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access4,4′-Diiodo-3,3′-dimethoxybiphenyl
aHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and bMolecular Structure Center, Chemistry Department, Clemson University, Clemson, SC 29634-0973, USA
*Correspondence e-mail: raza_shahm@yahoo.com
The molecules of the title compound, C14H12I2O2, lie on inversion centers and are linked by I⋯O interactions with intermolecular distances of 3.324 (3) Å. The aromatic rings display no significant intercalation or stacking interactions.
Related literature
For related literature see: Sakai & Matile (2003![[Sakai, N. & Matile, S. (2003). Chem. Commun. pp. 2514-2523.]](../../../../../../logos/arrows/e_arr.gif "Sakai, N. & Matile, S. (2003). Chem. Commun. pp. 2514-2523.")
); Sakai et al. (1997); Anelli et al. (2001); Baumeister et al. (2001); Fidzinski et al. (2003); Mullen & Wegner (1998); Schwab & Levin (1999); Sisson et al. (2006).
![[Scheme 1]](pv2077scheme1.gif)
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku/MSC, 2006); cell CrystalClear; data reduction: REQAB (Jacobson, 1998) and 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.
Supporting information
contains datablocks I, global. DOI: 10.1107/S160053680801129X/pv2077sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S160053680801129X/pv2077Isup2.hkl
Fast Blue B salt (o-dianisidine bisdiazotated zinc double salt, 10.00 g, 21 mmol), was added to a solution of KI (28 g, 0.17 mmol) in water (200 ml). The mixture was stirred at room temperature for 14 h. After dilution with dichloromethane, the crude reaction mixture was concentrated in vacuo. Purification of the crude product on silica gel (dichloromethane:hexane 1:4) followed by evaporation of the solvent under in vacuo gave the pure desired product as a pale yellow solid in 70% yield. Single crystals suitable for X-ray crystallography were obtained by slow evaporation of a solution of pale yellow solid in ethanol at room temperature.
All H atoms were geometrically positioned and were allowed to ride on the corresponding C-atoms with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) of the attached C atom for methyl H atoms and 1.2Ueq(C) for other H atoms. The highest peak in the final difference Fourier map corresponding to a residual electron density of 1.08 e/Å3 was located at 1.2 Å from H5 and was deemed meaningless.
Data collection: CrystalClear (Rigaku/MSC, 2006); cell CrystalClear (Rigaku/MSC, 2006); data reduction: REQAB (Jacobson, 1998) and CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./pv2077fig1thm.gif) | Fig. 1. A thermal ellipsoid plot of the title compound drawn at 50% probability level. The symmetry related atoms have been identified by the letter A in atomic labels. |
![[Figure 2]](./pv2077fig2thm.gif) | Fig. 2. Packing diagram of the structure viewed down the b axis. Hydrogen bonds have been indicated with dashed lines. |
| C14H12I2O2 | F(000) = 436 |
| Mr = 466.04 | Dx = 2.222 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2340 reflections |
| a = 6.8616 (14) Å | θ = 3.0–26.4° |
| b = 7.7386 (15) Å | µ = 4.51 mm−1 |
| c = 13.435 (3) Å | T = 153 K |
| β = 102.43 (3)° | Chip, colorless |
| V = 696.7 (2) Å3 | 0.36 × 0.26 × 0.24 mm |
| Z = 2 |
| Rigaku Mercury CCD diffractometer | 1417 independent reflections |
| Radiation source: Sealed Tube | 1381 reflections with I > 2σ(I) |
| Graphite Monochromator monochromator | Rint = 0.039 |
| Detector resolution: 14.6306 pixels mm-1 | θmax = 26.4°, θmin = 3.1° |
| ω scans | h = −8→8 |
| Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −9→9 |
| Tmin = 0.241, Tmax = 0.337 | l = −16→11 |
| 5295 measured reflections |
| 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)] = 0.024 | H-atom parameters constrained |
| wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0318P)2 + 1.081P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.13 | (Δ/σ)max < 0.001 |
| 1417 reflections | Δρmax = 1.08 e Å−3 |
| 84 parameters | Δρmin = −0.90 e Å−3 |
| 0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0437 (19) |
| C14H12I2O2 | V = 696.7 (2) Å3 |
| Mr = 466.04 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 6.8616 (14) Å | µ = 4.51 mm−1 |
| b = 7.7386 (15) Å | T = 153 K |
| c = 13.435 (3) Å | 0.36 × 0.26 × 0.24 mm |
| β = 102.43 (3)° |
| Rigaku Mercury CCD diffractometer | 1417 independent reflections |
| Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 1381 reflections with I > 2σ(I) |
| Tmin = 0.241, Tmax = 0.337 | Rint = 0.039 |
| 5295 measured reflections |
| R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
| wR(F2) = 0.062 | H-atom parameters constrained |
| S = 1.13 | Δρmax = 1.08 e Å−3 |
| 1417 reflections | Δρmin = −0.90 e Å−3 |
| 84 parameters |
Experimental. 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 > 2sigma(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. |
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. |
| x | y | z | Uiso*/Ueq | ||
| I1 | 0.28040 (3) | 0.14667 (2) | 0.340534 (14) | 0.01974 (14) | |
| O1 | 0.5702 (3) | 0.3479 (3) | 0.22987 (17) | 0.0195 (5) | |
| C1 | 0.5402 (4) | 0.2888 (3) | 0.3985 (2) | 0.0152 (5) | |
| C2 | 0.6482 (4) | 0.3641 (3) | 0.3325 (2) | 0.0129 (6) | |
| C3 | 0.8273 (4) | 0.4479 (4) | 0.3731 (2) | 0.0151 (5) | |
| H3 | 0.9008 | 0.5005 | 0.3278 | 0.018* | |
| C4 | 0.9026 (4) | 0.4569 (3) | 0.4787 (2) | 0.0139 (5) | |
| C5 | 0.7896 (4) | 0.3821 (4) | 0.5427 (2) | 0.0183 (6) | |
| H5 | 0.8366 | 0.3884 | 0.6153 | 0.022* | |
| C6 | 0.6107 (4) | 0.2990 (4) | 0.5026 (2) | 0.0203 (6) | |
| H6 | 0.5353 | 0.2483 | 0.5475 | 0.024* | |
| C7 | 0.6900 (5) | 0.4047 (5) | 0.1613 (2) | 0.0230 (7) | |
| H7A | 0.7072 | 0.5277 | 0.1668 | 0.035* | |
| H7B | 0.6251 | 0.3752 | 0.0927 | 0.035* | |
| H7C | 0.8180 | 0.3493 | 0.1783 | 0.035* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| I1 | 0.01475 (17) | 0.02317 (18) | 0.02110 (17) | −0.00579 (6) | 0.00339 (9) | −0.00124 (6) |
| O1 | 0.0194 (10) | 0.0253 (12) | 0.0136 (10) | −0.0088 (8) | 0.0029 (8) | −0.0017 (7) |
| C1 | 0.0090 (11) | 0.0127 (12) | 0.0230 (13) | −0.0005 (10) | 0.0019 (10) | −0.0010 (10) |
| C2 | 0.0140 (13) | 0.0108 (13) | 0.0137 (14) | 0.0005 (9) | 0.0024 (10) | −0.0009 (9) |
| C3 | 0.0156 (12) | 0.0141 (12) | 0.0161 (13) | −0.0002 (10) | 0.0042 (10) | 0.0009 (10) |
| C4 | 0.0119 (12) | 0.0111 (11) | 0.0180 (13) | 0.0021 (10) | 0.0019 (10) | 0.0018 (10) |
| C5 | 0.0143 (13) | 0.0267 (14) | 0.0121 (13) | −0.0008 (12) | −0.0014 (10) | 0.0032 (11) |
| C6 | 0.0148 (13) | 0.0258 (15) | 0.0200 (14) | 0.0004 (12) | 0.0028 (10) | 0.0021 (12) |
| C7 | 0.0239 (14) | 0.0306 (17) | 0.0145 (14) | −0.0100 (14) | 0.0038 (11) | −0.0008 (12) |
| I1—C1 | 2.097 (3) | C4—C5 | 1.401 (4) |
| O1—C2 | 1.373 (4) | C4—C4i | 1.493 (5) |
| O1—C7 | 1.429 (4) | C5—C6 | 1.388 (4) |
| C1—C6 | 1.380 (4) | C5—H5 | 0.9600 |
| C1—C2 | 1.399 (4) | C6—H6 | 0.9600 |
| C2—C3 | 1.392 (4) | C7—H7A | 0.9599 |
| C3—C4 | 1.404 (4) | C7—H7B | 0.9599 |
| C3—H3 | 0.9600 | C7—H7C | 0.9599 |
| C2—O1—C7 | 117.8 (2) | C6—C5—C4 | 120.8 (3) |
| C6—C1—C2 | 120.0 (3) | C6—C5—H5 | 119.6 |
| C6—C1—I1 | 119.4 (2) | C4—C5—H5 | 119.6 |
| C2—C1—I1 | 120.5 (2) | C1—C6—C5 | 120.5 (3) |
| O1—C2—C3 | 123.8 (3) | C1—C6—H6 | 119.7 |
| O1—C2—C1 | 117.0 (2) | C5—C6—H6 | 119.7 |
| C3—C2—C1 | 119.3 (3) | O1—C7—H7A | 109.5 |
| C2—C3—C4 | 121.4 (3) | O1—C7—H7B | 109.5 |
| C2—C3—H3 | 119.3 | H7A—C7—H7B | 109.5 |
| C4—C3—H3 | 119.3 | O1—C7—H7C | 109.5 |
| C5—C4—C3 | 117.9 (2) | H7A—C7—H7C | 109.5 |
| C5—C4—C4i | 121.2 (3) | H7B—C7—H7C | 109.5 |
| C3—C4—C4i | 120.9 (3) |
| Symmetry code: (i) −x+2, −y+1, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C14H12I2O2 |
| Mr | 466.04 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 153 |
| a, b, c (Å) | 6.8616 (14), 7.7386 (15), 13.435 (3) |
| β (°) | 102.43 (3) |
| V (Å3) | 696.7 (2) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 4.51 |
| Crystal size (mm) | 0.36 × 0.26 × 0.24 |
| Data collection | |
| Diffractometer | Rigaku Mercury CCD diffractometer |
| Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
| Tmin, Tmax | 0.241, 0.337 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5295, 1417, 1381 |
| Rint | 0.039 |
| (sin θ/λ)max (Å−1) | 0.625 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.062, 1.13 |
| No. of reflections | 1417 |
| No. of parameters | 84 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 1.08, −0.90 |
Computer programs: , REQAB (Jacobson, 1998) and CrystalClear (Rigaku/MSC, 2006), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors thank the Higher Education Commission of Pakistan for financial support.
References
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Over the last 25 years, much attention has been focused on the synthesis of artificial ion channels due to their potential applications in biomedical and material sciences (Schwab & Levin, 1999; Mullen & Wegner, 1998; Fidzinski et al., 2003). The title compound has been used as a precursor for the synthesis of oligo(p-phenylene)s (Baumeister et al., 2001) and as a source of hydrophobicity and rigidity (Sakai et al., 1997; Sakai & Matile, 2003) in artificial ion channels. When a macrocycles like porphyrin is attached to the oligo(p-phenylene)s, the π-π stacking of porphyrin and the antiperiplanar arrangement of the oligo(p-phenylene)s should result in cylindrical self-assembly process and ultimately lead to the formation of functionalized pores (Sisson et al., 2006). Furthermore, iodinated biphenyl has a bright prospect as X-ray contrast media (Anelli et al., 2001).
In this paper, we report the sysnthesis and crystal structure of the title compound, (I). The molecules of (I) lie on crystallographic inversion centers. The I1—O1 intermolecular distance is 3.324 (3) Å which is significantly shorter than 3.50 Å, the sum of the van der Waals radii for I and O, supporting the idea that oxygen atom of methoxy disturbs the electronic cloud surrounding the iodide, hence creating polarization over iodide and subsequently causes reduction in the I1—O1 intermolecular distance. The crystal structures of three hexaiododerivatives of biphenyl have been reported (Anelli et al., (2001).