4-Iodo-3,3′-dimethoxy­biphen­yl

Qamar Ali; Zahid Hussain; Muhammad Raza Shah; Donald VanDerveer

doi:10.1107/S1600536808019557

. 2008 Jul 5;64(Pt 8):o1377. doi: 10.1107/S1600536808019557

4-Iodo-3,3′-dimethoxybiphenyl

Qamar Ali ^a, Zahid Hussain ^a, Muhammad Raza Shah ^a,^*, Donald VanDerveer ^b

PMCID: PMC2962011 PMID: 21203098

Abstract

Molecules of the title compound, C₁₄H₁₃IO₂, exhibit no π–π interactions. The dihedral angle between the two aromatic rings is 43.72 (9)°. The shortest intermolecular I⋯O distance is 3.408 (2) Å, which is significantly less than the sum of the van der Waals radii for I and O (3.50 Å).

Related literature

For related literature, see: Litvinchuk et al. (2004 ▶); Baudry et al. (2006 ▶); Sisson et al. (2006 ▶); Ali et al. (2008 ▶); Ibad et al. (2008 ▶); Baumeister et al. (2001 ▶).

Experimental

Crystal data

C₁₄H₁₃IO₂
M _r = 340.14
Monoclinic,
a = 11.932 (2) Å
b = 15.382 (3) Å
c = 6.9940 (14) Å
β = 90.68 (3)°
V = 1283.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.48 mm⁻¹
T = 153 (2) K
0.43 × 0.38 × 0.36 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ▶) T _min = 0.415, T _max = 0.469 (expected range = 0.362–0.409)
9179 measured reflections
2337 independent reflections
2206 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.053
S = 1.09
2337 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 1.19 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019557/bt2736sup1.cif

e-64-o1377-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019557/bt2736Isup2.hkl

e-64-o1377-Isup2.hkl^{(114.9KB, hkl)}

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

Acknowledgments

The authors thank the Higher Education Commission of Pakistan for financial support.

supplementary crystallographic information

Comment

Self-assembling molecules based on oligo(p-phenylene)s are receiving increased attention as building blocks for supramolecular structures, such as artficial ion channels (Litvinchuk et al., 2004; Baudry et al.,2 006). One can envision that incorporation of a conjugated macrocycle such as porphyrin into an oligo(p-phenylene)s, extends the cylindrical supramolecular organization capabilities of the oligo(pphenylene)s (Sisson et al., 2006) and can result in functionalized pores. The titled compound can be used as a precursor for the synthesis of oligo(p-phenylene)s (Baumeister et al., 2001). The I1—O1 intermolecular distance is 3.408 (2) Å which is significantly less than 3.50 Å, the sum of the van der Waals radii for I and O. Reported data (Ali et al., 2008) indicate that the oxygen atom of a methoxy group polarizes the electronic cloud surrounding the iodide causing a reduction in the I—O intermolecular distance. The phenyl rings are twisted by a dihedral angle of 43.72 (9)°, which is typical for biphenyl molecules (Ibad et al., 2008). The presence of a iodo group at only one phenyl ring least to a twist between the two rings, whereas the rings are coplanar when both phenyl rings bore a iodo group (Ali et al., 2008). The crystal packing diagram (Fig.2) shows that the molecules are interlinked by I—O interactions.

Experimental

5 g (10.7 mmol) of 4,4`-diiodo-3`-methoxy[1,1`-biphenyl]-3-yl-methyl ether was dissolved in 30 ml of THF in a 250 ml round bottom flask. The reaction mixture was stirred until a clear solution formed. Then a tert-butyl lithium solution (8.2 ml, 1.7 M in pentane 13.9 mmol) was added at 0 C. The reaction was monitored after an interval of 5 minutes through TLC.The reaction was stirred for thirty five minutes until a spot of 4-iodo-3,3`-dimethoxy-1,1`-biphenyl appeared on the TLC and was then quenched with 10 ml (1 N HCl) and extracted with 30 ml of chloroform three times. The crude reaction mixture was concentrated using a rotary evaporator. A super saturated solution of crude reaction mixture was prepared in chlorofrom and then methanol was added to this super-saturated solution of reaction mixture, two layers were formed which were separated and analysed by TLC (Hexane:Chloroform 1:1). The methanol layer contained 4-iodo-3,3'-dimethoxybiphenyl as the major product. The slow evaporation of methanol at room temperature yielded colorless crystals.