Diethyl 4,4′-(ethane-1,2-diyldi­oxy)dibenzoate

Ma, Z.; Yang, H.

doi:10.1107/S1600536811021258

organic compounds

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Volume 67| Part 7| July 2011| Page o1623

doi:10.1107/S1600536811021258

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Diethyl 4,4′-(ethane-1,2-diyldioxy)dibenzoate

Zhen Ma ^a ^* and Huang Yang ^a

^aSchool of Chemistry and Chemical Engineering, Guangxi University, Guangxi 530004, People's Republic of China
^*Correspondence e-mail: mzmz2009@sohu.com

(Received 25 April 2011; accepted 2 June 2011; online 11 June 2011)

The title compound, C₂₀H₂₂O₆, was obtained by the reaction of ethyl 4-hydroxybenzoate with 1,2-dichloroethane in dimethylformamide. The molecule lies around the crystallographic inversion center at (0,0,0), with the asymmetric unit consisting of one half of the molecule. The two ethyl groups are in trans positions. The ethyl, carboxyl, aryl and O—CH₂ groups are coplanar with an r.m.s. deviation of 0.0208 (9) Å. The whole molecule is planar with an r.m.s. deviation of 0.0238 (9) Å for the 19 atoms used in the calculation and 0.0071 (9) Å for the two aryl groups in the molecule. A weak intermolecular C—H⋯O hydrogen bond and a C—H⋯π interaction help to consolidate the three-dimensional network.

Related literature

For the synthesis and structures of diesters, see Hou & Kan (2007 ); Tashiro et al. (1990 ); Zhang et al. (2007 ). For the properties and applications of diesters, see: Chen & Liu (2002 ). For the synthesis of the title compound, see: Ma & Liu (2002 ); Ma & Cao (2011 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₀H₂₂O₆
M_r = 358.38
Monoclinic, P 2₁ /c
a = 4.8504 (10) Å
b = 15.847 (3) Å
c = 12.0159 (19) Å
β = 104.250 (8)°
V = 895.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.49 × 0.35 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.960, T_max = 0.979
8592 measured reflections
1980 independent reflections
1713 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.130
S = 1.02
1980 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O2ⁱ	0.93	2.47	3.2784 (16)	146
C10—H10B⋯Cgⁱⁱ	0.97	2.65	3.741 (2)	143
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x+1, y, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2002 ); data reduction: SAINT; 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 I, global. DOI: 10.1107/S1600536811021258/ez2245sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021258/ez2245Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811021258/ez2245Isup3.cml

checkCIF report

Comment top

There has been, in recent years, a considerable interest in the study of esters (Hou & Kan, 2007; Tashiro et al., 1990; Zhang et al., 2007), since these compounds are commodity chemicals used as intermediates in the manufacture of acids and to produce many important industrial products. Hence, our current work aims to prepare esters to produce acids and investigate their coordination behaviors with metal ions and study their applications in many fields (Chen & Liu, 2002). Herein, we report a new diester which was obtained by reaction of ethyl 4-hydroxybenzoate with 1,2-dichloroethane in DMF and its structure was confirmed by elemental analysis, IR, NMR spectra and X-ray crystal analysis.

The structure consists of a neutral molecular unit (Fig. 1).The molecule lies on a crystallographic inversion center at (0, 0, 0), thus leading to one half of the molecule being present per asymmetric unit. All bond lengths and angles are within normal ranges (Allen et al., 1987). The ethyl, aryl, carboxyl and the O—CH₂ groups of one half molecule are coplanar to form one plane with an r.m.s. deviation of 0.0208 (9) Å. By symmetry, the whole molecule is coplanar with an r.m.s deviation of 0.0238 (9) Å for 19 atoms being used for calculation and 0.0071 (9) Å for the two aryl groups at the molecule. Because of the symmetry of the inversion center, the two ethyl groups at the molecule are in a trans position. One weak hydrogen bond between one hydrogen atom and the oxygen atom of a neighboring molecule is present in the structure: H6A on C6 and O2ⁱⁱ [symmetry code: (ii) x, -y+1/2, z-1/2] (Table 1). The molecules display intermolecular C—H···π interactions between a –CH₂-(C10) and a neighboring aryl group [H..Cg 2.647 Å, Cg is the centroid of the six membered ring of C4ⁱⁱⁱ-C9ⁱⁱⁱ, symmetry code: (iii) x+1, y, z].

Related literature top

For the synthesis and structures of diesters, see Hou & Kan (2007); Tashiro et al. (1990); Zhang et al. (2007). For the properties and applications of diesters, see: Chen & Liu (2002). For the synthesis of the title compound, see: Ma & Liu (2002); Ma & Cao (2011). For standard bond lengths, see: Allen et al. (1987).

Experimental top

The title compound was obtained by the reaction of ethyl 4-hydroxybenzoate with 1,2-dichloroethane in N,N'-dimethylformamide (DMF) according to a reported procedure (Ma & Liu, 2002; Ma & Cao, 2011). In a 100 cm³ flask fitted with a funnel, ethyl 4-hydroxybenzoate (8.3 g, 50 mM) and potassium carbonate were mixed in 50 cm³ of DMF. To this solution was added dropwise a stoichiometric quantity of 1,2-dichloroethane (2.5 g, 25 mM) dissolved in 20 cm³ of DMF for a period of an hour with stirring. The mixture was then stirred for 24 h at 353 K. The solution was concentrated under reduced pressure and the white solid formed by adding a large quantity of water (200 cm³) was filtered off and recrystallized from ethanol and decolored with activated carbon. A colorless solid was obtained (yield 30 %, m.p: 388–390 K). Slow evaporation of a solution of the title compound in ethanol and dichloromethane (1:1) led to the formation of colorless crystals, which were suitable for X-ray characterization. Anal. Calcd. for [C₂₀H₂₂O₆] (%): C, 67.03; H, 6.19; found: C, 66.75; H, 6.46; IR(KBr), (cm^-1): 1711, (C=O), 1605, 1509, 1477 (C=C of aryl), 1280, 1252, 1165, 1105 (CH₂—O—CH₂), 1045, 1027, 870-715, (Ar—H). ¹H NMR (CDCl₃): 7.97 (d, 4H, J = 8.8 Hz, aryl, c), 6.94 (d, 4H, J = 8.8 Hz, aryl, d), 4.34 (d, 4H, OCH₂CH₂, f), 4.31 (d, 4H, COOCH₂, g), 1.35 (t, 6H, –CH₃, h). ¹³C NMR: 166.4 (–COO, a), 162.4 (aryl, b), 131.8 (aryl, c), 123.7 (aryl, e), 114.4 (aryl, d), 66.6 (CH₂CH₂, f), 60.9 (CH₂CH₂, g), 14.6 (–CH₃, h). (see Figure 3 for the NMR atom number assignment).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius. [Symmetry code: (i) -x, -y, -z]
	Fig. 2. A view of the crystal packing along the a axis. The thin dashed lines are used to show the hydrogen bonds. The thick dashed line is used to show the intermolecular CH-π interactions of –CH₂-(C6) and the neighboring aryl groups, from their H atoms to the centroids of the rings of the aryl groups.
	Fig. 3. An additional scheme with the numbering scheme used for the NMR spectra.

Diethyl 4,4'-(ethane-1,2-diyldioxy)dibenzoate top

Crystal data top

C₂₀H₂₂O₆	F(000) = 380
M_r = 358.38	D_x = 1.330 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8592 reflections
a = 4.8504 (10) Å	θ = 2.2–27.2°
b = 15.847 (3) Å	µ = 0.10 mm⁻¹
c = 12.0159 (19) Å	T = 298 K
β = 104.250 (8)°	Prism, colorless
V = 895.2 (3) Å³	0.49 × 0.35 × 0.22 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	1980 independent reflections
Radiation source: fine-focus sealed tube	1713 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 0 pixels mm^-1	θ_max = 27.2°, θ_min = 2.2°
ϕ and ω scans	h = −6→5
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −20→20
T_min = 0.960, T_max = 0.979	l = −15→14
8592 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0876P)² + 0.1852P] where P = (F_o² + 2F_c²)/3
1980 reflections	(Δ/σ)_max < 0.001
119 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₂₀H₂₂O₆	V = 895.2 (3) Å³
M_r = 358.38	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.8504 (10) Å	µ = 0.10 mm⁻¹
b = 15.847 (3) Å	T = 298 K
c = 12.0159 (19) Å	0.49 × 0.35 × 0.22 mm
β = 104.250 (8)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1980 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1713 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.979	R_int = 0.032
8592 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.02	Δρ_max = 0.34 e Å⁻³
1980 reflections	Δρ_min = −0.34 e Å⁻³
119 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	−1.19587 (17)	0.35479 (5)	−0.09590 (7)	0.0219 (2)
O2	−0.9567 (2)	0.37413 (6)	0.08774 (8)	0.0313 (3)
O3	−0.30202 (17)	0.06258 (5)	−0.06554 (7)	0.0209 (2)
C1	−1.5949 (3)	0.43801 (8)	−0.19241 (11)	0.0302 (3)
H1A	−1.7199	0.4833	−0.1843	0.045*
H1B	−1.7026	0.3869	−0.2106	0.045*
H1C	−1.5046	0.4510	−0.2530	0.045*
C2	−1.3723 (3)	0.42675 (7)	−0.08179 (11)	0.0234 (3)
H2A	−1.2566	0.4772	−0.0643	0.028*
H2B	−1.4617	0.4164	−0.0192	0.028*
C3	−0.9916 (2)	0.33543 (7)	−0.00155 (10)	0.0199 (3)
C4	−0.8119 (2)	0.26316 (7)	−0.01966 (10)	0.0188 (3)
C5	−0.8593 (2)	0.21922 (7)	−0.12413 (10)	0.0199 (3)
H5A	−1.0097	0.2346	−0.1851	0.024*
C6	−0.6832 (2)	0.15314 (7)	−0.13669 (10)	0.0196 (3)
H6A	−0.7145	0.1243	−0.2060	0.024*
C7	−0.4580 (2)	0.12990 (7)	−0.04481 (10)	0.0174 (3)
C8	−0.4063 (2)	0.17353 (7)	0.05940 (10)	0.0197 (3)
H8A	−0.2549	0.1584	0.1201	0.024*
C9	−0.5851 (2)	0.23998 (7)	0.07089 (10)	0.0197 (3)
H9A	−0.5526	0.2693	0.1400	0.024*
C10	−0.0671 (2)	0.03624 (7)	0.02485 (9)	0.0182 (3)
H10A	−0.1317	0.0179	0.0912	0.022*
H10B	0.0678	0.0820	0.0478	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0219 (4)	0.0201 (4)	0.0220 (4)	0.0073 (3)	0.0025 (3)	−0.0001 (3)
O2	0.0341 (5)	0.0299 (5)	0.0257 (5)	0.0111 (4)	−0.0005 (4)	−0.0075 (4)
O3	0.0185 (4)	0.0204 (4)	0.0212 (4)	0.0056 (3)	0.0002 (3)	−0.0036 (3)
C1	0.0313 (7)	0.0299 (7)	0.0275 (7)	0.0108 (5)	0.0034 (5)	0.0042 (5)
C2	0.0235 (6)	0.0183 (5)	0.0281 (6)	0.0065 (4)	0.0058 (5)	−0.0008 (4)
C3	0.0199 (6)	0.0182 (5)	0.0209 (6)	0.0009 (4)	0.0040 (4)	0.0011 (4)
C4	0.0188 (6)	0.0169 (5)	0.0210 (6)	0.0006 (4)	0.0053 (4)	0.0014 (4)
C5	0.0198 (6)	0.0192 (5)	0.0194 (6)	0.0013 (4)	0.0025 (4)	0.0023 (4)
C6	0.0217 (6)	0.0190 (5)	0.0176 (5)	−0.0001 (4)	0.0036 (4)	−0.0007 (4)
C7	0.0163 (5)	0.0154 (5)	0.0210 (6)	0.0002 (4)	0.0053 (4)	0.0007 (4)
C8	0.0176 (5)	0.0200 (5)	0.0200 (6)	0.0009 (4)	0.0019 (4)	0.0004 (4)
C9	0.0208 (6)	0.0186 (5)	0.0191 (6)	−0.0001 (4)	0.0039 (4)	−0.0022 (4)
C10	0.0158 (5)	0.0176 (5)	0.0200 (5)	0.0017 (4)	0.0021 (4)	−0.0008 (4)

Geometric parameters (Å, º) top

O1—C3	1.3446 (14)	C4—C5	1.4040 (16)
O1—C2	1.4604 (13)	C5—C6	1.3829 (15)
O2—C3	1.2109 (15)	C5—H5A	0.9300
O3—C7	1.3659 (13)	C6—C7	1.3977 (16)
O3—C10	1.4294 (13)	C6—H6A	0.9300
C1—C2	1.5027 (18)	C7—C8	1.3978 (16)
C1—H1A	0.9600	C8—C9	1.3925 (16)
C1—H1B	0.9600	C8—H8A	0.9300
C1—H1C	0.9600	C9—H9A	0.9300
C2—H2A	0.9700	C10—C10ⁱ	1.513 (2)
C2—H2B	0.9700	C10—H10A	0.9700
C3—C4	1.4874 (15)	C10—H10B	0.9700
C4—C9	1.3928 (16)

C3—O1—C2	114.29 (9)	C6—C5—H5A	119.9
C7—O3—C10	117.60 (8)	C4—C5—H5A	119.9
C2—C1—H1A	109.5	C5—C6—C7	119.79 (10)
C2—C1—H1B	109.5	C5—C6—H6A	120.1
H1A—C1—H1B	109.5	C7—C6—H6A	120.1
C2—C1—H1C	109.5	O3—C7—C6	114.96 (10)
H1A—C1—H1C	109.5	O3—C7—C8	124.36 (10)
H1B—C1—H1C	109.5	C6—C7—C8	120.68 (10)
O1—C2—C1	107.71 (10)	C9—C8—C7	118.94 (11)
O1—C2—H2A	110.2	C9—C8—H8A	120.5
C1—C2—H2A	110.2	C7—C8—H8A	120.5
O1—C2—H2B	110.2	C8—C9—C4	120.89 (10)
C1—C2—H2B	110.2	C8—C9—H9A	119.6
H2A—C2—H2B	108.5	C4—C9—H9A	119.6
O2—C3—O1	123.03 (10)	O3—C10—C10ⁱ	105.17 (11)
O2—C3—C4	124.07 (11)	O3—C10—H10A	110.7
O1—C3—C4	112.89 (10)	C10ⁱ—C10—H10A	110.7
C9—C4—C5	119.45 (10)	O3—C10—H10B	110.7
C9—C4—C3	117.87 (10)	C10ⁱ—C10—H10B	110.7
C5—C4—C3	122.68 (11)	H10A—C10—H10B	108.8
C6—C5—C4	120.23 (11)

C3—O1—C2—C1	−177.91 (10)	C10—O3—C7—C6	179.46 (9)
C2—O1—C3—O2	0.12 (16)	C10—O3—C7—C8	−1.26 (16)
C2—O1—C3—C4	−178.70 (9)	C5—C6—C7—O3	178.44 (9)
O2—C3—C4—C9	−1.66 (17)	C5—C6—C7—C8	−0.88 (16)
O1—C3—C4—C9	177.15 (9)	O3—C7—C8—C9	−178.42 (10)
O2—C3—C4—C5	179.57 (11)	C6—C7—C8—C9	0.83 (16)
O1—C3—C4—C5	−1.62 (16)	C7—C8—C9—C4	−0.16 (16)
C9—C4—C5—C6	0.41 (16)	C5—C4—C9—C8	−0.45 (16)
C3—C4—C5—C6	179.16 (10)	C3—C4—C9—C8	−179.26 (10)
C4—C5—C6—C7	0.25 (16)	C7—O3—C10—C10ⁱ	−178.04 (10)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2ⁱⁱ	0.93	2.47	3.2784 (16)	146
C10—H10B···Cgⁱⁱⁱ	0.97	2.65	3.741 (2)	143

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

Experimental details

Crystal data
Chemical formula	C₂₀H₂₂O₆
M_r	358.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	4.8504 (10), 15.847 (3), 12.0159 (19)
β (°)	104.250 (8)
V (Å³)	895.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.49 × 0.35 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.960, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	8592, 1980, 1713
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.644

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.130, 1.02
No. of reflections	1980
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.34

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2ⁱ	0.93	2.47	3.2784 (16)	145.8
C10—H10B···Cgⁱⁱ	0.97	2.65	3.741 (2)	143

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

Acknowledgements

The authors are grateful for financial support from the Scientific Fund of Guangxi University (grant No. X061144).

References

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