4-Iodo-3,3′-dimethoxy­biphen­yl

doi:10.1107/S1600536808019557

Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1377.

Published online 2008 July 5. doi: 10.1107/S1600536808019557

PMCID: PMC2962011

4-Iodo-3,3′-dimethoxybiphenyl

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

^aHEJ Research Institute of Chemistry, International Center for Chemical & Biological Sciences, University of Karachi, Karachi 75270, Pakistan

^bChemistry Department, Clemson University, Clemson, SC 29634-0973, USA

Correspondence e-mail: raza_shahm/at/yahoo.com

Received June 26, 2008; Accepted June 27, 2008.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

This article has been cited by other articles in PMC.

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

An external file that holds a picture, illustration, etc.
Object name is e-64-o1377-scheme1.jpg Object name is e-64-o1377-scheme1.jpg

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

Click here to view.^{(17K, cif)}

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

Click here to view.^{(115K, 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.

Figures

Fig. 1.

A perspective thermal elipsoid drawing (50% probability) of the molecule showing the atom labelling scheme.

Fig. 2.

A packing diagram along the a axis showing the short I - O contacts with dashed lines.

Crystal data

C₁₄H₁₃IO₂	F₀₀₀ = 664
M_r = 340.14	D_x = 1.760 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation λ = 0.71073 Å
a = 11.932 (2) Å	Cell parameters from 4368 reflections
b = 15.382 (3) Å	θ = 2.9–26.4º
c = 6.9940 (14) Å	µ = 2.48 mm⁻¹
β = 90.68 (3)º	T = 153 (2) K
V = 1283.6 (4) Å³	Chip, colorless
Z = 4	0.43 × 0.38 × 0.36 mm

Data collection

Rigaku Mercury CCD diffractometer	2337 independent reflections
Radiation source: Sealed Tube	2206 reflections with I > 2σ(I)
Monochromator: Graphite Monochromator	R_int = 0.021
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.4º
T = 153(2) K	θ_min = 3.2º
ω scans	h = −14→14
Absorption correction: multi-scan(Jacobson, 1998)	k = −18→18
T_min = 0.415, T_max = 0.469	l = −8→6
9179 measured reflections

Refinement

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)] = 0.022	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0234P)² + 1.6489P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2337 reflections	Δρ_max = 1.19 e Å⁻³
156 parameters	Δρ_min = −0.45 e Å⁻³
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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)

	x	y	z	U_iso*/U_eq
I1	0.351251 (14)	0.680339 (10)	0.13178 (2)	0.02636 (8)
C1	0.3045 (2)	0.59482 (15)	0.3506 (3)	0.0207 (5)
C2	0.37606 (19)	0.58357 (15)	0.5087 (3)	0.0187 (5)
C3	0.34448 (17)	0.52906 (15)	0.6519 (3)	0.0158 (4)
H3A	0.3926	0.5222	0.7618	0.019*
C4	0.2424 (2)	0.48233 (15)	0.6425 (3)	0.0203 (5)
C5	0.1732 (2)	0.49371 (17)	0.4818 (4)	0.0251 (5)
H5A	0.1037	0.4625	0.4718	0.030*
C6	0.2044 (2)	0.55002 (17)	0.3361 (4)	0.0250 (5)
H6A	0.1566	0.5577	0.2261	0.030*
C7	0.2107 (2)	0.42139 (15)	0.7984 (3)	0.0203 (5)
C8	0.2903 (2)	0.36430 (16)	0.8774 (3)	0.0219 (5)
H8A	0.3663	0.3652	0.8341	0.026*
C9	0.2583 (2)	0.30671 (16)	1.0183 (4)	0.0233 (5)
H9A	0.3129	0.2672	1.0707	0.028*
C10	0.1492 (2)	0.30429 (16)	1.0864 (4)	0.0235 (5)
H10A	0.1285	0.2638	1.1844	0.028*
C11	0.0710 (2)	0.36164 (16)	1.0095 (4)	0.0226 (5)
C12	0.1018 (2)	0.41935 (16)	0.8648 (4)	0.0222 (5)
H12A	0.0468	0.4580	0.8107	0.027*
C13	0.5475 (2)	0.62115 (17)	0.6703 (4)	0.0259 (5)
H13A	0.6153	0.6529	0.6478	0.039*
H13B	0.5651	0.5611	0.6924	0.039*
H13C	0.5108	0.6446	0.7803	0.039*
C14	−0.0733 (3)	0.31310 (18)	1.2189 (4)	0.0340 (7)
H14A	−0.1489	0.3273	1.2525	0.051*
H14B	−0.0248	0.3222	1.3275	0.051*
H14C	−0.0696	0.2533	1.1802	0.051*
O1	0.47461 (14)	0.62845 (11)	0.5063 (2)	0.0238 (4)
O2	−0.03855 (15)	0.36749 (13)	1.0649 (3)	0.0334 (4)

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02789 (11)	0.02800 (11)	0.02336 (11)	0.00115 (6)	0.00705 (7)	0.00536 (6)
C1	0.0225 (12)	0.0197 (11)	0.0200 (12)	−0.0003 (9)	0.0043 (9)	0.0001 (9)
C2	0.0185 (11)	0.0174 (11)	0.0205 (11)	−0.0006 (9)	0.0036 (9)	−0.0022 (9)
C3	0.0133 (10)	0.0184 (11)	0.0156 (11)	0.0032 (8)	−0.0027 (8)	−0.0051 (8)
C4	0.0206 (11)	0.0204 (11)	0.0200 (12)	−0.0002 (9)	0.0016 (9)	−0.0006 (9)
C5	0.0201 (12)	0.0284 (13)	0.0267 (13)	−0.0055 (10)	−0.0031 (10)	0.0035 (10)
C6	0.0220 (12)	0.0302 (13)	0.0226 (12)	−0.0008 (10)	−0.0047 (10)	0.0019 (10)
C7	0.0224 (11)	0.0176 (11)	0.0209 (12)	−0.0035 (9)	−0.0037 (9)	−0.0022 (9)
C8	0.0206 (12)	0.0229 (12)	0.0222 (12)	−0.0008 (9)	−0.0026 (9)	−0.0011 (10)
C9	0.0248 (13)	0.0243 (12)	0.0208 (12)	0.0030 (10)	−0.0053 (10)	−0.0015 (10)
C10	0.0290 (13)	0.0228 (12)	0.0188 (12)	−0.0031 (10)	−0.0017 (10)	0.0026 (10)
C11	0.0213 (12)	0.0226 (12)	0.0239 (12)	−0.0018 (9)	0.0008 (10)	0.0013 (10)
C12	0.0211 (12)	0.0197 (11)	0.0259 (13)	0.0017 (9)	−0.0010 (9)	0.0030 (10)
C13	0.0215 (12)	0.0306 (13)	0.0257 (13)	−0.0047 (10)	0.0006 (10)	−0.0071 (11)
C14	0.0318 (15)	0.0372 (16)	0.0331 (16)	−0.0057 (11)	0.0109 (12)	0.0092 (12)
O1	0.0195 (8)	0.0284 (9)	0.0236 (9)	−0.0066 (7)	0.0013 (7)	−0.0004 (7)
O2	0.0239 (9)	0.0370 (11)	0.0396 (11)	0.0024 (8)	0.0080 (8)	0.0157 (9)

Geometric parameters (Å, °)

I1—C1	2.098 (2)	C9—C10	1.393 (4)
C1—C6	1.382 (3)	C9—H9A	0.9600
C1—C2	1.400 (3)	C10—C11	1.388 (4)
C2—C3	1.363 (3)	C10—H10A	0.9600
C2—O1	1.364 (3)	C11—O2	1.370 (3)
C3—C4	1.416 (3)	C11—C12	1.399 (3)
C3—H3A	0.9600	C12—H12A	0.9600
C4—C5	1.397 (3)	C13—O1	1.436 (3)
C4—C7	1.490 (3)	C13—H13A	0.9599
C5—C6	1.391 (4)	C13—H13B	0.9599
C5—H5A	0.9600	C13—H13C	0.9599
C6—H6A	0.9600	C14—O2	1.429 (3)
C7—C12	1.386 (3)	C14—H14A	0.9599
C7—C8	1.402 (3)	C14—H14B	0.9599
C8—C9	1.382 (4)	C14—H14C	0.9599
C8—H8A	0.9600

I1···O1ⁱ	3.408 (2)

C6—C1—C2	121.0 (2)	C8—C9—H9A	119.1
C6—C1—I1	119.76 (18)	C10—C9—H9A	119.1
C2—C1—I1	119.25 (17)	C11—C10—C9	118.5 (2)
C3—C2—O1	124.5 (2)	C11—C10—H10A	120.7
C3—C2—C1	119.0 (2)	C9—C10—H10A	120.7
O1—C2—C1	116.5 (2)	O2—C11—C10	124.8 (2)
C2—C3—C4	121.6 (2)	O2—C11—C12	115.0 (2)
C2—C3—H3A	119.2	C10—C11—C12	120.1 (2)
C4—C3—H3A	119.2	C7—C12—C11	120.8 (2)
C5—C4—C3	118.3 (2)	C7—C12—H12A	119.6
C5—C4—C7	121.0 (2)	C11—C12—H12A	119.6
C3—C4—C7	120.7 (2)	O1—C13—H13A	109.5
C6—C5—C4	120.4 (2)	O1—C13—H13B	109.5
C6—C5—H5A	119.8	H13A—C13—H13B	109.5
C4—C5—H5A	119.8	O1—C13—H13C	109.5
C1—C6—C5	119.7 (2)	H13A—C13—H13C	109.5
C1—C6—H6A	120.1	H13B—C13—H13C	109.5
C5—C6—H6A	120.1	O2—C14—H14A	109.5
C12—C7—C8	119.1 (2)	O2—C14—H14B	109.5
C12—C7—C4	120.4 (2)	H14A—C14—H14B	109.5
C8—C7—C4	120.4 (2)	O2—C14—H14C	109.5
C9—C8—C7	119.4 (2)	H14A—C14—H14C	109.5
C9—C8—H8A	120.3	H14B—C14—H14C	109.5
C7—C8—H8A	120.3	C2—O1—C13	117.71 (19)
C8—C9—C10	121.9 (2)	C11—O2—C14	117.4 (2)

C6—C1—C2—C3	−1.6 (4)	C3—C4—C7—C8	−43.5 (3)
I1—C1—C2—C3	178.93 (16)	C12—C7—C8—C9	0.6 (4)
C6—C1—C2—O1	177.8 (2)	C4—C7—C8—C9	−178.3 (2)
I1—C1—C2—O1	−1.7 (3)	C7—C8—C9—C10	−0.8 (4)
O1—C2—C3—C4	−178.0 (2)	C8—C9—C10—C11	0.0 (4)
C1—C2—C3—C4	1.3 (3)	C9—C10—C11—O2	−178.8 (2)
C2—C3—C4—C5	−0.4 (3)	C9—C10—C11—C12	1.0 (4)
C2—C3—C4—C7	178.5 (2)	C8—C7—C12—C11	0.4 (4)
C3—C4—C5—C6	−0.4 (4)	C4—C7—C12—C11	179.2 (2)
C7—C4—C5—C6	−179.2 (2)	O2—C11—C12—C7	178.7 (2)
C2—C1—C6—C5	0.9 (4)	C10—C11—C12—C7	−1.2 (4)
I1—C1—C6—C5	−179.64 (19)	C3—C2—O1—C13	−3.3 (3)
C4—C5—C6—C1	0.1 (4)	C1—C2—O1—C13	177.3 (2)
C5—C4—C7—C12	−43.6 (3)	C10—C11—O2—C14	2.9 (4)
C3—C4—C7—C12	137.6 (2)	C12—C11—O2—C14	−176.9 (2)
C5—C4—C7—C8	135.3 (3)

Symmetry codes: (i) x, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2736).

References

Ali, Q., Shah, M. R. & VanDerveer, D. (2008). Acta Cryst. E64, o910. [PMC free article] [PubMed]
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Litvinchuk, S., Bollot, G., Mareda, J., Som, A., Ronan, D., Shah, M. R., Perrottet, P., Sakai, N. & Matile, S. (2004). J. Am. Chem. Soc.126, 10067–10075. [PubMed]
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