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

Shah, K.; Raza Shah, M.; Ng, S.W.

doi:10.1107/S1600536811003874

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o568

doi:10.1107/S1600536811003874

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

Kiramat Shah,^a M. Raza Shah ^a and Seik Weng Ng ^b ^*

^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 ).

Experimental

Crystal data

C₁₈H₁₄I₄O₂
M_r = 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 ) T_min = 0.467, T_max = 1.000
8121 measured reflections
4502 independent reflections
4118 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.079
S = 1.04
4502 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 3.38 e Å⁻³
Δρ_min = −1.69 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003874/jh2264sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003874/jh2264Isup2.hkl

checkCIF report

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.

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

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

C₁₈H₁₄I₄O₂	Z = 2
M_r = 769.89	F(000) = 700
Triclinic, P1	D_x = 2.520 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0470 (4) Å	Cell parameters from 5987 reflections
b = 10.2267 (4) Å	θ = 2.4–29.2°
c = 11.3581 (4) Å	µ = 6.15 mm⁻¹
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 Source	4118 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
ω scans	h = −12→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −13→13
T_min = 0.467, T_max = 1.000	l = −9→14
8121 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0391P)² + 2.8781P] where P = (F_o² + 2F_c²)/3
4502 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 3.38 e Å⁻³
0 restraints	Δρ_min = −1.69 e Å⁻³

Crystal data top

C₁₈H₁₄I₄O₂	γ = 108.211 (4)°
M_r = 769.89	V = 1014.45 (7) Å³
Triclinic, P1	Z = 2
a = 10.0470 (4) Å	Mo Kα radiation
b = 10.2267 (4) Å	µ = 6.15 mm⁻¹
c = 11.3581 (4) Å	T = 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)
T_min = 0.467, T_max = 1.000	R_int = 0.026
8121 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.04	Δρ_max = 3.38 e Å⁻³
4502 reflections	Δρ_min = −1.69 e Å⁻³
217 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.52321 (3)	0.89339 (3)	0.77411 (3)	0.02006 (8)
I2	0.05784 (3)	0.47289 (3)	0.70014 (3)	0.02903 (10)
I3	0.69630 (3)	−0.38925 (3)	0.56256 (3)	0.02370 (9)
I4	1.15769 (3)	−0.03766 (3)	0.91544 (3)	0.02524 (9)
O1	0.5470 (4)	0.7096 (3)	0.9645 (3)	0.0202 (6)
O2	0.8521 (4)	−0.0703 (3)	0.5344 (3)	0.0200 (6)
C1	0.2354 (5)	0.6460 (5)	0.6979 (5)	0.0207 (9)
H1	0.2259	0.6735	0.6242	0.025*
C2	0.3610 (5)	0.7193 (5)	0.7945 (4)	0.0181 (9)
C3	0.3993 (5)	0.7013 (5)	0.9214 (4)	0.0194 (9)
H3A	0.3862	0.7788	0.9867	0.023*
H3B	0.3297	0.6046	0.9150	0.023*
C4	0.5783 (5)	0.5922 (5)	0.9042 (4)	0.0177 (9)
C5	0.7224 (5)	0.6043 (5)	0.9543 (4)	0.0182 (9)
H5	0.7893	0.6881	1.0270	0.022*
C6	0.7679 (5)	0.4940 (5)	0.8981 (4)	0.0184 (9)
H6	0.8666	0.5044	0.9316	0.022*
C7	0.6700 (5)	0.3677 (5)	0.7927 (4)	0.0167 (8)
C8	0.5257 (5)	0.3563 (5)	0.7479 (4)	0.0193 (9)
H8	0.4568	0.2704	0.6782	0.023*
C9	0.4797 (5)	0.4667 (5)	0.8023 (4)	0.0194 (9)
H9	0.3806	0.4559	0.7696	0.023*
C10	0.7198 (5)	0.2529 (5)	0.7296 (4)	0.0160 (8)
C11	0.6679 (5)	0.1820 (5)	0.5947 (4)	0.0189 (9)
H11	0.5995	0.2077	0.5448	0.023*
C12	0.7143 (5)	0.0756 (5)	0.5334 (4)	0.0191 (9)
H12	0.6784	0.0294	0.4424	0.023*
C13	0.8144 (5)	0.0367 (4)	0.6066 (4)	0.0163 (8)
C14	0.8670 (5)	0.1041 (5)	0.7393 (4)	0.0181 (9)
H14	0.9346	0.0775	0.7891	0.022*
C15	0.8192 (5)	0.2116 (5)	0.7992 (4)	0.0172 (8)
H15	0.8558	0.2579	0.8902	0.021*
C16	0.9582 (5)	−0.1128 (5)	0.6013 (4)	0.0192 (9)
H16A	1.0423	−0.0230	0.6631	0.023*
H16B	0.9961	−0.1666	0.5386	0.023*
C17	0.8964 (5)	−0.2085 (5)	0.6726 (4)	0.0172 (8)
C18	0.9551 (5)	−0.1992 (5)	0.7908 (4)	0.0201 (9)
H18	0.9018	−0.2705	0.8211	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01788 (15)	0.02009 (15)	0.01828 (15)	0.00200 (11)	0.00372 (11)	0.00864 (12)
I2	0.01896 (17)	0.01891 (16)	0.0441 (2)	0.00325 (12)	0.01327 (14)	0.00592 (14)
I3	0.01724 (16)	0.02002 (16)	0.02533 (16)	0.00179 (12)	0.00369 (12)	0.00383 (13)
I4	0.02077 (16)	0.02426 (17)	0.02344 (16)	0.01197 (13)	−0.00226 (12)	0.00046 (13)
O1	0.0246 (17)	0.0183 (15)	0.0189 (15)	0.0112 (13)	0.0053 (13)	0.0061 (13)
O2	0.0263 (17)	0.0199 (16)	0.0201 (15)	0.0149 (13)	0.0081 (13)	0.0091 (13)
C1	0.014 (2)	0.014 (2)	0.031 (2)	0.0025 (17)	0.0072 (18)	0.0052 (19)
C2	0.016 (2)	0.014 (2)	0.025 (2)	0.0055 (16)	0.0100 (18)	0.0060 (18)
C3	0.025 (2)	0.019 (2)	0.020 (2)	0.0116 (18)	0.0126 (18)	0.0093 (18)
C4	0.024 (2)	0.016 (2)	0.019 (2)	0.0100 (17)	0.0108 (18)	0.0092 (17)
C5	0.022 (2)	0.014 (2)	0.018 (2)	0.0051 (17)	0.0054 (17)	0.0076 (17)
C6	0.016 (2)	0.020 (2)	0.020 (2)	0.0060 (17)	0.0037 (17)	0.0105 (18)
C7	0.020 (2)	0.016 (2)	0.018 (2)	0.0073 (17)	0.0059 (17)	0.0100 (17)
C8	0.019 (2)	0.018 (2)	0.021 (2)	0.0078 (18)	0.0058 (17)	0.0058 (18)
C9	0.018 (2)	0.021 (2)	0.022 (2)	0.0095 (18)	0.0062 (18)	0.0090 (19)
C10	0.016 (2)	0.014 (2)	0.018 (2)	0.0027 (16)	0.0060 (16)	0.0086 (17)
C11	0.017 (2)	0.020 (2)	0.021 (2)	0.0087 (18)	0.0041 (17)	0.0096 (18)
C12	0.021 (2)	0.019 (2)	0.017 (2)	0.0074 (18)	0.0055 (17)	0.0070 (18)
C13	0.017 (2)	0.0123 (19)	0.022 (2)	0.0045 (16)	0.0078 (17)	0.0088 (17)
C14	0.019 (2)	0.016 (2)	0.021 (2)	0.0067 (17)	0.0061 (17)	0.0113 (18)
C15	0.016 (2)	0.014 (2)	0.018 (2)	0.0037 (16)	0.0021 (16)	0.0054 (17)
C16	0.020 (2)	0.019 (2)	0.025 (2)	0.0107 (18)	0.0099 (18)	0.0131 (19)
C17	0.014 (2)	0.014 (2)	0.021 (2)	0.0053 (16)	0.0051 (17)	0.0041 (17)
C18	0.019 (2)	0.017 (2)	0.023 (2)	0.0063 (17)	0.0042 (18)	0.0077 (18)

Geometric parameters (Å, º) top

I1—C2	2.107 (4)	C7—C10	1.482 (6)
I2—C1	2.094 (4)	C8—C9	1.389 (6)
I3—C17	2.109 (4)	C8—H8	0.9500
I4—C18	2.089 (5)	C9—H9	0.9500
O1—C4	1.372 (5)	C10—C15	1.390 (6)
O1—C3	1.435 (6)	C10—C11	1.410 (6)
O2—C13	1.381 (5)	C11—C12	1.386 (6)
O2—C16	1.432 (5)	C11—H11	0.9500
C1—C2	1.331 (7)	C12—C13	1.400 (6)
C1—H1	0.9500	C12—H12	0.9500
C2—C3	1.493 (6)	C13—C14	1.386 (6)
C3—H3A	0.9900	C14—C15	1.398 (6)
C3—H3B	0.9900	C14—H14	0.9500
C4—C9	1.383 (6)	C15—H15	0.9500
C4—C5	1.399 (6)	C16—C17	1.500 (6)
C5—C6	1.392 (6)	C16—H16A	0.9900
C5—H5	0.9500	C16—H16B	0.9900
C6—C7	1.403 (6)	C17—C18	1.319 (6)
C6—H6	0.9500	C18—H18	0.9500
C7—C8	1.395 (6)

C4—O1—C3	118.0 (3)	C8—C9—H9	120.1
C13—O2—C16	117.6 (3)	C15—C10—C11	117.5 (4)
C2—C1—I2	123.3 (4)	C15—C10—C7	122.1 (4)
C2—C1—H1	118.3	C11—C10—C7	120.4 (4)
I2—C1—H1	118.3	C12—C11—C10	121.5 (4)
C1—C2—C3	128.2 (4)	C12—C11—H11	119.3
C1—C2—I1	117.0 (3)	C10—C11—H11	119.3
C3—C2—I1	114.7 (3)	C11—C12—C13	119.5 (4)
O1—C3—C2	113.8 (4)	C11—C12—H12	120.2
O1—C3—H3A	108.8	C13—C12—H12	120.2
C2—C3—H3A	108.8	C14—C13—O2	125.7 (4)
O1—C3—H3B	108.8	C14—C13—C12	120.3 (4)
C2—C3—H3B	108.8	O2—C13—C12	114.0 (4)
H3A—C3—H3B	107.7	C13—C14—C15	119.2 (4)
O1—C4—C9	125.3 (4)	C13—C14—H14	120.4
O1—C4—C5	115.2 (4)	C15—C14—H14	120.4
C9—C4—C5	119.5 (4)	C10—C15—C14	122.0 (4)
C6—C5—C4	120.2 (4)	C10—C15—H15	119.0
C6—C5—H5	119.9	C14—C15—H15	119.0
C4—C5—H5	119.9	O2—C16—C17	113.0 (4)
C5—C6—C7	120.9 (4)	O2—C16—H16A	109.0
C5—C6—H6	119.5	C17—C16—H16A	109.0
C7—C6—H6	119.5	O2—C16—H16B	109.0
C8—C7—C6	117.5 (4)	C17—C16—H16B	109.0
C8—C7—C10	121.5 (4)	H16A—C16—H16B	107.8
C6—C7—C10	121.0 (4)	C18—C17—C16	128.5 (4)
C9—C8—C7	122.0 (4)	C18—C17—I3	116.8 (3)
C9—C8—H8	119.0	C16—C17—I3	114.6 (3)
C7—C8—H8	119.0	C17—C18—I4	124.2 (4)
C4—C9—C8	119.8 (4)	C17—C18—H18	117.9
C4—C9—H9	120.1	I4—C18—H18	117.9

I2—C1—C2—C3	−3.1 (7)	C8—C7—C10—C11	37.3 (6)
I2—C1—C2—I1	−178.41 (19)	C6—C7—C10—C11	−141.2 (4)
C4—O1—C3—C2	−73.4 (5)	C15—C10—C11—C12	−0.3 (7)
C1—C2—C3—O1	139.5 (5)	C7—C10—C11—C12	179.2 (4)
I1—C2—C3—O1	−45.1 (4)	C10—C11—C12—C13	0.3 (7)
C3—O1—C4—C9	1.6 (6)	C16—O2—C13—C14	−2.1 (6)
C3—O1—C4—C5	−177.3 (4)	C16—O2—C13—C12	177.8 (4)
O1—C4—C5—C6	−177.9 (4)	C11—C12—C13—C14	−0.1 (7)
C9—C4—C5—C6	3.1 (6)	C11—C12—C13—O2	−179.9 (4)
C4—C5—C6—C7	−1.5 (7)	O2—C13—C14—C15	179.6 (4)
C5—C6—C7—C8	−0.9 (6)	C12—C13—C14—C15	−0.2 (6)
C5—C6—C7—C10	177.6 (4)	C11—C10—C15—C14	0.0 (6)
C6—C7—C8—C9	1.8 (7)	C7—C10—C15—C14	−179.5 (4)
C10—C7—C8—C9	−176.8 (4)	C13—C14—C15—C10	0.3 (7)
O1—C4—C9—C8	178.9 (4)	C13—O2—C16—C17	74.9 (5)
C5—C4—C9—C8	−2.3 (7)	O2—C16—C17—C18	−135.0 (5)
C7—C8—C9—C4	−0.2 (7)	O2—C16—C17—I3	49.6 (4)
C8—C7—C10—C15	−143.3 (4)	C16—C17—C18—I4	1.3 (7)
C6—C7—C10—C15	38.2 (6)	I3—C17—C18—I4	176.6 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄I₄O₂
M_r	769.89
Crystal system, space group	Triclinic, 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)
V (Å³)	1014.45 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.15
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.467, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8121, 4502, 4118
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.04
No. of reflections	4502
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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