2,4-Diiodo-3-nitro­anisole

Li, X.; Cao, L.; Ruan, C.; Ji, B.; Zhou, L.

doi:10.1107/S160053681200952X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1500

doi:10.1107/S160053681200952X

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2,4-Diiodo-3-nitroanisole

Xianfei Li,^a Lei Cao,^b Chuansheng Ruan,^c Baoming Ji ^d and Le Zhou ^a ^*

^aCollege of Science, Northwest Agriculture and Forest University, Yangling 712100, People's Republic of China, ^bCollege of Life Science, Northwest Agriculture and Forest University, Yangling 712100, People's Republic of China, ^cZhengzhou University, People's Republic of China, and ^dCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: zhoulechem@yahoo.com.cn

(Received 27 February 2012; accepted 4 March 2012; online 21 April 2012)

In the title compound (systematic name: 1,3-diiodo-4-methoxy-2-nitrobenzene), C₇H₅I₂NO₃, the dihedral angle between the benzene ring and the nitro group is 88.0 (3)°, and the methyl group lies almost in the same plane as the ring [deviation = 0.034 (6) Å]. In the crystal, aromatic π–π stacking occurs between inversion-related rings [centroid–centroid separation = 3.865 (3) Å and slippage = 0.642 Å]. A possible weak C—I⋯π interaction occurs [I⋯π = 3.701 (2) Å and C—I⋯π = 130.18 (13)°], but there are no significant intermolecular I⋯I contacts.

Related literature

For the crystal structures of isomers of the title compound, see: Garden et al. (2002 , 2004 ).

Experimental

Crystal data

C₇H₅I₂NO₃
M_r = 404.92
Monoclinic, P 2₁ /c
a = 9.264 (2) Å
b = 8.756 (2) Å
c = 13.549 (3) Å
β = 108.835 (2)°
V = 1040.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 6.02 mm⁻¹
T = 296 K
0.36 × 0.33 × 0.14 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.220, T_max = 0.486
7459 measured reflections
1937 independent reflections
1712 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.065
S = 1.00
2689 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 1.06 e Å⁻³
Δρ_min = −1.25 e Å⁻³

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681200952X/hb6662sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200952X/hb6662Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200952X/hb6662Isup3.cml

checkCIF report

Comment top

We report here the molecular and supramolecular structures of the title compound, (I), which is isomeric with 2,6-diiodo-4-nitroanisole (Garden etal., 2002) and 2,4-diiodo-6-nitroanisole (Garden et al., 2003). The changed position of iodo, nitro and methoxy may lead to different interactions such as iodo-nitro interactions, and aromatic π···π stacking interactions.

The asymmetric unit of the title compound comprise a whole molecule of 2,4-diiodo-3-nitroanisole (Fig. 1). Atoms I1, I2, C7 and O3 are almost coplanar with the benzene ring. On the contrary, the plane defined by the nitro group is almost perpendicular to the plane of the aromatic ring and form a dihedral angle of 88.0 (4)°. In contrast with 2,6-diiodo-4-nitroanisole (Garden et al., 2002) and 2,4-diiodo-6-nitroanisole (Garden et al., 2003), there is no iodo-nitro interaction in the compound, each molecule link three others by π···π stacking interaction and C—I···π interaction, leading to the formation of a sheet (Fig. 2). The aryl ring planes (centroid Cg1) of two molecules are parallel, show a π···π stacking interaction Cg1···Cg1^viii [symmetry codes: (viii) 1 - x, 2 - y, -z), and the centroid distance is 3.865 (3) Å. C—I···π interaction also occurs in the compound, I1 aim to the phenyl ring [I1···Cg1^ix 3.701 (2) Å, C2—I1···Cg1^ix 130.1 (1)°; symmetry code: (ix) 1 - x, 1/2 + y, 1/2 - z].

Related literature top

For the crystal structures of isomers of the title compound, see: Garden et al. (2002, 2004).

Experimental top

The title compound was obtained from 2-iodo-3-nitrophenol, a solution of 2-iodo-3-nitrophenol (2 mmol) in acetone (20 ml) was added K₂CO₃ (5 mmol). The mixture was stirred at room temperature for 30 min, then CH₃I (5 mmol) was added at once. The resulting solution was then stirred at 343 K for 3 h. The addition of ice (20 g) prompted the precipitation of the title compound, which was collected by filtration and crystallized from ethyl acetate as yellow blocks (yield 90%, m.p. 406–408 K).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The moleuclar sturcture of (I) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of the title compound, showing formation of a sheet built from π···π stacking interactions, and C—I···π interactions.

1,3-diiodo-4-methoxy-2-nitrobenzene top

Crystal data top

C₇H₅I₂NO₃	F(000) = 736
M_r = 404.92	D_x = 2.586 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.264 (2) Å	Cell parameters from 3452 reflections
b = 8.756 (2) Å	θ = 2.8–27.0°
c = 13.549 (3) Å	µ = 6.02 mm⁻¹
β = 108.835 (2)°	T = 296 K
V = 1040.2 (4) Å³	Block, yellow
Z = 4	0.36 × 0.33 × 0.14 mm

Data collection top

Bruker SMART CCD diffractometer	1937 independent reflections
Radiation source: fine-focus sealed tube	1712 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→11
T_min = 0.220, T_max = 0.486	k = −10→10
7459 measured reflections	l = −16→16

Refinement top

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0264P)² + 3.0364P] where P = (F_o² + 2F_c²)/3
2689 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 1.06 e Å⁻³
0 restraints	Δρ_min = −1.25 e Å⁻³

Crystal data top

C₇H₅I₂NO₃	V = 1040.2 (4) Å³
M_r = 404.92	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.264 (2) Å	µ = 6.02 mm⁻¹
b = 8.756 (2) Å	T = 296 K
c = 13.549 (3) Å	0.36 × 0.33 × 0.14 mm
β = 108.835 (2)°

Data collection top

Bruker SMART CCD diffractometer	1937 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1712 reflections with I > 2σ(I)
T_min = 0.220, T_max = 0.486	R_int = 0.018
7459 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.00	Δρ_max = 1.06 e Å⁻³
2689 reflections	Δρ_min = −1.25 e Å⁻³
172 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)

are estimated using the full covariance matrix. The cell esds are taken

into account individually in the estimation of esds in distances, angles

and torsion angles; correlations between esds in cell parameters are only

used when they are defined by crystal symmetry. An approximate (isotropic)

treatment of cell esds is used for estimating esds involving l.s. planes.

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 > 2sigma(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) top

	x	y	z	U_iso*/U_eq
C1	0.3646 (5)	0.8010 (5)	0.0510 (3)	0.0431 (10)
C2	0.4466 (5)	0.8963 (5)	0.1324 (3)	0.0391 (9)
C3	0.6036 (5)	0.9031 (5)	0.1575 (3)	0.0405 (9)
C4	0.6821 (5)	0.8208 (6)	0.1041 (3)	0.0465 (11)
C5	0.5990 (6)	0.7285 (6)	0.0233 (3)	0.0519 (12)
H5	0.6490	0.6724	−0.0141	0.062*
C6	0.4412 (6)	0.7182 (6)	−0.0030 (3)	0.0488 (11)
H6	0.3870	0.6549	−0.0574	0.059*
C7	0.1252 (6)	0.7011 (7)	−0.0503 (4)	0.0659 (15)
H7A	0.1457	0.7238	−0.1138	0.099*
H7B	0.0185	0.7152	−0.0607	0.099*
H7C	0.1529	0.5971	−0.0306	0.099*
N1	0.6918 (5)	1.0000 (5)	0.2475 (3)	0.0507 (10)
O1	0.7319 (6)	0.9427 (5)	0.3316 (3)	0.0860 (14)
O2	0.7193 (5)	1.1291 (5)	0.2286 (3)	0.0831 (13)
O3	0.2116 (4)	0.8002 (4)	0.0299 (2)	0.0571 (9)
I1	0.33063 (4)	1.02858 (4)	0.21050 (3)	0.05654 (12)
I2	0.91883 (4)	0.82973 (6)	0.14145 (3)	0.08415 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.048 (2)	0.046 (2)	0.034 (2)	−0.002 (2)	0.0103 (18)	0.0012 (19)
C2	0.047 (2)	0.037 (2)	0.034 (2)	0.0034 (19)	0.0143 (18)	0.0028 (18)
C3	0.048 (2)	0.039 (2)	0.032 (2)	−0.0018 (19)	0.0096 (18)	0.0047 (18)
C4	0.044 (2)	0.056 (3)	0.041 (2)	0.007 (2)	0.0163 (19)	0.009 (2)
C5	0.067 (3)	0.054 (3)	0.040 (2)	0.009 (2)	0.024 (2)	−0.002 (2)
C6	0.062 (3)	0.049 (3)	0.033 (2)	0.000 (2)	0.011 (2)	−0.0057 (19)
C7	0.054 (3)	0.093 (4)	0.046 (3)	−0.021 (3)	0.009 (2)	−0.017 (3)
N1	0.050 (2)	0.056 (3)	0.043 (2)	−0.0101 (19)	0.0105 (18)	0.0048 (18)
O1	0.119 (4)	0.081 (3)	0.039 (2)	−0.024 (3)	−0.001 (2)	0.005 (2)
O2	0.105 (3)	0.064 (3)	0.065 (2)	−0.034 (2)	0.007 (2)	0.000 (2)
O3	0.0453 (18)	0.070 (2)	0.0505 (19)	−0.0050 (16)	0.0083 (15)	−0.0121 (17)
I1	0.0635 (2)	0.0536 (2)	0.0582 (2)	0.00317 (16)	0.02756 (16)	−0.01141 (15)
I2	0.0470 (2)	0.1373 (4)	0.0684 (3)	0.0114 (2)	0.01898 (18)	−0.0001 (2)

Geometric parameters (Å, º) top

C1—O3	1.353 (5)	C5—C6	1.391 (7)
C1—C6	1.378 (6)	C5—H5	0.9300
C1—C2	1.396 (6)	C6—H6	0.9300
C2—C3	1.384 (6)	C7—O3	1.419 (6)
C2—I1	2.086 (4)	C7—H7A	0.9600
C3—C4	1.382 (6)	C7—H7B	0.9600
C3—N1	1.493 (6)	C7—H7C	0.9600
C4—C5	1.379 (7)	N1—O1	1.189 (5)
C4—I2	2.087 (5)	N1—O2	1.205 (5)

O3—C1—C6	124.7 (4)	C6—C5—H5	119.6
O3—C1—C2	115.9 (4)	C1—C6—C5	120.6 (4)
C6—C1—C2	119.4 (4)	C1—C6—H6	119.7
C3—C2—C1	118.7 (4)	C5—C6—H6	119.7
C3—C2—I1	121.6 (3)	O3—C7—H7A	109.5
C1—C2—I1	119.6 (3)	O3—C7—H7B	109.5
C4—C3—C2	122.5 (4)	H7A—C7—H7B	109.5
C4—C3—N1	118.9 (4)	O3—C7—H7C	109.5
C2—C3—N1	118.6 (4)	H7A—C7—H7C	109.5
C5—C4—C3	117.9 (4)	H7B—C7—H7C	109.5
C5—C4—I2	119.2 (3)	O1—N1—O2	125.2 (4)
C3—C4—I2	122.9 (3)	O1—N1—C3	117.6 (4)
C4—C5—C6	120.8 (4)	O2—N1—C3	117.2 (4)
C4—C5—H5	119.6	C1—O3—C7	117.3 (4)

O3—C1—C2—C3	−179.6 (4)	C3—C4—C5—C6	−0.4 (7)
C6—C1—C2—C3	−1.0 (6)	I2—C4—C5—C6	179.2 (4)
O3—C1—C2—I1	−1.1 (5)	O3—C1—C6—C5	178.8 (4)
C6—C1—C2—I1	177.5 (3)	C2—C1—C6—C5	0.3 (7)
C1—C2—C3—C4	1.0 (6)	C4—C5—C6—C1	0.4 (7)
I1—C2—C3—C4	−177.5 (3)	C4—C3—N1—O1	−90.3 (6)
C1—C2—C3—N1	−177.4 (4)	C2—C3—N1—O1	88.1 (6)
I1—C2—C3—N1	4.2 (5)	C4—C3—N1—O2	88.1 (6)
C2—C3—C4—C5	−0.3 (7)	C2—C3—N1—O2	−93.5 (5)
N1—C3—C4—C5	178.0 (4)	C6—C1—O3—C7	3.3 (7)
C2—C3—C4—I2	−179.9 (3)	C2—C1—O3—C7	−178.2 (4)
N1—C3—C4—I2	−1.5 (6)

Experimental details

Crystal data
Chemical formula	C₇H₅I₂NO₃
M_r	404.92
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.264 (2), 8.756 (2), 13.549 (3)
β (°)	108.835 (2)
V (Å³)	1040.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.02
Crystal size (mm)	0.36 × 0.33 × 0.14

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.220, 0.486
No. of measured, independent and observed [I > 2σ(I)] reflections	7459, 1937, 1712
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.065, 1.00
No. of reflections	2689
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.06, −1.25

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 21072089)

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Garden, S. J., Cunha, F. R. da, Wardell, J. L., Skakle, J. M. S., Low, J. N. & Glidewell, C. (2002). Acta Cryst. C58, o463–o466. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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