organic compounds
Diethyl 2,2′-(ethane-1,2-diyldioxy)dibenzoate
aSchool of Chemistry and Chemical Engeneering, Guangxi University, Guangxi 530004, People's Republic of China
*Correspondence e-mail: mzmz2009@sohu.com
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.
CCDC reference: 995747
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 see: Chanthapally et al. (2012); Yan et al. (2012).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2002); cell 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.
Supporting information
CCDC reference: 995747
10.1107/S1600536814007673/wm5015sup1.cif
contains datablocks I, dierster-0. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814007673/wm5015Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814007673/wm5015Isup3.cml
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
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.All H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 - 0.97 Å and with Uiso(H) = 1.2 times Ueq(C) or 1.5 times Ueq (methyl C). The two carbon atoms of the ethyl group are disordered over two sets of sites with an occupancy ratio of 0.59 (2):0.41 (2). The C atoms of this group were additionally refined with the ISOR command in SHELXL.
Data collection: SMART (Bruker, 2002); cell
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: SHELXL97 (Sheldrick, 2008).C20H22O6 | F(000) = 760 |
Mr = 358.38 | Dx = 1.248 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 11280 reflections |
a = 21.805 (4) Å | θ = 1.9–27.6° |
b = 9.871 (2) Å | µ = 0.09 mm−1 |
c = 8.8646 (18) Å | T = 298 K |
V = 1908.0 (6) Å3 | Prism, colourless |
Z = 4 | 0.35 × 0.31 × 0.28 mm |
Bruker SMART CCD diffractometer | 2192 independent reflections |
Radiation source: fine-focus sealed tube | 1543 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 0 pixels mm-1 | θmax = 27.6°, θmin = 1.9° |
phi and ω scans | h = −28→27 |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | k = −10→12 |
Tmin = 0.858, Tmax = 1.000 | l = −10→11 |
11280 measured reflections |
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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0606P)2 + 0.335P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2192 reflections | Δρmax = 0.17 e Å−3 |
140 parameters | Δρmin = −0.14 e Å−3 |
24 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: 0.0102 (19) |
C20H22O6 | V = 1908.0 (6) Å3 |
Mr = 358.38 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 21.805 (4) Å | µ = 0.09 mm−1 |
b = 9.871 (2) Å | T = 298 K |
c = 8.8646 (18) Å | 0.35 × 0.31 × 0.28 mm |
Bruker SMART CCD diffractometer | 2192 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1543 reflections with I > 2σ(I) |
Tmin = 0.858, Tmax = 1.000 | Rint = 0.023 |
11280 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 24 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.17 e Å−3 |
2192 reflections | Δρmin = −0.14 e Å−3 |
140 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.36609 (7) | 0.94335 (11) | 0.09160 (14) | 0.0784 (4) | |
O2 | 0.41410 (7) | 0.77861 (13) | −0.03024 (15) | 0.0880 (5) | |
O3 | 0.43658 (5) | 0.59258 (11) | 0.20505 (13) | 0.0632 (3) | |
C1 | 0.38057 (7) | 0.81417 (15) | 0.06775 (17) | 0.0570 (4) | |
C02A | 0.3859 (9) | 1.0477 (15) | −0.0051 (11) | 0.075 (3) | 0.41 (2) |
H02A | 0.4024 | 1.0099 | −0.0976 | 0.090* | 0.41 (2) |
H02B | 0.3518 | 1.1066 | −0.0307 | 0.090* | 0.41 (2) |
C02B | 0.4008 (7) | 1.0397 (13) | −0.0105 (13) | 0.114 (4) | 0.59 (2) |
H02C | 0.4421 | 1.0064 | −0.0273 | 0.137* | 0.59 (2) |
H02D | 0.3804 | 1.0466 | −0.1074 | 0.137* | 0.59 (2) |
C2 | 0.34747 (7) | 0.72278 (14) | 0.17329 (15) | 0.0522 (4) | |
C01A | 0.4309 (8) | 1.120 (2) | 0.0708 (15) | 0.127 (4) | 0.41 (2) |
H01A | 0.4127 | 1.1683 | 0.1536 | 0.191* | 0.41 (2) |
H01B | 0.4497 | 1.1835 | 0.0029 | 0.191* | 0.41 (2) |
H01C | 0.4614 | 1.0587 | 0.1084 | 0.191* | 0.41 (2) |
C01B | 0.4030 (7) | 1.1719 (7) | 0.0618 (8) | 0.119 (3) | 0.59 (2) |
H01D | 0.3620 | 1.2059 | 0.0738 | 0.179* | 0.59 (2) |
H01E | 0.4262 | 1.2333 | 0.0004 | 0.179* | 0.59 (2) |
H01F | 0.4220 | 1.1637 | 0.1590 | 0.179* | 0.59 (2) |
C3 | 0.28631 (8) | 0.74645 (17) | 0.20651 (18) | 0.0654 (4) | |
H3A | 0.2668 | 0.8215 | 0.1650 | 0.078* | |
C4 | 0.25382 (8) | 0.6610 (2) | 0.3000 (2) | 0.0766 (5) | |
H4A | 0.2126 | 0.6773 | 0.3198 | 0.092* | |
C5 | 0.28283 (8) | 0.55161 (18) | 0.3634 (2) | 0.0730 (5) | |
H5A | 0.2611 | 0.4946 | 0.4275 | 0.088* | |
C6 | 0.34359 (7) | 0.52495 (15) | 0.33381 (19) | 0.0634 (4) | |
H6A | 0.3627 | 0.4505 | 0.3778 | 0.076* | |
C7 | 0.37642 (7) | 0.60994 (14) | 0.23769 (16) | 0.0518 (4) | |
C8 | 0.46777 (7) | 0.48215 (15) | 0.27597 (19) | 0.0609 (4) | |
H8A | 0.4482 | 0.3972 | 0.2493 | 0.073* | |
H8B | 0.4662 | 0.4922 | 0.3848 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1251 (11) | 0.0471 (6) | 0.0631 (7) | 0.0001 (6) | 0.0089 (7) | 0.0031 (5) |
O2 | 0.1222 (11) | 0.0685 (8) | 0.0732 (8) | 0.0098 (7) | 0.0363 (8) | 0.0084 (6) |
O3 | 0.0597 (6) | 0.0607 (6) | 0.0692 (7) | 0.0009 (5) | 0.0008 (5) | 0.0183 (5) |
C1 | 0.0753 (9) | 0.0505 (8) | 0.0451 (7) | 0.0019 (7) | −0.0047 (7) | −0.0018 (6) |
C02A | 0.128 (7) | 0.054 (4) | 0.043 (3) | −0.014 (4) | −0.014 (4) | 0.008 (3) |
C02B | 0.174 (9) | 0.065 (4) | 0.104 (6) | −0.006 (4) | 0.034 (5) | 0.020 (4) |
C2 | 0.0654 (9) | 0.0485 (7) | 0.0425 (7) | −0.0015 (6) | −0.0024 (6) | −0.0060 (6) |
C01A | 0.146 (10) | 0.103 (9) | 0.133 (7) | −0.059 (7) | 0.022 (6) | 0.010 (7) |
C01B | 0.228 (10) | 0.057 (3) | 0.073 (3) | −0.031 (4) | −0.001 (4) | 0.003 (2) |
C3 | 0.0717 (10) | 0.0647 (9) | 0.0597 (9) | 0.0118 (8) | 0.0008 (8) | −0.0057 (8) |
C4 | 0.0655 (10) | 0.0869 (12) | 0.0774 (12) | −0.0004 (9) | 0.0129 (9) | −0.0070 (10) |
C5 | 0.0767 (11) | 0.0687 (10) | 0.0735 (11) | −0.0147 (9) | 0.0173 (9) | 0.0001 (9) |
C6 | 0.0733 (10) | 0.0530 (8) | 0.0640 (9) | −0.0065 (7) | 0.0039 (8) | 0.0054 (7) |
C7 | 0.0580 (8) | 0.0487 (7) | 0.0488 (8) | −0.0043 (6) | −0.0011 (6) | −0.0018 (6) |
C8 | 0.0677 (8) | 0.0487 (8) | 0.0662 (9) | −0.0034 (7) | −0.0087 (7) | 0.0060 (7) |
O1—C1 | 1.3306 (18) | C01A—H01B | 0.9600 |
O1—C02A | 1.408 (14) | C01A—H01C | 0.9600 |
O1—C02B | 1.516 (14) | C01B—H01D | 0.9600 |
O2—C1 | 1.1884 (19) | C01B—H01E | 0.9600 |
O3—C7 | 1.3541 (18) | C01B—H01F | 0.9600 |
O3—C8 | 1.4304 (17) | C3—C4 | 1.379 (2) |
C1—C2 | 1.487 (2) | C3—H3A | 0.9300 |
C02A—C01A | 1.39 (2) | C4—C5 | 1.372 (3) |
C02A—H02A | 0.9700 | C4—H4A | 0.9300 |
C02A—H02B | 0.9700 | C5—C6 | 1.376 (2) |
C02B—C01B | 1.455 (15) | C5—H5A | 0.9300 |
C02B—H02C | 0.9700 | C6—C7 | 1.394 (2) |
C02B—H02D | 0.9700 | C6—H6A | 0.9300 |
C2—C3 | 1.386 (2) | C8—C8i | 1.479 (3) |
C2—C7 | 1.402 (2) | C8—H8A | 0.9700 |
C01A—H01A | 0.9600 | C8—H8B | 0.9700 |
C1—O1—C02A | 122.1 (7) | C02B—C01B—H01F | 109.5 |
C1—O1—C02B | 112.8 (5) | H01D—C01B—H01F | 109.5 |
C02A—O1—C02B | 12.6 (12) | H01E—C01B—H01F | 109.5 |
C7—O3—C8 | 117.59 (11) | C4—C3—C2 | 121.27 (16) |
O2—C1—O1 | 123.04 (15) | C4—C3—H3A | 119.4 |
O2—C1—C2 | 125.41 (14) | C2—C3—H3A | 119.4 |
O1—C1—C2 | 111.49 (13) | C5—C4—C3 | 119.41 (16) |
C01A—C02A—O1 | 107.4 (10) | C5—C4—H4A | 120.3 |
C01A—C02A—H02A | 110.2 | C3—C4—H4A | 120.3 |
O1—C02A—H02A | 110.2 | C4—C5—C6 | 121.09 (16) |
C01A—C02A—H02B | 110.2 | C4—C5—H5A | 119.5 |
O1—C02A—H02B | 110.2 | C6—C5—H5A | 119.5 |
H02A—C02A—H02B | 108.5 | C5—C6—C7 | 119.74 (15) |
C01B—C02B—O1 | 108.4 (10) | C5—C6—H6A | 120.1 |
C01B—C02B—H02C | 110.0 | C7—C6—H6A | 120.1 |
O1—C02B—H02C | 110.0 | O3—C7—C6 | 123.51 (13) |
C01B—C02B—H02D | 110.0 | O3—C7—C2 | 116.73 (12) |
O1—C02B—H02D | 110.0 | C6—C7—C2 | 119.73 (14) |
H02C—C02B—H02D | 108.4 | O3—C8—C8i | 108.37 (12) |
C3—C2—C7 | 118.74 (14) | O3—C8—H8A | 110.0 |
C3—C2—C1 | 119.91 (13) | C8i—C8—H8A | 110.0 |
C7—C2—C1 | 121.32 (13) | O3—C8—H8B | 110.0 |
C02B—C01B—H01D | 109.5 | C8i—C8—H8B | 110.0 |
C02B—C01B—H01E | 109.5 | H8A—C8—H8B | 108.4 |
H01D—C01B—H01E | 109.5 | ||
C02A—O1—C1—O2 | 4.9 (7) | C1—C2—C3—C4 | 177.81 (15) |
C02B—O1—C1—O2 | −4.7 (6) | C2—C3—C4—C5 | 1.1 (3) |
C02A—O1—C1—C2 | −172.4 (7) | C3—C4—C5—C6 | −0.8 (3) |
C02B—O1—C1—C2 | 177.9 (6) | C4—C5—C6—C7 | −0.1 (3) |
C1—O1—C02A—C01A | −107.6 (14) | C8—O3—C7—C6 | −1.2 (2) |
C02B—O1—C02A—C01A | −63 (4) | C8—O3—C7—C2 | 176.78 (13) |
C1—O1—C02B—C01B | −156.1 (10) | C5—C6—C7—O3 | 178.61 (15) |
C02A—O1—C02B—C01B | 64 (4) | C5—C6—C7—C2 | 0.7 (2) |
O2—C1—C2—C3 | −136.02 (18) | C3—C2—C7—O3 | −178.45 (13) |
O1—C1—C2—C3 | 41.24 (19) | C1—C2—C7—O3 | 3.3 (2) |
O2—C1—C2—C7 | 42.3 (2) | C3—C2—C7—C6 | −0.4 (2) |
O1—C1—C2—C7 | −140.48 (14) | C1—C2—C7—C6 | −178.72 (13) |
C7—C2—C3—C4 | −0.5 (2) | C7—O3—C8—C8i | 179.76 (14) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C20H22O6 |
Mr | 358.38 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 298 |
a, b, c (Å) | 21.805 (4), 9.871 (2), 8.8646 (18) |
V (Å3) | 1908.0 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.31 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.858, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11280, 2192, 1543 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.132, 1.04 |
No. of reflections | 2192 |
No. of parameters | 140 |
No. of restraints | 24 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.14 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors are grateful for financial support from the National Fundation of China (21261002).
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.