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

Huaduan Shi; Haisha Qin; Zhen Ma

doi:10.1107/S1600536814007673

. 2014 Apr 12;70(Pt 5):o552. doi: 10.1107/S1600536814007673

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

Huaduan Shi ^a, Haisha Qin ^a, Zhen Ma ^a,^*

PMCID: PMC4011244 PMID: 24860360

Abstract

The molecular title compound, C₂₀H₂₂O₆, was obtained by the reaction of ethyl 2-hydroxybenzoate with 1,2-dichloroethane. The molecule lies on a twofold rotation axis which passes through the middle of the central ethylene bridge. This group exhibits a gauche conformation with the corresponding O—C—C—O torsion angle being 73.2 (2)°. The C atoms of the carboxyl group, the aryl and the O—CH₂ group are coplanar, with an r.m.s. deviation of 0.01 Å. The two aryl rings form a dihedral angle of 67.94 (4)°. The ester ethyl group is disordered over two sets of sites with an occupancy ratio of 0.59 (2):0.41 (2). The crystal packing is dominated by van der Waals forces.

Related literature

For synthesis and structures of diesters, see: Ma et al. (2012 ▶); Hou & Kan (2007 ▶). For properties and applications of diesters, see: Chen & Liu (2002 ▶). For the synthesis of the title compound, see: Ma & Liu (2002 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For background to the applications of organic acids and esters, see: Chanthapally et al. (2012 ▶); Yan et al. (2012 ▶).

Experimental

Crystal data

C₂₀H₂₂O₆
M _r = 358.38
Orthorhombic,
a = 21.805 (4) Å
b = 9.871 (2) Å
c = 8.8646 (18) Å
V = 1908.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.35 × 0.31 × 0.28 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.858, T _max = 1.000
11280 measured reflections
2192 independent reflections
1543 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.132
S = 1.04
2192 reflections
140 parameters
24 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, dierster-0. DOI: 10.1107/S1600536814007673/wm5015sup1.cif

e-70-0o552-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814007673/wm5015Isup2.hkl

e-70-0o552-Isup2.hkl^{(107.9KB, hkl)}

Click here for additional data file.^{(6.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814007673/wm5015Isup3.cml

CCDC reference: 995747

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are grateful for financial support from the National Fundation of China (21261002).

supplementary crystallographic information

1. Comment

In recent years the chemistry of carboxylic compounds has been the subject of intense studies because of the potential applications of these compounds as ligands for metal complexes or of potential applications as luminescent, non-linear optical, electrical conductive and liquid-crystalline materials (Yan et al., 2012. Chanthapally et al., 2012). Esters are also very important since these compounds are commodity chemicals used as intermediates in the manufacture of acids and in the production of numerous important industrial products. Hence, the current work aims to synthesize new esters for acid production and for investigation of their coordination behaviors with metal ions (Ma et al., 2012; Chen & Liu, 2002). Here, we report the crystal structure of a new diester, C₂₀H₂₂O₆, which was obtained by reaction of ethyl 2-hydroxybenzoate with 1,2-dichloroethane.

The structure of C₂₀H₂₂O₆ consists of a neutral molecular unit (Fig. 1). The molecule lies on a twofold rotation axis which passes through the middle of the central ethylene bridge that has a gauche conformation with the corresponding O—C—C—O torsion angle being 73.2 (2) °. All bond lengths and angles are within normal ranges (Allen et al., 1987). The carbon atom of the carboxyl group, and the aryl and O—CH₂ moeities of one half molecule are coplanar with an r.m.s. deviation of 0.01 Å. The two aryl rings form a dihedral angle of 67.94 (4) °. The ester ethyl group is disordered over two sets of sites in a 0.59 (2):0.41 (2) occupancy ratio. The packing of the molecules in the crystal structure is shown in Fig. 2.

2. Experimental

The title compound was obtained by the reaction of ethyl 2- hydroxybenzoate with 1,2-dichloroethane in N,N'- dimethylformamide (DMF) according to a reported procedure (Ma & Liu, 2002). In a 100 cm³ flask fitted with a funnel, ethyl 2- 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 under stirring. The mixture was further stirred for 24 h at 353 K. The solution was concentrated under reduced pressure and the white solid precipitated 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 finally obtained (yield 81 %, m.p: 417–419 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.