1-Iodo-4-meth­oxy-2-nitro­benzene

Wardell, J.L.; Tiekink, E.R.T.

doi:10.1107/S1600536812006484

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o761

doi:10.1107/S1600536812006484

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1-Iodo-4-methoxy-2-nitrobenzene

James L. Wardell ^a ‡ and Edward R. T. Tiekink ^b ^*

^aCentro de Desenvolvimento Tecnológico em Saúde (CDTS), Fundação Oswaldo Cruz (FIOCRUZ), Casa Amarela, Campus de Manguinhos, Avenida Brasil 4365, 21040-900 Rio de Janeiro, RJ, Brazil, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 12 February 2012; accepted 14 February 2012; online 17 February 2012)

In the title compound, C₇H₆INO₃, the 12 non-H atoms are planar, with an r.m.s. deviation of 0.016 Å. A close intramolecular I⋯O interaction [3.0295 (13) Å] is present. Intermolecular I⋯O interactions [3.3448 (13) Å] lead to the formation of zigzag chains along the b axis. These are assembled into layers by weak π–π interactions [centroid–centroid distance = 3.8416 (9) Å], and the layers stack along the a axis, being connected by C—H⋯O contacts.

Related literature

For general background to halogen bonding, see: Metrangolo et al. (2008 ); Pennington et al. (2008 ). For previous structural studies probing iodo–nitro interactions, see: Glidewell et al. (2002 , 2004 ); Garden et al. (2002 ). For van der Waals radii, see: Bondi (1964 ).

Experimental

Crystal data

C₇H₆INO₃
M_r = 279.03
Orthorhombic, P b c a
a = 18.6370 (13) Å
b = 11.6257 (5) Å
c = 7.4740 (3) Å
V = 1619.38 (15) Å³
Z = 8
Mo Kα radiation
μ = 3.92 mm⁻¹
T = 100 K
0.13 × 0.09 × 0.01 mm

Data collection

Rigaku Saturn724+ (2 × 2 bin mode) diffractometer
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011 ) T_min = 0.755, T_max = 1.000
8053 measured reflections
1841 independent reflections
1615 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.014
wR(F²) = 0.039
S = 1.04
1841 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O1ⁱ	0.98	2.58	3.4503 (19)	148
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812006484/hg5176sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812006484/hg5176Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812006484/hg5176Isup3.cml

checkCIF report

Comment top

In connection with previous structural studies of iodo···nitro interactions (Glidewell et al., 2002; Garden et al., 2002; Glidewell et al., 2004), the crystal and molecular structure of the title compound (I) was undertaken in order to probe the structure for possible I···O halogen bonding (Metrangolo et al., 2008; Pennington et al., 2008).

The 12 non-hydrogen atoms comprising (I), Fig. 1, are co-planar with a rm.s. deviation = 0.016 Å; the maximum deviations of ±0.026 Å being found for the nitro-O atoms. A close intramolecular I1···O1 interaction of 3.0295 (13) Å is noted that is significantly less than the sum of the van der Waals radii for these atoms, i.e. 3.50 Å (Bondi, 1964). There are also notable intermolecular I1···O interactions, the shortest of 3.3448 (13) Å occurs with the O1ⁱ atom [symmetry operation i: 3/2 - x, 1/2 + y, z]. A longer interaction [3.4530 (13) Å] is formed with the O2 atom of the same nitro group. The I1···O1ⁱ interactions lead to the formation of zigzag chains along the b axis, Fig. 2. The supramolecular chains are assembled into layers in the bc plane by weak π–π interactions [ring centroid···centroid distance = 3.8416 (9) Å for symmetry operation x, 3/2 - y, -1/2 + z]. Layers stack along the a axis and are connected by C—H···O contacts, Fig. 3 and Table 1.

Related literature top

For general background to halogen bonding, see: Metrangolo et al. (2008); Pennington et al. (2008). For previous structural studies probing iodo–nitro interactions, see: Glidewell et al. (2002, 2004); Garden et al. (2002). For van der Waals radii, see: Bondi (1964).

Experimental top

The commercial compound (Aldrich) was recrystallized from EtOH; M.pt: 334–335 K.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the linear supramolecular chain along the b axis in (I). The I···O interactions are shown as blue dashed lines.
	Fig. 3. A view in projection down the c axis of the packing of supramolecular chains in (I). The I···O, C—H···O and π–π interactions are shown as blue, orange and purple dashed lines, respectively.

1-Iodo-4-methoxy-2-nitrobenzene top

Crystal data top

C₇H₆INO₃	F(000) = 1056
M_r = 279.03	D_x = 2.289 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6840 reflections
a = 18.6370 (13) Å	θ = 3.4–27.4°
b = 11.6257 (5) Å	µ = 3.92 mm⁻¹
c = 7.4740 (3) Å	T = 100 K
V = 1619.38 (15) Å³	Plate, dark-orange
Z = 8	0.13 × 0.09 × 0.01 mm

Data collection top

Rigaku Saturn724+ (2x2 bin mode) diffractometer	1841 independent reflections
Radiation source: Rotating Anode	1615 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.017
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
profile data from ω–scans	h = −15→24
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011)	k = −14→14
T_min = 0.755, T_max = 1.000	l = −9→8
8053 measured reflections

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)] = 0.014	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.039	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0188P)² + 0.9351P] where P = (F_o² + 2F_c²)/3
1841 reflections	(Δ/σ)_max = 0.002
110 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₇H₆INO₃	V = 1619.38 (15) Å³
M_r = 279.03	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 18.6370 (13) Å	µ = 3.92 mm⁻¹
b = 11.6257 (5) Å	T = 100 K
c = 7.4740 (3) Å	0.13 × 0.09 × 0.01 mm

Data collection top

Rigaku Saturn724+ (2x2 bin mode) diffractometer	1841 independent reflections
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011)	1615 reflections with I > 2σ(I)
T_min = 0.755, T_max = 1.000	R_int = 0.017
8053 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.014	0 restraints
wR(F²) = 0.039	H-atom parameters constrained
S = 1.04	Δρ_max = 0.42 e Å⁻³
1841 reflections	Δρ_min = −0.25 e Å⁻³
110 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 > 2σ(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
I1	0.697282 (5)	0.925416 (9)	−0.003362 (13)	0.01546 (5)
O1	0.70514 (6)	0.66598 (11)	−0.03589 (18)	0.0231 (3)
O2	0.62939 (7)	0.52986 (10)	0.01236 (15)	0.0214 (3)
O3	0.41118 (6)	0.68759 (8)	0.23820 (15)	0.0148 (2)
N1	0.64607 (7)	0.63180 (12)	0.01188 (16)	0.0133 (3)
C1	0.60441 (8)	0.83551 (12)	0.0734 (2)	0.0119 (3)
C2	0.59202 (8)	0.71660 (12)	0.0719 (2)	0.0116 (3)
C3	0.52698 (8)	0.67047 (12)	0.12652 (19)	0.0122 (3)
H3	0.5199	0.5896	0.1236	0.015*
C4	0.47214 (8)	0.74173 (12)	0.1854 (2)	0.0115 (3)
C5	0.48273 (8)	0.86045 (12)	0.1870 (2)	0.0128 (3)
H5	0.4455	0.9104	0.2254	0.015*
C6	0.54812 (8)	0.90498 (12)	0.1319 (2)	0.0131 (3)
H6	0.5548	0.9860	0.1342	0.016*
C7	0.35196 (8)	0.75849 (13)	0.2943 (2)	0.0157 (3)
H7A	0.3658	0.8025	0.4007	0.024*
H7B	0.3107	0.7096	0.3228	0.024*
H7C	0.3391	0.8116	0.1977	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01244 (8)	0.01476 (8)	0.01918 (8)	−0.00280 (4)	0.00198 (3)	0.00187 (4)
O1	0.0129 (6)	0.0209 (6)	0.0354 (7)	0.0015 (5)	0.0054 (5)	−0.0037 (5)
O2	0.0223 (7)	0.0104 (5)	0.0315 (7)	0.0033 (5)	0.0035 (5)	−0.0004 (4)
O3	0.0109 (5)	0.0121 (5)	0.0214 (6)	−0.0013 (4)	0.0029 (4)	−0.0001 (4)
N1	0.0128 (6)	0.0149 (6)	0.0124 (6)	0.0025 (5)	−0.0020 (4)	−0.0002 (5)
C1	0.0108 (7)	0.0137 (7)	0.0113 (7)	−0.0019 (6)	−0.0011 (5)	0.0018 (5)
C2	0.0122 (7)	0.0115 (6)	0.0111 (7)	0.0038 (6)	−0.0016 (5)	−0.0007 (5)
C3	0.0146 (7)	0.0091 (6)	0.0130 (7)	0.0003 (5)	−0.0024 (5)	0.0004 (5)
C4	0.0101 (6)	0.0135 (7)	0.0109 (7)	−0.0013 (5)	−0.0014 (5)	0.0007 (5)
C5	0.0116 (7)	0.0121 (6)	0.0148 (7)	0.0027 (6)	−0.0009 (5)	−0.0010 (5)
C6	0.0154 (7)	0.0097 (6)	0.0143 (7)	−0.0006 (6)	−0.0014 (6)	0.0003 (6)
C7	0.0110 (7)	0.0170 (7)	0.0191 (8)	0.0009 (6)	0.0019 (6)	0.0001 (6)

Geometric parameters (Å, º) top

I1—C1	2.1017 (14)	C3—C4	1.387 (2)
O1—N1	1.2238 (18)	C3—H3	0.9500
O2—N1	1.225 (2)	C4—C5	1.394 (2)
O3—C4	1.3574 (18)	C5—C6	1.386 (2)
O3—C7	1.4398 (18)	C5—H5	0.9500
N1—C2	1.4791 (19)	C6—H6	0.9500
C1—C6	1.395 (2)	C7—H7A	0.9800
C1—C2	1.4017 (19)	C7—H7B	0.9800
C2—C3	1.387 (2)	C7—H7C	0.9800

C4—O3—C7	117.44 (11)	O3—C4—C5	125.10 (13)
O1—N1—O2	122.90 (14)	C3—C4—C5	119.30 (13)
O1—N1—C2	119.00 (13)	C6—C5—C4	119.44 (13)
O2—N1—C2	118.10 (13)	C6—C5—H5	120.3
C6—C1—C2	116.72 (13)	C4—C5—H5	120.3
C6—C1—I1	114.66 (10)	C5—C6—C1	122.56 (13)
C2—C1—I1	128.62 (11)	C5—C6—H6	118.7
C3—C2—C1	121.54 (13)	C1—C6—H6	118.7
C3—C2—N1	115.27 (12)	O3—C7—H7A	109.5
C1—C2—N1	123.19 (13)	O3—C7—H7B	109.5
C2—C3—C4	120.42 (13)	H7A—C7—H7B	109.5
C2—C3—H3	119.8	O3—C7—H7C	109.5
C4—C3—H3	119.8	H7A—C7—H7C	109.5
O3—C4—C3	115.59 (12)	H7B—C7—H7C	109.5

C6—C1—C2—C3	−0.2 (2)	C7—O3—C4—C3	−177.84 (13)
I1—C1—C2—C3	−179.68 (11)	C7—O3—C4—C5	2.3 (2)
C6—C1—C2—N1	179.41 (13)	C2—C3—C4—O3	−179.07 (13)
I1—C1—C2—N1	−0.1 (2)	C2—C3—C4—C5	0.8 (2)
O1—N1—C2—C3	−178.97 (13)	O3—C4—C5—C6	179.05 (14)
O2—N1—C2—C3	1.04 (19)	C3—C4—C5—C6	−0.9 (2)
O1—N1—C2—C1	1.5 (2)	C4—C5—C6—C1	0.4 (2)
O2—N1—C2—C1	−178.54 (14)	C2—C1—C6—C5	0.1 (2)
C1—C2—C3—C4	−0.3 (2)	I1—C1—C6—C5	179.73 (12)
N1—C2—C3—C4	−179.93 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱ	0.98	2.58	3.4503 (19)	148

Symmetry code: (i) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₆INO₃
M_r	279.03
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	18.6370 (13), 11.6257 (5), 7.4740 (3)
V (Å³)	1619.38 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.92
Crystal size (mm)	0.13 × 0.09 × 0.01

Data collection
Diffractometer	Rigaku Saturn724+ (2x2 bin mode) diffractometer
Absorption correction	Multi-scan (CrystalClear-SM Expert; Rigaku, 2011)
T_min, T_max	0.755, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8053, 1841, 1615
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.014, 0.039, 1.04
No. of reflections	1841
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.25

Computer programs: CrystalClear-SM Expert (Rigaku, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1ⁱ	0.98	2.58	3.4503 (19)	148

Symmetry code: (i) x−1/2, y, −z+1/2.

Footnotes

‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.

Acknowledgements

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil). We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM·C/HIR/MOHE/SC/12).

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