organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4,4′-Bis[(E)-(2,3-di­iodo­prop-2-en-1-yl)­­oxy]biphen­yl

aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 7527, Pakistan, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 29 January 2011; accepted 30 January 2011; online 5 February 2011)

Iodine adds across both triple bonds of 4,4′-bis­(prop-2-yn­­yl­oxy)biphenyl, yielding the 4,4′-bis­(2,3-diiodo­all­yloxy)biphenyl title compound, C18H14I4O2; the 2,3-diiodo­ally­oxy substituents have the I atoms in an E configuration. In the biphenyl portion of the mol­ecule, the aromatic rings are inclined by 37.8 (2)°.

Related literature

For the structure of 4,4′-bis­(prop-2-yn­yloxy)biphenyl, see: Zhang et al. (2008[Zhang, W., Yao, L. & Tao, R.-J. (2008). Acta Cryst. E64, o307.]).

[Scheme 1]

Experimental

Crystal data
  • C18H14I4O2

  • Mr = 769.89

  • Triclinic, [P \overline 1]

  • a = 10.0470 (4) Å

  • b = 10.2267 (4) Å

  • c = 11.3581 (4) Å

  • α = 105.760 (4)°

  • β = 101.433 (3)°

  • γ = 108.211 (4)°

  • V = 1014.45 (7) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 6.15 mm−1

  • T = 100 K

  • 0.20 × 0.10 × 0.05 mm

Data collection
  • Agilent SuperNova Dual diffractometer with an Atlas detector

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.467, Tmax = 1.000

  • 8121 measured reflections

  • 4502 independent reflections

  • 4118 reflections with I > 2σ(I)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.079

  • S = 1.04

  • 4502 reflections

  • 217 parameters

  • H-atom parameters constrained

  • Δρmax = 3.38 e Å−3

  • Δρmin = −1.69 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

We have intended to activate the triple bond of 4,4'-bis(prop-2-ynyloxy)biphenyl (Zhang et al., 2008) in order to polymerize the compound by using a cuprous iodide/iodine catalytic system. The attempt yielded instead the iodinated title compound (Scheme I, Fig. 1). The aromatic rings are twisted 37.8 (2) °.

Related literature top

For the structure of 4,4'-bis(prop-2-ynyloxy)biphenyl, see: Zhang et al. (2008).

Experimental top

Potassium carbonate (3 g, 1 mmol) and biphenyl-4,4'-diol (1 g, 5.3 mmol) were dissolved in ethanol (30 ml). The solution was heated for 1 h. This was followed by the addition propargyl bromide (1.5 ml, 17 mmol). The mixture was heated for another 8 h. The solvent was removed and the residue dissolved in a mixture of water (30 ml) and dichloromethane (30 ml). The aqueous layer was extracted three times with dichloromethane. Slow evaporation of dichloromethane gave colorless crystals (70%) of 4,4'-bis(prop-2-ynyloxy)biphenyl. This compound (1 g, 3.8 mmol) was dissolved an ethanol solution of cuprous iodide and iodine in an attempt to activate the triple bond. Slow evaporation of the solvent yielded the iodinated product in 80% yield.

Refinement top

Carbon-bound H-atoms were placed in calculated positions [C—H 0.95 to 0.99 Å, Uiso(H) 1.2Ueq(C)] and were included in the refinement in the riding model approximation.

The final difference Fourier map had a peak at 0.96 Å from I2 and a hole at 0.60 Å from the same atom.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C18H14I4O4 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
4,4'-Bis[(E)-(2,3-diiodoprop-2-en-1-yl)oxy]biphenyl top
Crystal data top
C18H14I4O2Z = 2
Mr = 769.89F(000) = 700
Triclinic, P1Dx = 2.520 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.0470 (4) ÅCell parameters from 5987 reflections
b = 10.2267 (4) Åθ = 2.4–29.2°
c = 11.3581 (4) ŵ = 6.15 mm1
α = 105.760 (4)°T = 100 K
β = 101.433 (3)°Prism, colorless
γ = 108.211 (4)°0.20 × 0.10 × 0.05 mm
V = 1014.45 (7) Å3
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
4502 independent reflections
Radiation source: SuperNova (Mo) X-ray Source4118 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.026
Detector resolution: 10.4041 pixels mm-1θmax = 27.5°, θmin = 2.4°
ω scansh = 129
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
k = 1313
Tmin = 0.467, Tmax = 1.000l = 914
8121 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0391P)2 + 2.8781P]
where P = (Fo2 + 2Fc2)/3
4502 reflections(Δ/σ)max = 0.001
217 parametersΔρmax = 3.38 e Å3
0 restraintsΔρmin = 1.69 e Å3
Crystal data top
C18H14I4O2γ = 108.211 (4)°
Mr = 769.89V = 1014.45 (7) Å3
Triclinic, P1Z = 2
a = 10.0470 (4) ÅMo Kα radiation
b = 10.2267 (4) ŵ = 6.15 mm1
c = 11.3581 (4) ÅT = 100 K
α = 105.760 (4)°0.20 × 0.10 × 0.05 mm
β = 101.433 (3)°
Data collection top
Agilent SuperNova Dual
diffractometer with an Atlas detector
4502 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
4118 reflections with I > 2σ(I)
Tmin = 0.467, Tmax = 1.000Rint = 0.026
8121 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.079H-atom parameters constrained
S = 1.04Δρmax = 3.38 e Å3
4502 reflectionsΔρmin = 1.69 e Å3
217 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.52321 (3)0.89339 (3)0.77411 (3)0.02006 (8)
I20.05784 (3)0.47289 (3)0.70014 (3)0.02903 (10)
I30.69630 (3)0.38925 (3)0.56256 (3)0.02370 (9)
I41.15769 (3)0.03766 (3)0.91544 (3)0.02524 (9)
O10.5470 (4)0.7096 (3)0.9645 (3)0.0202 (6)
O20.8521 (4)0.0703 (3)0.5344 (3)0.0200 (6)
C10.2354 (5)0.6460 (5)0.6979 (5)0.0207 (9)
H10.22590.67350.62420.025*
C20.3610 (5)0.7193 (5)0.7945 (4)0.0181 (9)
C30.3993 (5)0.7013 (5)0.9214 (4)0.0194 (9)
H3A0.38620.77880.98670.023*
H3B0.32970.60460.91500.023*
C40.5783 (5)0.5922 (5)0.9042 (4)0.0177 (9)
C50.7224 (5)0.6043 (5)0.9543 (4)0.0182 (9)
H50.78930.68811.02700.022*
C60.7679 (5)0.4940 (5)0.8981 (4)0.0184 (9)
H60.86660.50440.93160.022*
C70.6700 (5)0.3677 (5)0.7927 (4)0.0167 (8)
C80.5257 (5)0.3563 (5)0.7479 (4)0.0193 (9)
H80.45680.27040.67820.023*
C90.4797 (5)0.4667 (5)0.8023 (4)0.0194 (9)
H90.38060.45590.76960.023*
C100.7198 (5)0.2529 (5)0.7296 (4)0.0160 (8)
C110.6679 (5)0.1820 (5)0.5947 (4)0.0189 (9)
H110.59950.20770.54480.023*
C120.7143 (5)0.0756 (5)0.5334 (4)0.0191 (9)
H120.67840.02940.44240.023*
C130.8144 (5)0.0367 (4)0.6066 (4)0.0163 (8)
C140.8670 (5)0.1041 (5)0.7393 (4)0.0181 (9)
H140.93460.07750.78910.022*
C150.8192 (5)0.2116 (5)0.7992 (4)0.0172 (8)
H150.85580.25790.89020.021*
C160.9582 (5)0.1128 (5)0.6013 (4)0.0192 (9)
H16A1.04230.02300.66310.023*
H16B0.99610.16660.53860.023*
C170.8964 (5)0.2085 (5)0.6726 (4)0.0172 (8)
C180.9551 (5)0.1992 (5)0.7908 (4)0.0201 (9)
H180.90180.27050.82110.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01788 (15)0.02009 (15)0.01828 (15)0.00200 (11)0.00372 (11)0.00864 (12)
I20.01896 (17)0.01891 (16)0.0441 (2)0.00325 (12)0.01327 (14)0.00592 (14)
I30.01724 (16)0.02002 (16)0.02533 (16)0.00179 (12)0.00369 (12)0.00383 (13)
I40.02077 (16)0.02426 (17)0.02344 (16)0.01197 (13)0.00226 (12)0.00046 (13)
O10.0246 (17)0.0183 (15)0.0189 (15)0.0112 (13)0.0053 (13)0.0061 (13)
O20.0263 (17)0.0199 (16)0.0201 (15)0.0149 (13)0.0081 (13)0.0091 (13)
C10.014 (2)0.014 (2)0.031 (2)0.0025 (17)0.0072 (18)0.0052 (19)
C20.016 (2)0.014 (2)0.025 (2)0.0055 (16)0.0100 (18)0.0060 (18)
C30.025 (2)0.019 (2)0.020 (2)0.0116 (18)0.0126 (18)0.0093 (18)
C40.024 (2)0.016 (2)0.019 (2)0.0100 (17)0.0108 (18)0.0092 (17)
C50.022 (2)0.014 (2)0.018 (2)0.0051 (17)0.0054 (17)0.0076 (17)
C60.016 (2)0.020 (2)0.020 (2)0.0060 (17)0.0037 (17)0.0105 (18)
C70.020 (2)0.016 (2)0.018 (2)0.0073 (17)0.0059 (17)0.0100 (17)
C80.019 (2)0.018 (2)0.021 (2)0.0078 (18)0.0058 (17)0.0058 (18)
C90.018 (2)0.021 (2)0.022 (2)0.0095 (18)0.0062 (18)0.0090 (19)
C100.016 (2)0.014 (2)0.018 (2)0.0027 (16)0.0060 (16)0.0086 (17)
C110.017 (2)0.020 (2)0.021 (2)0.0087 (18)0.0041 (17)0.0096 (18)
C120.021 (2)0.019 (2)0.017 (2)0.0074 (18)0.0055 (17)0.0070 (18)
C130.017 (2)0.0123 (19)0.022 (2)0.0045 (16)0.0078 (17)0.0088 (17)
C140.019 (2)0.016 (2)0.021 (2)0.0067 (17)0.0061 (17)0.0113 (18)
C150.016 (2)0.014 (2)0.018 (2)0.0037 (16)0.0021 (16)0.0054 (17)
C160.020 (2)0.019 (2)0.025 (2)0.0107 (18)0.0099 (18)0.0131 (19)
C170.014 (2)0.014 (2)0.021 (2)0.0053 (16)0.0051 (17)0.0041 (17)
C180.019 (2)0.017 (2)0.023 (2)0.0063 (17)0.0042 (18)0.0077 (18)
Geometric parameters (Å, º) top
I1—C22.107 (4)C7—C101.482 (6)
I2—C12.094 (4)C8—C91.389 (6)
I3—C172.109 (4)C8—H80.9500
I4—C182.089 (5)C9—H90.9500
O1—C41.372 (5)C10—C151.390 (6)
O1—C31.435 (6)C10—C111.410 (6)
O2—C131.381 (5)C11—C121.386 (6)
O2—C161.432 (5)C11—H110.9500
C1—C21.331 (7)C12—C131.400 (6)
C1—H10.9500C12—H120.9500
C2—C31.493 (6)C13—C141.386 (6)
C3—H3A0.9900C14—C151.398 (6)
C3—H3B0.9900C14—H140.9500
C4—C91.383 (6)C15—H150.9500
C4—C51.399 (6)C16—C171.500 (6)
C5—C61.392 (6)C16—H16A0.9900
C5—H50.9500C16—H16B0.9900
C6—C71.403 (6)C17—C181.319 (6)
C6—H60.9500C18—H180.9500
C7—C81.395 (6)
C4—O1—C3118.0 (3)C8—C9—H9120.1
C13—O2—C16117.6 (3)C15—C10—C11117.5 (4)
C2—C1—I2123.3 (4)C15—C10—C7122.1 (4)
C2—C1—H1118.3C11—C10—C7120.4 (4)
I2—C1—H1118.3C12—C11—C10121.5 (4)
C1—C2—C3128.2 (4)C12—C11—H11119.3
C1—C2—I1117.0 (3)C10—C11—H11119.3
C3—C2—I1114.7 (3)C11—C12—C13119.5 (4)
O1—C3—C2113.8 (4)C11—C12—H12120.2
O1—C3—H3A108.8C13—C12—H12120.2
C2—C3—H3A108.8C14—C13—O2125.7 (4)
O1—C3—H3B108.8C14—C13—C12120.3 (4)
C2—C3—H3B108.8O2—C13—C12114.0 (4)
H3A—C3—H3B107.7C13—C14—C15119.2 (4)
O1—C4—C9125.3 (4)C13—C14—H14120.4
O1—C4—C5115.2 (4)C15—C14—H14120.4
C9—C4—C5119.5 (4)C10—C15—C14122.0 (4)
C6—C5—C4120.2 (4)C10—C15—H15119.0
C6—C5—H5119.9C14—C15—H15119.0
C4—C5—H5119.9O2—C16—C17113.0 (4)
C5—C6—C7120.9 (4)O2—C16—H16A109.0
C5—C6—H6119.5C17—C16—H16A109.0
C7—C6—H6119.5O2—C16—H16B109.0
C8—C7—C6117.5 (4)C17—C16—H16B109.0
C8—C7—C10121.5 (4)H16A—C16—H16B107.8
C6—C7—C10121.0 (4)C18—C17—C16128.5 (4)
C9—C8—C7122.0 (4)C18—C17—I3116.8 (3)
C9—C8—H8119.0C16—C17—I3114.6 (3)
C7—C8—H8119.0C17—C18—I4124.2 (4)
C4—C9—C8119.8 (4)C17—C18—H18117.9
C4—C9—H9120.1I4—C18—H18117.9
I2—C1—C2—C33.1 (7)C8—C7—C10—C1137.3 (6)
I2—C1—C2—I1178.41 (19)C6—C7—C10—C11141.2 (4)
C4—O1—C3—C273.4 (5)C15—C10—C11—C120.3 (7)
C1—C2—C3—O1139.5 (5)C7—C10—C11—C12179.2 (4)
I1—C2—C3—O145.1 (4)C10—C11—C12—C130.3 (7)
C3—O1—C4—C91.6 (6)C16—O2—C13—C142.1 (6)
C3—O1—C4—C5177.3 (4)C16—O2—C13—C12177.8 (4)
O1—C4—C5—C6177.9 (4)C11—C12—C13—C140.1 (7)
C9—C4—C5—C63.1 (6)C11—C12—C13—O2179.9 (4)
C4—C5—C6—C71.5 (7)O2—C13—C14—C15179.6 (4)
C5—C6—C7—C80.9 (6)C12—C13—C14—C150.2 (6)
C5—C6—C7—C10177.6 (4)C11—C10—C15—C140.0 (6)
C6—C7—C8—C91.8 (7)C7—C10—C15—C14179.5 (4)
C10—C7—C8—C9176.8 (4)C13—C14—C15—C100.3 (7)
O1—C4—C9—C8178.9 (4)C13—O2—C16—C1774.9 (5)
C5—C4—C9—C82.3 (7)O2—C16—C17—C18135.0 (5)
C7—C8—C9—C40.2 (7)O2—C16—C17—I349.6 (4)
C8—C7—C10—C15143.3 (4)C16—C17—C18—I41.3 (7)
C6—C7—C10—C1538.2 (6)I3—C17—C18—I4176.6 (2)

Experimental details

Crystal data
Chemical formulaC18H14I4O2
Mr769.89
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)10.0470 (4), 10.2267 (4), 11.3581 (4)
α, β, γ (°)105.760 (4), 101.433 (3), 108.211 (4)
V3)1014.45 (7)
Z2
Radiation typeMo Kα
µ (mm1)6.15
Crystal size (mm)0.20 × 0.10 × 0.05
Data collection
DiffractometerAgilent SuperNova Dual
diffractometer with an Atlas detector
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2010)
Tmin, Tmax0.467, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8121, 4502, 4118
Rint0.026
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.079, 1.04
No. of reflections4502
No. of parameters217
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)3.38, 1.69

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

 

Acknowledgements

We thank the Higher Education Commission of Pakistan and the University of Malaya for supporting this study.

References

First citationAgilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England.  Google Scholar
First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhang, W., Yao, L. & Tao, R.-J. (2008). Acta Cryst. E64, o307.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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