2-Iodo-1,3-dimethoxy­benzene

Xue, L.-P.; Qin, J.-H.

doi:10.1107/S1600536809025264

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1790

doi:10.1107/S1600536809025264

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2-Iodo-1,3-dimethoxybenzene

Li-Ping Xue ^a ^* and Jian-Hua Qin ^a

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: lpxue@163.com

(Received 12 June 2009; accepted 30 June 2009; online 8 July 2009)

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 [0 $[\overline{1}]$ 1]. 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 ). For a novel system for decarboxylative bromination, see: Telvekar & Chettiar (2007 ). For related structures, see: Kirsop et al. (2004 ); Ali et al. (2008 ). For a database study of C-halogen–π interactions and their influence on molecular conformation and crystal packing, see: Prasanna & Guru Row (2000 ). For structure validation in chemical crystallography, see: Spek (2009 ).

Experimental

Crystal data

C₈H₉IO₂
M_r = 264.05
Orthorhombic, C m c 2₁
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 ) 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[F² > 2σ(F²)] = 0.019
wR(F²) = 0.046
S = 1.12
850 reflections
55 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −0.84 e Å⁻³
Absolute structure: Flack (1983 ), 362 Friedel pairs
Flack parameter: −0.05 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cg1ⁱ	0.93	2.94	3.824 (9)	159
Symmetry code: (i) -x, y+1, z. Cg1 is the centroid of the C1–C4/C3A/C2A ring.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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 and PLATON (Spek, 2009).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

For the developement of a decarboxylative palladation reaction and its use in a Heck-type olefination of arene carboxylates, see: Myers et al. (2002). For a novel system for decarboxylative bromination, see: Telvekar & Chettiar (2007). For the structure of 1-allyloxy-2-bromo-3-(3-phenylallyloxy)benzene, see: Kirsop et al. (2004). For the structure of 4,4'-diiodo-3,3'-dimethoxybiphenyl, see: Ali et al. (2008). For a database study of C-halogen–π interactions and their influence on molecular conformation and crystal packing, see: Prasanna & Guru Row (2000). For structure validation in chemical crystallography, see: Spek (2009). Cg1 is the centroid of the C1–C4,C3A,C2A ring.

Experimental top

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.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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) and PLATON (Spek, 2009).

Figures top

	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.

2-Iodo-1,3-dimethoxybenzene top

Crystal data top

C₈H₉IO₂	F(000) = 504
M_r = 264.05	D_x = 1.905 Mg m⁻³
Orthorhombic, Cmc2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 1365 reflections
a = 12.5767 (13) Å	θ = 3.7–27.5°
b = 8.6788 (8) Å	µ = 3.43 mm⁻¹
c = 8.4338 (9) Å	T = 296 K
V = 920.55 (16) Å³	Prism, white
Z = 4	0.23 × 0.19 × 0.16 mm

Data collection top

Bruker P4 diffractometer	850 independent reflections
Radiation source: fine-focus sealed tube	840 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 25.5°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −15→15
T_min = 0.500, T_max = 0.616	k = −10→7
2731 measured reflections	l = −9→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.019	H-atom parameters constrained
wR(F²) = 0.046	w = 1/[σ²(F_o²) + (0.0245P)² + 0.6278P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.001
850 reflections	Δρ_max = 1.02 e Å⁻³
55 parameters	Δρ_min = −0.84 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 362 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (4)

Crystal data top

C₈H₉IO₂	V = 920.55 (16) Å³
M_r = 264.05	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 12.5767 (13) Å	µ = 3.43 mm⁻¹
b = 8.6788 (8) Å	T = 296 K
c = 8.4338 (9) Å	0.23 × 0.19 × 0.16 mm

Data collection top

Bruker P4 diffractometer	850 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	840 reflections with I > 2σ(I)
T_min = 0.500, T_max = 0.616	R_int = 0.017
2731 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	H-atom parameters constrained
wR(F²) = 0.046	Δρ_max = 1.02 e Å⁻³
S = 1.12	Δρ_min = −0.84 e Å⁻³
850 reflections	Absolute structure: Flack (1983), 362 Friedel pairs
55 parameters	Absolute structure parameter: −0.05 (4)
1 restraint

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

	x	y	z	U_iso*/U_eq
I1	1.0000	0.95668 (3)	0.54168 (9)	0.04533 (12)
O1	0.8137 (2)	0.7922 (4)	0.7118 (3)	0.0562 (8)
C1	1.0000	0.5564 (7)	0.9408 (11)	0.073 (2)
H1A	1.0000	0.4784	1.0163	0.088*
C2	0.9046 (4)	0.6130 (5)	0.8860 (6)	0.0637 (12)
H2A	0.8409	0.5739	0.9250	0.076*
C3	0.9038 (3)	0.7287 (4)	0.7725 (4)	0.0432 (9)
C4	1.0000	0.7859 (5)	0.7165 (6)	0.0374 (11)
C5	0.7137 (4)	0.7340 (7)	0.7685 (7)	0.0776 (16)
H5A	0.6566	0.7868	0.7160	0.116*
H5B	0.7087	0.7505	0.8808	0.116*
H5C	0.7091	0.6256	0.7464	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.04655 (17)	0.05029 (18)	0.0391 (2)	0.000	0.000	0.01194 (17)
O1	0.0454 (16)	0.0700 (18)	0.0531 (19)	−0.0124 (14)	0.0033 (14)	0.0111 (15)
C1	0.099 (6)	0.052 (4)	0.068 (5)	0.000	0.000	0.030 (3)
C2	0.085 (3)	0.051 (2)	0.055 (3)	−0.016 (2)	0.009 (2)	0.014 (2)
C3	0.058 (2)	0.0384 (16)	0.033 (2)	−0.0055 (16)	0.0005 (16)	−0.0015 (15)
C4	0.055 (3)	0.030 (2)	0.027 (3)	0.000	0.000	−0.0008 (19)
C5	0.056 (3)	0.086 (4)	0.091 (5)	−0.023 (3)	0.010 (3)	0.007 (3)

Geometric parameters (Å, º) top

I1—C4	2.090 (5)	C2—H2A	0.9300
O1—C3	1.359 (5)	C3—C4	1.391 (5)
O1—C5	1.437 (6)	C4—C3ⁱ	1.391 (5)
C1—C2	1.376 (6)	C5—H5A	0.9600
C1—C2ⁱ	1.376 (6)	C5—H5B	0.9600
C1—H1A	0.9300	C5—H5C	0.9600
C2—C3	1.388 (5)

C3—O1—C5	117.5 (4)	C3ⁱ—C4—C3	121.0 (5)
C2—C1—C2ⁱ	121.3 (6)	C3ⁱ—C4—I1	119.5 (2)
C2—C1—H1A	119.3	C3—C4—I1	119.5 (2)
C2ⁱ—C1—H1A	119.3	O1—C5—H5A	109.5
C1—C2—C3	119.8 (5)	O1—C5—H5B	109.5
C1—C2—H2A	120.1	H5A—C5—H5B	109.5
C3—C2—H2A	120.1	O1—C5—H5C	109.5
O1—C3—C2	124.0 (4)	H5A—C5—H5C	109.5
O1—C3—C4	116.9 (3)	H5B—C5—H5C	109.5
C2—C3—C4	119.1 (4)

C2ⁱ—C1—C2—C3	0.5 (11)	O1—C3—C4—C3ⁱ	179.6 (3)
C5—O1—C3—C2	−0.7 (6)	C2—C3—C4—C3ⁱ	0.1 (7)
C5—O1—C3—C4	179.9 (4)	O1—C3—C4—I1	−1.9 (5)
C1—C2—C3—O1	−179.7 (5)	C2—C3—C4—I1	178.6 (3)
C1—C2—C3—C4	−0.3 (7)

Symmetry code: (i) −x+2, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cg1ⁱⁱ	0.93	2.94	3.824 (9)	159

Symmetry code: (ii) −x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₈H₉IO₂
M_r	264.05
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	296
a, b, c (Å)	12.5767 (13), 8.6788 (8), 8.4338 (9)
V (Å³)	920.55 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.43
Crystal size (mm)	0.23 × 0.19 × 0.16

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.500, 0.616
No. of measured, independent and observed [I > 2σ(I)] reflections	2731, 850, 840
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.046, 1.12
No. of reflections	850
No. of parameters	55
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.02, −0.84
Absolute structure	Flack (1983), 362 Friedel pairs
Absolute structure parameter	−0.05 (4)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cg1ⁱ	0.93	2.94	3.824 (9)	159

Symmetry code: (i) −x, y+1, z.

Acknowledgements

The authors thank Luoyang Normal University for supporting this work.

References

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