831.81 (7) ų

• 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 ▶) 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

• Δρ_max = 0.66 e Å⁻³

• Δρ_min = −0.60 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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.

Supplementary Material

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

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 U_iso(H) = 1.2U_eq(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

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

Data collection

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

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

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, °)

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.