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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1790.
Published online 2009 July 8. doi:  10.1107/S1600536809025264
PMCID: PMC2977187

2-Iodo-1,3-dimethoxy­benzene

Abstract

Crystals of the title compound, C8H9IO2, were obtained from a dimethyl sulfoxide solution of 2,6-dimethoxy­benzoic acid and iodo­benzene diacetate under a nitro­gen atmosphere at 353 K. In the crystal structure, mol­ecules are linked by weak C—H(...)π inter­actions, generating inter­penetrating one-dimensional chains of perpendicularly oriented mol­ecules extending along [011] and [0An external file that holds a picture, illustration, etc.
Object name is e-65-o1790-efi1.jpg1]. Chains are also formed through non-bonding C—I(...)π contacts extending in the same directions, projecting a zigzag motif in view down [100]. The I(...)Cg distance is 3.695 (2) Å and the C—I(...)Cg angle is 164.17 (14)°. The mol­ecular symmetry m coincides with the mirror plane of the space group Cmc21, resulting in a half-mol­ecule in the asymmetric unit (Z′ = ½).

Related literature

For the development of a deca­rboxylative palladation reaction and its use in a Heck-type olefination of arene carboxyl­ates, see: Myers et al. (2002 [triangle]). For a novel system for deca­rboxylative bromination, see: Telvekar & Chettiar (2007 [triangle]). For related structures, see: Kirsop et al. (2004 [triangle]); Ali et al. (2008 [triangle]). For a database study of C-halogen–π inter­actions and their influence on mol­ecular conformation and crystal packing, see: Prasanna & Guru Row (2000 [triangle]). For structure validation in chemical crystallography, see: Spek (2009 [triangle]).

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Object name is e-65-o1790-scheme1.jpg

Experimental

Crystal data

  • C8H9IO2
  • M r = 264.05
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1790-efi2.jpg
  • a = 12.5767 (13) Å
  • b = 8.6788 (8) Å
  • c = 8.4338 (9) Å
  • V = 920.55 (16) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.43 mm−1
  • T = 296 K
  • 0.23 × 0.19 × 0.16 mm

Data collection

  • Bruker P4 diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.500, T max = 0.616 (expected range = 0.469–0.578)
  • 2731 measured reflections
  • 850 independent reflections
  • 840 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.019
  • wR(F 2) = 0.046
  • S = 1.12
  • 850 reflections
  • 55 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 1.02 e Å−3
  • Δρmin = −0.84 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 362 Friedel pairs
  • Flack parameter: −0.05 (4)

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025264/si2185sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025264/si2185Isup2.hkl

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

Acknowledgments

The authors thank Luoyang Normal University for supporting this work.

supplementary crystallographic information

Comment

Decarboxylation arene carboxylic acids accompanied by simultaneous replacement with different function groups is a useful reaction in organic chemistry (Myers et al., 2002;). Especially iodobenzene derivatives have been found widespread application in organic synthesis because of their selectivity and simplicity of use (Telvekar & Chettiar, 2007). Recently, we found iodobenzene derivatives could be formed by arene carboxylic acid with reaction of PhI(OAc)2. As part of our studies, we report herein the synthesis and crystal structure of the title compound (Fig. 1). The asymmetric unit of the cell contains a half-molecule (Z' = 1/2), which is completed by the space group symmetry m. Atoms I1, C4, C1, H1A occupy the special positions in the mirror plane m. The bond length of C4—I1 is 2.090 (5) Å. The two I—C—C angles, related by mirror symmetry, are 119.5 (2)°.

The molecules in the crystal structure are linked by weak C—H···π interactions to generate a one-dimensional supramolecular structure (Fig. 2). The bond length of C1—H1A···Cg1 is 3.824 (9) Å (Table. 1), Cg1 is the centroid of the C1 C2 C3 C4 C3A C2A ring. In a CSD database study, Prasanna & Guru Row (2000) reported about C-halogen···π interactions and their influence on molecular conformation and crystal packing. The authors found 171 intermolecular C—I···π contacts in the literature, with a mean I···C(π-system) atomic distance of 3.698 (13) Å. In the course of the structure validation (Spek, 2009) of the title compound, a similar geometric parameter (I1···Cg1ii = 3.695 (2) Å) has been found. The C4···Cg1ii distance amounts to 5.735 (5) Å, and the angle C4—I1···Cgii is 164.17 (14) Å. Symmetry code: (ii = -x, y + 2, z - 1). The C4—H1A···π and nonbonding C4—I1···π contacts generate interpenetrating one-dimensional chains of perpendicularly oriented molecules extending along the [0 1 1] and [0 1 1] directions, projecting a zigzag motif in view down [1 0 0] (Fig.3).

Experimental

The title compound was obtained from a mixture of 2,6-Dimethoxybenzoic acid (36 mg) with Iodobenzene diacetate (77 mg) in DMSO (2 ml) under a nitrogen atmosphere at 353 K for 24 h. The crude product was isolated and purified by silica gel column chromatography. Colorless prism-shaped crystals of (I) suitable for X-ray diffraction were grown by slow evaporation of a dichloromethane solution at room temperature.

Refinement

All hydrogen atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å (CH) and Uiso(H) = 1.2Ueq(C), and with C—H = 0.96 Å (CH3) and Uiso(H) = 1.5Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound. Symmetry code: (2 - x, y, z). Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.
Fig. 2.
A view of the one-dimensional weak C—H···π contacts in the title compound.
Fig. 3.
A view down the a axis showing a section of the zigzag motif of the title compound.

Crystal data

C8H9IO2F(000) = 504
Mr = 264.05Dx = 1.905 Mg m3
Orthorhombic, Cmc21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2Cell parameters from 1365 reflections
a = 12.5767 (13) Åθ = 3.7–27.5°
b = 8.6788 (8) ŵ = 3.43 mm1
c = 8.4338 (9) ÅT = 296 K
V = 920.55 (16) Å3Prism, white
Z = 40.23 × 0.19 × 0.16 mm

Data collection

Bruker P4 diffractometer850 independent reflections
Radiation source: fine-focus sealed tube840 reflections with I > 2σ(I)
graphiteRint = 0.017
ω scansθmax = 25.5°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −15→15
Tmin = 0.500, Tmax = 0.616k = −10→7
2731 measured reflectionsl = −9→10

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.019H-atom parameters constrained
wR(F2) = 0.046w = 1/[σ2(Fo2) + (0.0245P)2 + 0.6278P] where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.001
850 reflectionsΔρmax = 1.02 e Å3
55 parametersΔρmin = −0.84 e Å3
1 restraintAbsolute structure: Flack (1983), 362 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.05 (4)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
I11.00000.95668 (3)0.54168 (9)0.04533 (12)
O10.8137 (2)0.7922 (4)0.7118 (3)0.0562 (8)
C11.00000.5564 (7)0.9408 (11)0.073 (2)
H1A1.00000.47841.01630.088*
C20.9046 (4)0.6130 (5)0.8860 (6)0.0637 (12)
H2A0.84090.57390.92500.076*
C30.9038 (3)0.7287 (4)0.7725 (4)0.0432 (9)
C41.00000.7859 (5)0.7165 (6)0.0374 (11)
C50.7137 (4)0.7340 (7)0.7685 (7)0.0776 (16)
H5A0.65660.78680.71600.116*
H5B0.70870.75050.88080.116*
H5C0.70910.62560.74640.116*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.04655 (17)0.05029 (18)0.0391 (2)0.0000.0000.01194 (17)
O10.0454 (16)0.0700 (18)0.0531 (19)−0.0124 (14)0.0033 (14)0.0111 (15)
C10.099 (6)0.052 (4)0.068 (5)0.0000.0000.030 (3)
C20.085 (3)0.051 (2)0.055 (3)−0.016 (2)0.009 (2)0.014 (2)
C30.058 (2)0.0384 (16)0.033 (2)−0.0055 (16)0.0005 (16)−0.0015 (15)
C40.055 (3)0.030 (2)0.027 (3)0.0000.000−0.0008 (19)
C50.056 (3)0.086 (4)0.091 (5)−0.023 (3)0.010 (3)0.007 (3)

Geometric parameters (Å, °)

I1—C42.090 (5)C2—H2A0.9300
O1—C31.359 (5)C3—C41.391 (5)
O1—C51.437 (6)C4—C3i1.391 (5)
C1—C21.376 (6)C5—H5A0.9600
C1—C2i1.376 (6)C5—H5B0.9600
C1—H1A0.9300C5—H5C0.9600
C2—C31.388 (5)
C3—O1—C5117.5 (4)C3i—C4—C3121.0 (5)
C2—C1—C2i121.3 (6)C3i—C4—I1119.5 (2)
C2—C1—H1A119.3C3—C4—I1119.5 (2)
C2i—C1—H1A119.3O1—C5—H5A109.5
C1—C2—C3119.8 (5)O1—C5—H5B109.5
C1—C2—H2A120.1H5A—C5—H5B109.5
C3—C2—H2A120.1O1—C5—H5C109.5
O1—C3—C2124.0 (4)H5A—C5—H5C109.5
O1—C3—C4116.9 (3)H5B—C5—H5C109.5
C2—C3—C4119.1 (4)
C2i—C1—C2—C30.5 (11)O1—C3—C4—C3i179.6 (3)
C5—O1—C3—C2−0.7 (6)C2—C3—C4—C3i0.1 (7)
C5—O1—C3—C4179.9 (4)O1—C3—C4—I1−1.9 (5)
C1—C2—C3—O1−179.7 (5)C2—C3—C4—I1178.6 (3)
C1—C2—C3—C4−0.3 (7)

Symmetry codes: (i) −x+2, y, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1A···Cg1ii0.932.943.824 (9)159

Symmetry codes: (ii) −x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2185).

References

  • Ali, Q., Shah, M. R. & VanDerveer, D. (2008). Acta Cryst. E64, o910. [PMC free article] [PubMed]
  • Bruker (1997). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Kirsop, P., Storey, J. M. D. & Harrison, W. T. A. (2004). Acta Cryst. E60, o1147–o1148.
  • Myers, A. G., Tanaka, D. & Mannion, M. R. (2002). J. Am. Chem. Soc.124, 11250-11251. [PubMed]
  • Prasanna, M. D. & Guru Row, T. N. (2000). Cryst. Eng.3, 135–154.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Telvekar, V. N. & Chettiar, S. N. (2007). Tetrahedron Lett.48, 4529-4532.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography