1-Iodo-4-meth­oxy-2-nitro­benzene

Abstract

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,

• a = 18.6370 (13) Å

• b = 11.6257 (5) Å

• c = 7.4740 (3) Å

• V = 1619.38 (15) ų

• 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[F ² > 2σ(F ²)] = 0.014

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812006484/hg5176Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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

Refinement

The C-bound H atoms were geometrically placed (C—H = 0.95–0.98 Å) and refined as riding with U_iso(H) = 1.2–1.5U_eq(C).

Figures

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.

Crystal data

C7H6INO3	F(000) = 1056
Mr = 279.03	Dx = 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

Rigaku Saturn724+ (2x2 bin mode) diffractometer	1841 independent reflections
Radiation source: Rotating Anode	1615 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.017
Detector resolution: 28.5714 pixels mm-1	θmax = 27.5°, θmin = 3.4°
profile data from ω–scans	h = −15→24
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011)	k = −14→14
Tmin = 0.755, Tmax = 1.000	l = −9→8
8053 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)] = 0.014	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.039	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0188P)2 + 0.9351P] where P = (Fo2 + 2Fc2)/3
1841 reflections	(Δ/σ)max = 0.002
110 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.