1,2-Bis(4-meth­oxy­phen­oxy)ethane

Ji, J.; Zhang, X.Q.; Wang, K.; Ju, C.F.; Chen, Q.

doi:10.1107/S1600536813007009

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page o547

doi:10.1107/S1600536813007009

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1,2-Bis(4-methoxyphenoxy)ethane

Jun Ji,^a XiuQin Zhang,^b Kai Wang,^b ChaoFan Ju ^a and Qiang Chen ^b ^*

^aSchool of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, People's Republic of China, and ^bHigh Technology Research Institute of Nanjing University, Changzhou 213162, Jiangsu, People's Republic of China
^*Correspondence e-mail: wkcoool@yahoo.cn

(Received 12 March 2013; accepted 13 March 2013; online 16 March 2013)

The whole molecule of the title compound, C₁₆H₁₈O₄, is generated by twofold rotational symmetry; the twofold axis bisects the central C—C bond. The O—C—C—O torsion angle about the central C—C bond is 69.45 (16)°. Symmetry-related benzene rings are inclined to one another by 64.91 (8)°. In the crystal, molecules are connected by C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For the synthesis, uses and properties of the title compound, see: Saito et al. (1988 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₈O₄
M_r = 274.32
Monoclinic, C 2/c
a = 26.073 (4) Å
b = 5.5538 (8) Å
c = 9.7591 (14) Å
β = 102.211 (3)°
V = 1381.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.981, T_max = 0.986
3780 measured reflections
1277 independent reflections
976 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.224
S = 1.10
1277 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O1ⁱ	0.96	2.60	3.453 (2)	148
C6—H6⋯O2ⁱⁱ	0.93	2.59	3.490 (2)	163
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) -x, -y+2, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, gobal. DOI: 10.1107/S1600536813007009/su2572sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813007009/su2572Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813007009/su2572Isup3.cml

checkCIF report

Comment top

The tittle compound is used as an important organic synthesis intermediate. It is used as a sensitizer for thermal recording materials and materials for polyester-resin monomers and fire-resistant materials (Saito et al.,1988). We report herein on the crystal structure of the title compound.

The molecular structure of the title molecule is shown in Fig. 1. The bond lengths (Allen et al., 1987) and angles are within normal ranges. The molecule has two-fold rotational symmetry, the 2-fold axis bisecting bond C8-C8A. The central O2-C8-C8A-O2A torsion angles is 69.45 (16) °. The symmetry related benzene rings [C2-C7 and C2A-C7A; symmetry code (A) -x, y, -z-1/2], are inclined to one another by 64.91 (8) °.

In the crystal, molecules are linked via C—H···O hydrogen bonds forming a three-dimensional network (Fig. 2 and Table 1).

Related literature top

For the synthesis, uses and properties of the title compound, see: Saito et al. (1988). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by a method reported in literature (Saito et al., 1988). To a solution of 1,2-dibromoethane (2.3 g, 12 mmol) and 4-methoxyphenol (3.1 g, 25 mmol) in acetonitrile (100 ml) was added anhydrous potassium carbonate (6.2 g, 45 mmol), and the mixture was stirred overnight at 338 K. The reaction mixture was filtered and the filtrate evaporated under reduced pressure. The residue was subjected to flash chromatography on silica gel, eluting with (10:1/ petroleum ether:ethyl acetate) to give title compound (Yield 2.13 g). Colourless block-like crystals of the title compound were obtained by slow evaporation of a solution in ethanol (20 ml) after about 7 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo,1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound, showing the C-H···O hydrogen bonds (dashed lines; see Table 1 for details; H atoms not involved in these interactions have been omitted for clarity).

1,2-Bis(4-methoxyphenoxy)ethane top

Crystal data top

C₁₆H₁₈O₄	F(000) = 584
M_r = 274.32	D_x = 1.319 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1571 reflections
a = 26.073 (4) Å	θ = 3.2–30.3°
b = 5.5538 (8) Å	µ = 0.09 mm⁻¹
c = 9.7591 (14) Å	T = 293 K
β = 102.211 (3)°	Block, colourless
V = 1381.2 (4) Å³	0.20 × 0.18 × 0.15 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	976 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.5°, θ_min = 1.6°
ω/2θ scans	h = −31→24
Absorption correction: ψ scan (North et al., 1968)	k = −6→5
T_min = 0.981, T_max = 0.986	l = −11→11
3780 measured reflections	3 standard reflections every 200 reflections
1277 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.224	w = 1/[σ²(F_o²) + (0.168P)²] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1277 reflections	Δρ_max = 0.26 e Å⁻³
93 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (6)

Crystal data top

C₁₆H₁₈O₄	V = 1381.2 (4) Å³
M_r = 274.32	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 26.073 (4) Å	µ = 0.09 mm⁻¹
b = 5.5538 (8) Å	T = 293 K
c = 9.7591 (14) Å	0.20 × 0.18 × 0.15 mm
β = 102.211 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	976 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.023
T_min = 0.981, T_max = 0.986	3 standard reflections every 200 reflections
3780 measured reflections	intensity decay: 1%
1277 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.224	H-atom parameters constrained
S = 1.10	Δρ_max = 0.26 e Å⁻³
1277 reflections	Δρ_min = −0.29 e Å⁻³
93 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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) top

	x	y	z	U_iso*/U_eq
O1	0.20123 (6)	0.7928 (2)	0.33002 (13)	0.0496 (5)
O2	0.02888 (5)	0.7020 (2)	−0.10672 (11)	0.0412 (5)
C1	0.20477 (9)	0.9943 (3)	0.42124 (19)	0.0545 (8)
C2	0.15790 (7)	0.7773 (3)	0.22314 (17)	0.0332 (6)
C3	0.15573 (7)	0.5837 (3)	0.13368 (16)	0.0364 (6)
C4	0.11377 (7)	0.5526 (3)	0.02195 (16)	0.0343 (6)
C5	0.07272 (7)	0.7183 (3)	−0.00101 (16)	0.0316 (5)
C6	0.07499 (7)	0.9113 (3)	0.08874 (15)	0.0352 (6)
C7	0.11697 (7)	0.9435 (3)	0.20009 (16)	0.0361 (6)
C8	0.02601 (7)	0.5040 (3)	−0.20015 (15)	0.0369 (6)
H1A	0.20640	1.13950	0.36900	0.0820*
H1B	0.23590	0.98070	0.49380	0.0820*
H1C	0.17450	0.99880	0.46250	0.0820*
H3	0.18300	0.47210	0.14870	0.0440*
H4	0.11300	0.42150	−0.03770	0.0410*
H6	0.04770	1.02230	0.07400	0.0420*
H7	0.11790	1.07540	0.25930	0.0430*
H8A	0.03060	0.35460	−0.14740	0.0440*
H8B	0.05390	0.51580	−0.25180	0.0440*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0415 (9)	0.0576 (10)	0.0417 (9)	0.0100 (6)	−0.0089 (6)	−0.0100 (6)
O2	0.0360 (9)	0.0484 (9)	0.0342 (8)	0.0108 (5)	−0.0037 (6)	−0.0086 (5)
C1	0.0498 (13)	0.0594 (14)	0.0457 (12)	0.0018 (9)	−0.0094 (9)	−0.0141 (8)
C2	0.0324 (10)	0.0394 (11)	0.0261 (9)	0.0017 (7)	0.0024 (7)	0.0032 (6)
C3	0.0336 (11)	0.0408 (11)	0.0340 (10)	0.0103 (7)	0.0052 (7)	0.0028 (7)
C4	0.0373 (11)	0.0348 (10)	0.0307 (9)	0.0061 (7)	0.0067 (7)	−0.0021 (6)
C5	0.0302 (10)	0.0388 (10)	0.0250 (8)	0.0028 (6)	0.0041 (7)	0.0024 (6)
C6	0.0339 (10)	0.0355 (10)	0.0345 (10)	0.0087 (7)	0.0037 (8)	0.0003 (7)
C7	0.0393 (11)	0.0346 (10)	0.0335 (9)	0.0039 (7)	0.0054 (8)	−0.0039 (6)
C8	0.0375 (11)	0.0425 (11)	0.0286 (9)	0.0043 (6)	0.0024 (8)	−0.0033 (6)

Geometric parameters (Å, º) top

O1—C1	1.421 (2)	C8—C8ⁱ	1.493 (2)
O1—C2	1.369 (2)	C1—H1A	0.9600
O2—C5	1.371 (2)	C1—H1B	0.9600
O2—C8	1.4203 (19)	C1—H1C	0.9600
C2—C3	1.379 (2)	C3—H3	0.9300
C2—C7	1.393 (3)	C4—H4	0.9300
C3—C4	1.382 (2)	C6—H6	0.9300
C4—C5	1.393 (3)	C7—H7	0.9300
C5—C6	1.378 (2)	C8—H8A	0.9700
C6—C7	1.381 (2)	C8—H8B	0.9700

C1—O1—C2	117.44 (15)	H1A—C1—H1B	109.00
C5—O2—C8	117.16 (13)	H1A—C1—H1C	110.00
O1—C2—C3	116.64 (15)	H1B—C1—H1C	110.00
O1—C2—C7	124.21 (15)	C2—C3—H3	119.00
C3—C2—C7	119.16 (16)	C4—C3—H3	119.00
C2—C3—C4	121.10 (16)	C3—C4—H4	120.00
C3—C4—C5	119.81 (15)	C5—C4—H4	120.00
O2—C5—C4	124.55 (14)	C5—C6—H6	119.00
O2—C5—C6	116.53 (15)	C7—C6—H6	119.00
C4—C5—C6	118.91 (15)	C2—C7—H7	120.00
C5—C6—C7	121.42 (16)	C6—C7—H7	120.00
C2—C7—C6	119.60 (15)	O2—C8—H8A	110.00
O2—C8—C8ⁱ	109.61 (14)	O2—C8—H8B	110.00
O1—C1—H1A	109.00	H8A—C8—H8B	108.00
O1—C1—H1B	109.00	C8ⁱ—C8—H8A	110.00
O1—C1—H1C	109.00	C8ⁱ—C8—H8B	110.00

C1—O1—C2—C3	178.49 (16)	C3—C2—C7—C6	0.2 (3)
C1—O1—C2—C7	−1.2 (2)	C2—C3—C4—C5	−0.3 (3)
C8—O2—C5—C4	−1.2 (2)	C3—C4—C5—O2	−178.66 (16)
C8—O2—C5—C6	179.96 (15)	C3—C4—C5—C6	0.2 (3)
C5—O2—C8—C8ⁱ	175.16 (13)	O2—C5—C6—C7	179.05 (15)
O1—C2—C3—C4	−179.60 (16)	C4—C5—C6—C7	0.1 (2)
C7—C2—C3—C4	0.1 (3)	C5—C6—C7—C2	−0.3 (3)
O1—C2—C7—C6	179.87 (16)	O2—C8—C8ⁱ—O2ⁱ	69.45 (16)

Symmetry code: (i) −x, y, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱⁱ	0.96	2.60	3.453 (2)	148
C6—H6···O2ⁱⁱⁱ	0.93	2.59	3.490 (2)	163

Symmetry codes: (ii) −x+1/2, −y+3/2, −z+1; (iii) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈O₄
M_r	274.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	26.073 (4), 5.5538 (8), 9.7591 (14)
β (°)	102.211 (3)
V (Å³)	1381.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.981, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	3780, 1277, 976
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.224, 1.10
No. of reflections	1277
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.29

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.96	2.60	3.453 (2)	148
C6—H6···O2ⁱⁱ	0.93	2.59	3.490 (2)	163

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, −y+2, −z.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

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