Crystal structure of (E)-1-(4-tert-butyl­phen­yl)-2-(4-iodo­phen­yl)ethene

Zhiwei Chen; Graeme J Moxey

doi:10.1107/S2056989015007185

. 2015 Apr 15;71(Pt 5):o309–o310. doi: 10.1107/S2056989015007185

Crystal structure of (E)-1-(4-tert-butylphenyl)-2-(4-iodophenyl)ethene

Zhiwei Chen ^a, Graeme J Moxey ^a,^b,^*

PMCID: PMC4420064 PMID: 25995920

Abstract

The title compound, C₁₈H₁₉I, crystallized with two independent molecules (A and B) in the asymmetric unit. Both molecules have an E conformation about the bridging C=C bond. They differ in the orientation of the two benzene rings; the dihedral angle being 12.3 (5)° in molecule A, but only 1.0 (6)° in molecule B. In the crystal, the individual molecules are linked by C—I⋯π interactions forming zigzag A and zigzag B chains propagating along [001]. The structure was refined as an inversion twin [Flack parameter = 0.48 (2)].

Keywords: crystal structure, stilbene, iodoarene, C—I⋯π interactions

Related literature

For the syntheses of arylalkynes by Sonogashira cross-coupling of iodoarenes, see: Takahashi et al. (1980 ▸). For desilylation of the resultant trialkylsilylethynylarenes and the use of ethynylarenes in the construction of metal alkynyl complexes with enhanced non-linear optical properties, see: McDonagh et al. (1996a ▸,b ▸, 2003 ▸); Garcia et al. (2002 ▸). For related structures, see: Marras et al. (2006 ▸); Mariaca et al. (2009 ▸). graphic file with name e-71-0o309-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₉I
M _r = 362.23
Orthorhombic,
a = 32.5385 (9) Å
b = 6.10513 (15) Å
c = 15.8615 (3) Å
V = 3150.91 (14) Å³
Z = 8
Cu Kα radiation
μ = 15.83 mm⁻¹
T = 150 K
0.16 × 0.05 × 0.02 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, EosS2) diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2014 ▸) T _min = 0.854, T _max = 0.966
10293 measured reflections
3770 independent reflections
3559 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.133
S = 1.04
3770 reflections
350 parameters
67 restraints
H-atom parameters constrained
Δρ_max = 2.09 e Å⁻³
Δρ_min = −1.31 e Å⁻³
Absolute structure: Flack (1983 ▸), 570 Friedel pairs
Absolute structure parameter: 0.48 (2)

Data collection: CrysAlis PRO (Agilent, 2014 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989015007185/su5108sup1.cif

e-71-0o309-sup1.cif^{(393.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007185/su5108Isup2.hkl

e-71-0o309-Isup2.hkl^{(206.9KB, hkl)}

Click here for additional data file.^{(1.7MB, tif)}

A B . DOI: 10.1107/S2056989015007185/su5108fig1.tif

Molecular structure of the two independent molecules (A and B) of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 40% probability level.

Click here for additional data file.^{(1.6MB, tif)}

b A B . DOI: 10.1107/S2056989015007185/su5108fig2.tif

A view along the b axis of the crystal packing of the title compound. The C—I⋯π interactions are represented as dashed lines (see Table 1 for details; molecule A blue, molecule B red).

Click here for additional data file.^{(75.5KB, tif)}

1 . DOI: 10.1107/S2056989015007185/su5108fig3.tif

Atom numbering scheme of the title compound for ¹H NMR assignments.

CCDC reference: 1053466

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg2 and Cg4 are the centroids of the C9C14 and C27C32 rings, respectively.

DHA	DH	HA	D A	DHA
C1I1Cg2ⁱ	2.09(1)	3.63(1)	5.676(10)	166(1)
C19I2Cg4ⁱⁱ	2.10(1)	3.57(1)	5.526(11)	154(1)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We gratefully acknowledge support from the Australian Research Council (LE130100057) to purchase the Agilent Technologies SuperNova and XCalibur diffractometers. We thank Professors C. Zhang (Jiangnan University), M. P. Cifuentes (Australian National University) and M. G. Humphrey (Australian National University) for assistance.

supplementary crystallographic information

S1. Synthesis and crystallization

(E)-1-(4-tert-butylphenyl)-2-(4-bromophenyl)ethene (1.00 g, 3.17 mmol) was dissolved in distilled THF (40 mL) and cooled to 195 K (liquid nitrogen bath) under N₂ for 30 min. BuLi (2.97 mL, 1.6 M, 4.76 mmol) was added and the mixture was stirred for 2 h. A solution of I₂ (1.20 g, 4.76 mmol) in THF (20 mL) was then added and the reaction was allowed to warm to room temperature. A saturated solution of sodium thiosulfate (10 mL) and water (20 mL) were then added and the mixture stirred until clear. The mixture was then extracted with CH₂Cl₂, stirred over anhydrous MgSO₄, filtered and taken to dryness to yield the title compound as a yellow solid. The solid was extracted with a small amount of CH₂Cl₂ and the extract was passed through a pad of silica with petrol as eluent. The eluate was reduced in volume, affording the title compound as a white solid (yield: 1.0 g, 87%). The numbering scheme of the title compound for the NMR assignments is given in Fig. 3. ¹H-NMR (400 MHz, CDCl₃): δ 7.66 (d, J_HH = 8 Hz, 2H, H₇), 7.44 (d, J_HH = 8 Hz, 2H, H₃), 7.38 (d, J_HH = 8 Hz, 2H, H₂), 7.23 (d, J_HH = 8 Hz, 2H, H₆), 7.09 (d, J_HH = 16 Hz, 1H, H₄), 6.97 (d, J_HH = 16 Hz, 1H, H₅), 1.33 (s, 9H, H₁). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a solution in hexane.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized below. The H atoms were included in calculated positions and treated as riding: C—H = 0.93 - 0.96 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms. The structure was refined as an inversion twin: Flack parameter = 0.48 (2). Rigid bond restraints (RIGU) were applied to atoms C15, C16, C17, C18, C22, C25, C26, C27, C28, C32, C33, C34, C35, C36.