Diethyl 2,2′-(1,4-phenyl­enedi­oxy)­diacetate

Husson, J.; Knorr, M.; Rousselin, Y.; Kubicki, M.M.

doi:10.1107/S1600536812030747

organic compounds

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Volume 68| Part 8| August 2012| Page o2422

https://doi.org/10.1107/S1600536812030747

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Diethyl 2,2′-(1,4-phenylenedioxy)diacetate

Jérôme Husson,^a Michael Knorr,^a Yoann Rousselin ^b and Marek M. Kubicki ^b ^*

^aInstitute UTINAM UMR CNRS 6213, University of Franche-Comté, 16 Route de Gray, Besançon 25030, France, and ^bICMUB UMR CNRS 5260, University of Bourgogne, 9 Avenue A. Savary, Dijon 21078, France
^*Correspondence e-mail: marek.kubicki@u-bourgogne.fr

(Received 19 April 2012; accepted 5 July 2012; online 10 July 2012)

In the title compound, C₁₄H₁₈O₆, a crystallographic center at the centroid of the aromatic ring generates the complete molecule which is planar within 0.085 (1) Å for the non-H atoms. In the crystal, weak C—H⋯O and C—H⋯π interactions link the molecules.

Related literature

For the syntheses and applications of aryloxyacetic acid derivatives, see: Carter & Lawrence (1900 ); Moser (1950 ); Kassem (1997 ); Hodge et al. (2000 ). For related crystal structures, see: Zhuang & Wang (2009 ); Du et al. (2006 ); Gao et al. (2004 ).

Experimental

Crystal data

C₁₄H₁₈O₆
M_r = 282.28
Monoclinic, P 2₁ /c
a = 4.9254 (3) Å
b = 9.7194 (5) Å
c = 14.9170 (11) Å
β = 108.313 (3)°
V = 677.94 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 115 K
0.40 × 0.27 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
2560 measured reflections
1536 independent reflections
1344 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.114
S = 1.09
1536 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C3/C1ⁱ–C3ⁱ ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯Cgⁱ	0.99	2.57	3.426 (2)	145
C6—H6B⋯O1ⁱⁱ	0.99	2.65	3.340 (2)	127
C6—H6B⋯O2ⁱⁱ	0.99	2.68	3.401 (2)	130
Symmetry codes: (i) x-1, y, z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: COLLECT (Nonius, 2004 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812030747/jj2131sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812030747/jj2131Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812030747/jj2131Isup4.cdx

Supporting information file. DOI: https://doi.org/10.1107/S1600536812030747/jj2131Isup4.cml

checkCIF report

Comment top

The title compound has been synthesized by different paths including the reaction of hydroquinone with sodium ethoxide followed by a Williamson reaction of the resulting dianion with ethyl bromoacetate (Carter & Lawrence, 1900), or the esterification of the corresponding diacid in the presence of BF₃—Et₂O complex as a catalyst (Moser, 1950). It has been used in the preparation of polymers (Kassem, 1997) and polyrotaxanes (Hodge et al., 2000).

A crystallographic center at the centroid of the central aromatic ring generates the complete molecule which is planar within 0.085 (1)Å without the H atoms (Fig. 1). The largest deviation from planarity among the ten non-hydrogen atoms is derived from O1 (0.085 (1) Å). A similar molecular geometry has been reported for the analogous dimethyl 1,4-(p-phenylenedioxy)diacetate molecule (Zhuang & Wang, 2009) as well as for the corresponding diacid (Du et al., 2006) and dianion (Gao et al., 2004). Weak intermolecular C—H···O and C—H··· π-ring (methylene···aryl) interactions (Table 1, Cg is the centroid of the C1-C3/C1i-C3i π-ring) are observed which contribute to crystal packing in the crystal (Fig. 2).

Related literature top

For the syntheses and applications of aryloxyacetic acid derivatives, see: Carter & Lawrence (1900); Moser (1950); Kassem (1997); Hodge et al. (2000). For related crystal structures, see: Zhuang & Wang (2009); Du et al. (2006); Gao et al. (2004).

Experimental top

Sodium (4.60 g; 0.2 mol) was added portionwise to absolute ethanol (250 ml). Once all sodium reacted, hydroquinone (11.00 g; 0.1 mol) was added and the solution refluxed for five minutes. After cooling to room temperature, ethyl chloroacetate (21.3 ml; 0.1 mol) was added and the reaction mixture refluxed for five hours. The mixture was then poured onto distilled water (250 ml) and pH adjusted to 3 by addition of few drops of concentrated hydrochloric acid. The aqueous layer was extracted with methyl-tertbutyl ether (4τimes100 ml). The organic layers were then combined, washed with saturated sodium hydrogencarbonate (3τimes100 ml) and water (100 ml). The ethereal layer was dried over calcium sulfate and concentrated under vacuum to afford the title compound as a beige solid. The crude product was recrystallized from dilute ethanol to afford the pure compound as colorless needles (5.58 g, 47%).

Structure description top

For the syntheses and applications of aryloxyacetic acid derivatives, see: Carter & Lawrence (1900); Moser (1950); Kassem (1997); Hodge et al. (2000). For related crystal structures, see: Zhuang & Wang (2009); Du et al. (2006); Gao et al. (2004).

Computing details top

Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of title compound(I) showing the atom labeling scheme of the asymmetric unit and 50% probability displacement ellipsoids. A crystallographic inversion center at the centroid of the central aromatic ring generates the complete molecule.
	Fig. 2. Packing diagram of the title compound viewed roughly along the a axis. Dashed lines indicate weak C—H···π (represented by the centroid of aromatic ring) and C—H···O intermoleclar interactions. Hydrogen atoms not involved in these interactions have been removed for clarity.

Diethyl 2,2'-(1,4-phenylenedioxy)diacetate top

Crystal data top

C₁₄H₁₈O₆	F(000) = 300
M_r = 282.28	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1387 reflections
a = 4.9254 (3) Å	θ = 1.0–27.5°
b = 9.7194 (5) Å	µ = 0.11 mm⁻¹
c = 14.9170 (11) Å	T = 115 K
β = 108.313 (3)°	Prism, colourless
V = 677.94 (7) Å³	0.40 × 0.27 × 0.15 mm
Z = 2

Data collection top

Nonius KappaCCD diffractometer	1344 reflections with I > 2σ(I)
Radiation source: Enraf–Nonius FR590	R_int = 0.029
Horizonally mounted graphite crystal monochromator	θ_max = 27.4°, θ_min = 2.5°
Detector resolution: 9 pixels mm^-1	h = −6→6
CCD rotation images, thick slices scans	k = −9→12
2560 measured reflections	l = −19→19
1536 independent 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0388P)² + 0.4496P] where P = (F_o² + 2F_c²)/3
1536 reflections	(Δ/σ)_max < 0.001
92 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³
0 constraints

Crystal data top

C₁₄H₁₈O₆	V = 677.94 (7) Å³
M_r = 282.28	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.9254 (3) Å	µ = 0.11 mm⁻¹
b = 9.7194 (5) Å	T = 115 K
c = 14.9170 (11) Å	0.40 × 0.27 × 0.15 mm
β = 108.313 (3)°

Data collection top

Nonius KappaCCD diffractometer	1344 reflections with I > 2σ(I)
2560 measured reflections	R_int = 0.029
1536 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.09	Δρ_max = 0.29 e Å⁻³
1536 reflections	Δρ_min = −0.26 e Å⁻³
92 parameters

Special details top

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.

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	0.2542 (2)	0.85579 (11)	0.61485 (7)	0.0183 (3)
O2	0.0149 (3)	0.73769 (12)	0.73286 (7)	0.0253 (3)
O3	−0.2554 (2)	0.60124 (11)	0.61710 (7)	0.0204 (3)
C1	0.3679 (3)	0.92498 (14)	0.55420 (10)	0.0153 (3)
C2	0.2808 (3)	0.90691 (14)	0.45650 (10)	0.0160 (3)
H2	0.1321	0.8440	0.4268	0.019*
C3	0.4152 (3)	0.98254 (15)	0.40315 (10)	0.0162 (3)
H3	0.3575	0.9706	0.3366	0.019*
C4	0.0340 (3)	0.76022 (14)	0.57334 (10)	0.0164 (3)
H4A	0.1066	0.6860	0.5415	0.020*
H4B	−0.1269	0.8066	0.5259	0.020*
C5	−0.0652 (3)	0.70087 (15)	0.65171 (10)	0.0174 (3)
C6	−0.3690 (3)	0.53564 (16)	0.68587 (10)	0.0207 (3)
H6A	−0.4725	0.6039	0.7122	0.025*
H6B	−0.2112	0.4965	0.7384	0.025*
C7	−0.5696 (4)	0.42320 (16)	0.63551 (11)	0.0235 (3)
H7A	−0.7226	0.4628	0.5829	0.035*
H7B	−0.6530	0.3786	0.6797	0.035*
H7C	−0.4639	0.3550	0.6112	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0220 (5)	0.0212 (5)	0.0149 (5)	−0.0062 (4)	0.0106 (4)	0.0001 (4)
O2	0.0311 (6)	0.0298 (6)	0.0172 (6)	−0.0089 (5)	0.0106 (5)	0.0001 (5)
O3	0.0268 (6)	0.0205 (5)	0.0179 (5)	−0.0062 (4)	0.0128 (4)	0.0005 (4)
C1	0.0176 (7)	0.0154 (6)	0.0170 (7)	0.0024 (5)	0.0114 (5)	0.0030 (5)
C2	0.0177 (7)	0.0154 (6)	0.0175 (7)	0.0001 (5)	0.0091 (5)	−0.0011 (5)
C3	0.0182 (7)	0.0183 (7)	0.0141 (6)	0.0007 (5)	0.0080 (5)	−0.0008 (5)
C4	0.0198 (7)	0.0157 (6)	0.0167 (7)	−0.0023 (5)	0.0099 (5)	0.0001 (5)
C5	0.0187 (7)	0.0169 (7)	0.0193 (7)	0.0013 (5)	0.0100 (5)	0.0031 (5)
C6	0.0254 (8)	0.0218 (7)	0.0190 (7)	−0.0027 (6)	0.0130 (6)	0.0041 (6)
C7	0.0268 (8)	0.0194 (7)	0.0263 (8)	−0.0036 (6)	0.0111 (6)	0.0008 (6)

Geometric parameters (Å, º) top

O1—C1	1.3796 (16)	C3—H3	0.9500
O1—C4	1.4145 (17)	C4—C5	1.5157 (19)
O2—C5	1.2037 (18)	C4—H4A	0.9900
O3—C5	1.3334 (18)	C4—H4B	0.9900
O3—C6	1.4603 (16)	C6—C7	1.506 (2)
C1—C3ⁱ	1.388 (2)	C6—H6A	0.9900
C1—C2	1.395 (2)	C6—H6B	0.9900
C2—C3	1.3939 (19)	C7—H7A	0.9800
C2—H2	0.9500	C7—H7B	0.9800
C3—C1ⁱ	1.388 (2)	C7—H7C	0.9800

C1—O1—C4	116.52 (11)	H4A—C4—H4B	108.5
C5—O3—C6	115.01 (11)	O2—C5—O3	125.01 (13)
O1—C1—C3ⁱ	115.31 (12)	O2—C5—C4	125.40 (13)
O1—C1—C2	124.67 (13)	O3—C5—C4	109.59 (12)
C3ⁱ—C1—C2	120.02 (13)	O3—C6—C7	107.61 (12)
C3—C2—C1	118.99 (13)	O3—C6—H6A	110.2
C3—C2—H2	120.5	C7—C6—H6A	110.2
C1—C2—H2	120.5	O3—C6—H6B	110.2
C1ⁱ—C3—C2	120.99 (13)	C7—C6—H6B	110.2
C1ⁱ—C3—H3	119.5	H6A—C6—H6B	108.5
C2—C3—H3	119.5	C6—C7—H7A	109.5
O1—C4—C5	107.51 (11)	C6—C7—H7B	109.5
O1—C4—H4A	110.2	H7A—C7—H7B	109.5
C5—C4—H4A	110.2	C6—C7—H7C	109.5
O1—C4—H4B	110.2	H7A—C7—H7C	109.5
C5—C4—H4B	110.2	H7B—C7—H7C	109.5

C4—O1—C1—C3ⁱ	−179.61 (12)	C6—O3—C5—O2	0.2 (2)
C4—O1—C1—C2	0.03 (19)	C6—O3—C5—C4	−179.79 (11)
O1—C1—C2—C3	−179.44 (13)	O1—C4—C5—O2	5.5 (2)
C3ⁱ—C1—C2—C3	0.2 (2)	O1—C4—C5—O3	−174.54 (11)
C1—C2—C3—C1ⁱ	−0.2 (2)	C5—O3—C6—C7	−177.83 (12)
C1—O1—C4—C5	−178.01 (11)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1-C3/C1i-C3i ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Cgⁱⁱ	0.99	2.57	3.426 (2)	145
C6—H6B···O1ⁱⁱⁱ	0.99	2.65	3.340 (2)	127
C6—H6B···O2ⁱⁱⁱ	0.99	2.68	3.401 (2)	130

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈O₆
M_r	282.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	115
a, b, c (Å)	4.9254 (3), 9.7194 (5), 14.9170 (11)
β (°)	108.313 (3)
V (Å³)	677.94 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.40 × 0.27 × 0.15

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2560, 1536, 1344
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.114, 1.09
No. of reflections	1536
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.26

Computer programs: COLLECT (Nonius, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1-C3/C1i-C3i ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···Cgⁱ	0.990	2.572	3.426 (2)	144.5
C6—H6B···O1ⁱⁱ	0.990	2.645	3.340 (2)	127.3
C6—H6B···O2ⁱⁱ	0.990	2.681	3.401 (2)	129.9

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

Acknowledgements

The authors thank the CNRS for financial support.

References

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