Dimethyl 2,2′-(p-phenyl­enedi­oxy)­diacetate

Zhuang, L.; Wang, G.

doi:10.1107/S1600536809002980

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o403

doi:10.1107/S1600536809002980

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Dimethyl 2,2′-(p-phenylenedioxy)diacetate

Ling-hua Zhuang ^a and Guo-wei Wang ^b ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bDepartment of Light Chemical Engineering, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: kingwell2004@sina.com.cn

(Received 11 January 2009; accepted 23 January 2009; online 28 January 2009)

The title compound, C₁₂H₁₄O₆, was prepared by the Williamson reaction of 1,4-dihydroxybenzene and methyl chloroacetate with phase-transfer catalysis. The compound lies on an inversion center. The structure is stabilized by weak C—H⋯π interactions.

Related literature

For details of the synthesis procedure and the applications of benzothiazoles, see: Chakraborti et al. (2004 ); Seijas et al. (2007 ); Wang et al. (2009 ). For details of the synthesis procedure and the applications of aryloxyacetic acids, see: Nagy et al. (1997 ); Wei et al. (2005 ). For the use of phase-transfer catalysis in organic synthesis, see: Perreux et al. (2001 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₄O₆
M_r = 254.23
Monoclinic, P 2₁ /n
a = 7.4190 (15) Å
b = 7.0990 (14) Å
c = 11.785 (2) Å
β = 95.49 (3)°
V = 617.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.954, T_max = 0.977
1123 measured reflections
1123 independent reflections
769 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: 9%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.173
S = 1.00
1123 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C3/C1A–C3A ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6C⋯Cg1ⁱ	0.97	2.98	3.674 (2)	130
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809002980/dn2426sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809002980/dn2426Isup2.hkl

checkCIF report

Comment top

The derivatives of aryloxyacetic acids and their derivatives constitute a class of compounds for both biological activity and plant growth regulators (Nagy et al., 1997; Wei et al.,2005). The phase-transfer catalysis, with the advantages of simple experimental operations, mild reaction conditions, and inexpensive and environmentally benign reagents, has established its significance in organic synthesis as one of the most useful methods for the acceleration of heterogeneous reactions (Perreux & Loupy, 2001).

Benzothiazole are remarkable heterocyclic ring systems. They have been found to exhibit a wide spectrum of biological activities. Many kinds of 2-substituted benzothiazoles are utilized as vulcanization accelators in the manufacture of rubber,as fluorescent brightening agents in textile dyeing,and in the leather industry (Chakraborti et al.,2004; Seijas et al.,2007; Wang et al.,2009). There are numerous synthetic methods to produce 2-arylbenzothiazoles. The most important ones include the reaction of o-aminothiophenols with benzoic acids or their derivatives (Chakraborti et al.,2004; Seijas et al.,2007; Wang et al.,2009). We are focusing on the synthesis of new products of bisbenzothiazole. We here report the crystal structure of the title compound (I).

The compound (I) lies on an inversion center(Fig.1). All bond lengths are within normal ranges (Allen et al., 1987). There are no typical hydrogen bonds, while weak intermolecular C—H···π interactions involving benzene ring (C1/C3/C2/C1a/C3a/C2a) (Table 1) may help in stabilizing the structure.

Related literature top

For details of the synthesis procedure and the applications of benzothiazoles, see: Chakraborti et al. (2004); Seijas et al. (2007); Wang et al. (2009). For details of the synthesis procedure and the applications of aryloxyacetic acids, see: Nagy et al. (1997); Wei et al. (2005). For the use of phase-transfer catalysis in organic synthesis, see: Perreux et al. (2001). For bond-length data, see: Allen et al. (1987).

Experimental top

5.5 g (0.05 mole) hydroquinone was dissolved in 50 ml acetone, 6.9 g (0.05 mole) potassium carbonate, potassium iodide 0.8 g and tetrabutyl ammonium bromide 1.0 g were added. Then 8.8 ml L (0.10 mole) of methyl chloroacetate was dropped into the mixture. The mixture was boiled for 5 h with intensive stirring, cooled to room temperature, and filtered. The organic solution was evaporated under vacuum to dryness and the dry residue was recrystallized from methanol to obtain title compound. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of ethyl acetate. ¹H NMR (CDCl₃, δ, p.p.m.) 6.85 (m, 4H), 4.58 (s, 4H), 3.79 (s,6H).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular structure of (I) showing the atom-numbering scheme. Ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. [symmetry code: (A) 1/2-x, 1/2+y, 1/2-z].

Dimethyl 2,2'-(p-phenylenedioxy)diacetate top

Crystal data top

C₁₂H₁₄O₆	F(000) = 268
M_r = 254.23	D_x = 1.367 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 27 reflections
a = 7.4190 (15) Å	θ = 1–25°
b = 7.0990 (14) Å	µ = 0.11 mm⁻¹
c = 11.785 (2) Å	T = 293 K
β = 95.49 (3)°	Block, yellow
V = 617.8 (2) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	769 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.3°, θ_min = 3.1°
ω/2θ scans	h = −8→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.954, T_max = 0.977	l = 0→14
1123 measured reflections	3 standard reflections every 200 reflections
1123 independent reflections	intensity decay: 9%

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 0.23P] where P = (F_o² + 2F_c²)/3
1123 reflections	(Δ/σ)_max = 0.001
82 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₁₄O₆	V = 617.8 (2) Å³
M_r = 254.23	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4190 (15) Å	µ = 0.11 mm⁻¹
b = 7.0990 (14) Å	T = 293 K
c = 11.785 (2) Å	0.30 × 0.20 × 0.10 mm
β = 95.49 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	769 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.954, T_max = 0.977	3 standard reflections every 200 reflections
1123 measured reflections	intensity decay: 9%
1123 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
1123 reflections	Δρ_min = −0.24 e Å⁻³
82 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	1.1983 (3)	0.2968 (2)	−0.07350 (16)	0.0520 (6)
O2	1.3969 (3)	0.5931 (3)	−0.13385 (19)	0.0636 (7)
O3	1.6159 (2)	0.3997 (3)	−0.17937 (17)	0.0531 (6)
C1	0.8429 (3)	0.0447 (3)	0.0519 (2)	0.0431 (7)
H1A	0.7382	0.0734	0.0859	0.052*
C2	0.9507 (3)	0.1863 (4)	0.0139 (2)	0.0444 (7)
H2A	0.9186	0.3114	0.0235	0.053*
C3	1.1039 (3)	0.1452 (4)	−0.0376 (2)	0.0425 (7)
C4	1.3668 (3)	0.2569 (4)	−0.1199 (2)	0.0460 (7)
H4A	1.3449	0.1844	−0.1896	0.055*
H4B	1.4456	0.1845	−0.0658	0.055*
C5	1.4535 (3)	0.4417 (4)	−0.1439 (2)	0.0441 (7)
C6	1.7243 (4)	0.5536 (4)	−0.2101 (3)	0.0617 (8)
H6A	1.8350	0.5067	−0.2354	0.093*
H6B	1.7513	0.6340	−0.1452	0.093*
H6C	1.6595	0.6240	−0.2705	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0553 (11)	0.0450 (11)	0.0577 (12)	0.0023 (9)	0.0163 (9)	0.0020 (9)
O2	0.0667 (14)	0.0491 (12)	0.0760 (16)	0.0059 (10)	0.0130 (11)	−0.0036 (11)
O3	0.0517 (11)	0.0536 (12)	0.0555 (12)	−0.0040 (9)	0.0125 (9)	−0.0034 (9)
C1	0.0441 (14)	0.0464 (14)	0.0381 (14)	0.0046 (11)	−0.0002 (10)	−0.0050 (11)
C2	0.0433 (14)	0.0448 (14)	0.0444 (16)	0.0021 (11)	0.0006 (11)	−0.0049 (12)
C3	0.0451 (14)	0.0459 (14)	0.0356 (14)	0.0001 (11)	−0.0011 (11)	0.0007 (11)
C4	0.0395 (13)	0.0500 (15)	0.0473 (15)	−0.0007 (11)	−0.0018 (11)	0.0007 (12)
C5	0.0519 (15)	0.0476 (15)	0.0314 (13)	0.0028 (12)	−0.0031 (11)	−0.0023 (11)
C6	0.0703 (19)	0.0603 (18)	0.0553 (18)	−0.0192 (15)	0.0100 (14)	0.0034 (15)

Geometric parameters (Å, º) top

O1—C3	1.372 (3)	C2—C3	1.370 (4)
O1—C4	1.440 (3)	C2—H2A	0.9300
O2—C5	1.164 (3)	C4—C5	1.499 (4)
O3—C5	1.347 (3)	C4—H4A	0.9700
O3—C6	1.424 (3)	C4—H4B	0.9700
C1—C2	1.385 (4)	C6—H6A	0.9600
C1—C3ⁱ	1.419 (3)	C6—H6B	0.9600
C1—H1A	0.9300	C6—H6C	0.9600

C3—O1—C4	116.7 (2)	C5—C4—H4A	110.2
C5—O3—C6	116.9 (2)	O1—C4—H4B	110.2
C2—C1—C3ⁱ	118.4 (2)	C5—C4—H4B	110.2
C2—C1—H1A	120.8	H4A—C4—H4B	108.5
C3ⁱ—C1—H1A	120.8	O2—C5—O3	125.3 (3)
C3—C2—C1	121.2 (2)	O2—C5—C4	128.6 (3)
C3—C2—H2A	119.4	O3—C5—C4	106.1 (2)
C1—C2—H2A	119.4	O3—C6—H6A	109.5
C2—C3—O1	116.0 (2)	O3—C6—H6B	109.5
C2—C3—C1ⁱ	120.4 (2)	H6A—C6—H6B	109.5
O1—C3—C1ⁱ	123.5 (2)	O3—C6—H6C	109.5
O1—C4—C5	107.6 (2)	H6A—C6—H6C	109.5
O1—C4—H4A	110.2	H6B—C6—H6C	109.5

C3ⁱ—C1—C2—C3	0.9 (4)	C3—O1—C4—C5	−175.2 (2)
C1—C2—C3—O1	178.9 (2)	C6—O3—C5—O2	−1.9 (4)
C1—C2—C3—C1ⁱ	−0.9 (4)	C6—O3—C5—C4	178.7 (2)
C4—O1—C3—C2	175.4 (2)	O1—C4—C5—O2	−3.6 (4)
C4—O1—C3—C1ⁱ	−4.8 (4)	O1—C4—C5—O3	175.74 (19)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6C···Cg1ⁱⁱ	0.97	2.98	3.674 (2)	130

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄O₆
M_r	254.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.4190 (15), 7.0990 (14), 11.785 (2)
β (°)	95.49 (3)
V (Å³)	617.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.954, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	1123, 1123, 769
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.173, 1.00
No. of reflections	1123
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.24

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6C···Cg1ⁱ	0.97	2.98	3.674 (2)	130

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

Acknowledgements

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

References

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