Diethyl 4,4′-(3,6-dioxaoctane-1,8-diyl­dioxy)dibenzoate

Abstract

The title compound, C₂₄H₃₀O₈, was obtained by reaction of ethyl 4-hy­droxy­benzoate with 1,2-dichloro­ethane. The mol­ecule occupies a crystallographic inversion center, with its central ethyl­ene bridge in an anti conformation. The other ethyl­ene bridge has a gauche conformation, with the corresponding O—C—C—O torsion angle being 74.2 (1)°. The benzene rings are almost coplanar with the adjacent eth­oxy­carbonyl groups, with an r.m.s. deviation of 0.078 Å.

Related literature  

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

Experimental  

Crystal data  

• C₂₄H₃₀O₈

• M _r = 446.48

• Monoclinic,

• a = 9.2471 (17) Å

• b = 12.530 (2) Å

• c = 13.275 (2) Å

• β = 131.528 (10)°

• V = 1151.5 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 298 K

• 0.46 × 0.41 × 0.39 mm

Data collection  

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.957, T _max = 0.963

• 16767 measured reflections

• 5154 independent reflections

• 2879 reflections with I > 2σ(I)

• R _int = 0.028

Refinement  

• R[F ² > 2σ(F ²)] = 0.051

• wR(F ²) = 0.164

• S = 1.05

• 5154 reflections

• 146 parameters

• H-atom parameters constrained

• Δρ_max = 0.34 e Å⁻³

• Δρ_min = −0.23 e Å⁻³

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: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812004874/ld2043Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

This paper represents a part of our continuing study on the synthesis and structural characterization of dialdehydes and diesters (Ma & Liu, 2002; Ma & Cao, 2011a; Ma & Yang, 2011b). We are interested in utilization of these compounds as precusors for the synthesis of macrocyclic or macrobicyclic compounds, and for manufacturing of different coordination topologies (Chen & Liu 2002) for various applications (Hou & Kan, 2007; Tashiro et al., 1990; Zhang et al., 2007). We report here the X-ray structure of a new diester compound (Fig. 1) along with elemental analysis and IR data. All bond lengths are within normal ranges (Allen et al., 1987). The two aromatic rings are parallel to each other because of the molecular symmetry.

Experimental

The title compound was obtained by the reaction of ethyl 4-hydroxybenzoate with 1,2-bis(2-chloro-ethoxy)ethane in N,N'-dimethylformamide (DMF) in the presence of K₂CO₃ according to a reported procedure (Ma & Liu, 2002; Ma & Cao, 2011; Ma & Yang, 2011). In a 100 cm³ flask fitted with a funnel, ethyl 4-hydroxybenzoate (8.3 g, 50 mM) and potassium carbonate (14 g, 100 mM) were mixed in 50 cm³ of DMF. A stoichiometric quantity of 1,2-bis(2-chloro-ethoxy)ethane (4.7 g, 25 mM) dissolved in 20 cm³ of DMF has been added dropwise to this solution for a period of one hour with continuous 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 80 %, m.p: 337–339 K). Anal. Calcd. for [C₂₄H₃₀O₈](C₂H₆O)_1/2 (%): C, 63.95; H, 7.08; found: C, 64.23; H, 6.87; IR (KBr), (cm^-1): 2938 (w), 1707, (s, C=O), 1606, 1513, 1466 (s, C=C of aryl), 1281, 1253, 1175, 1131, 1106 (CH₂—O—CH₂), 1066, 1048, 1014, 929-653, (Ar—H). 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.

Refinement

All H atoms were positioned geometrically and refined using riding and rotating model with C—H = 0.93 - 0.97 Å, with U_iso(H) = 1.5 times U_eq(C) for methyl H atoms and U_iso(H) = 1.2 times U_eq(C) for all other H atoms.

Figures

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.

Crystal data

C24H30O8	F(000) = 476
Mr = 446.48	Dx = 1.288 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 16767 reflections
a = 9.2471 (17) Å	θ = 2.6–35.5°
b = 12.530 (2) Å	µ = 0.10 mm−1
c = 13.275 (2) Å	T = 298 K
β = 131.528 (10)°	Prism, colorless
V = 1151.5 (3) Å3	0.46 × 0.41 × 0.39 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	5154 independent reflections
Radiation source: fine-focus sealed tube	2879 reflections with I > 2σ(I)
Graphite Monochromator monochromator	Rint = 0.028
Detector resolution: 0 pixels mm-1	θmax = 35.5°, θmin = 2.6°
phi and ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −20→20
Tmin = 0.957, Tmax = 0.963	l = −21→20
16767 measured reflections

Refinement

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0674P)2 + 0.1605P] where P = (Fo2 + 2Fc2)/3
5154 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.82218 (13)	0.56947 (7)	−0.25960 (9)	0.0452 (2)
O2	−0.61141 (15)	0.54988 (8)	−0.28929 (11)	0.0530 (3)
O3	−0.42322 (12)	0.15018 (7)	0.07878 (8)	0.0403 (2)
O4	−0.11518 (12)	0.04803 (7)	0.33477 (8)	0.0406 (2)
C1	−0.68021 (16)	0.51813 (9)	−0.24305 (12)	0.0374 (2)
C2	−0.61826 (15)	0.41940 (9)	−0.16212 (11)	0.0341 (2)
C3	−0.68284 (16)	0.39335 (10)	−0.09580 (12)	0.0379 (2)
H3A	−0.7724	0.4370	−0.1051	0.045*
C4	−0.61502 (17)	0.30326 (10)	−0.01627 (12)	0.0392 (3)
H4A	−0.6582	0.2868	0.0283	0.047*
C5	−0.48191 (15)	0.23687 (9)	−0.00255 (11)	0.0332 (2)
C6	−0.41928 (18)	0.26088 (10)	−0.07013 (13)	0.0418 (3)
H6A	−0.3329	0.2159	−0.0631	0.050*
C7	−0.48635 (18)	0.35259 (10)	−0.14845 (13)	0.0421 (3)
H7A	−0.4423	0.3695	−0.1923	0.051*
C8	−0.27474 (17)	0.08362 (10)	0.10606 (11)	0.0384 (2)
H8A	−0.1616	0.1261	0.1424	0.046*
H8B	−0.3199	0.0500	0.0237	0.046*
C9	−0.22479 (18)	0.00033 (10)	0.20575 (11)	0.0399 (3)
H9A	−0.3420	−0.0305	0.1791	0.048*
H9B	−0.1505	−0.0563	0.2086	0.048*
C10	−0.06051 (19)	−0.02821 (10)	0.43318 (12)	0.0441 (3)
H10A	0.0132	−0.0852	0.4361	0.053*
H10B	−0.1743	−0.0590	0.4119	0.053*
C11	−0.8867 (2)	0.67038 (10)	−0.33238 (13)	0.0460 (3)
H1	−0.7765	0.7084	−0.3088	0.055*
H2	−0.9433	0.7141	−0.3060	0.055*
C12	−1.0324 (2)	0.65276 (11)	−0.48130 (15)	0.0538 (3)
H3	−1.0756	0.7204	−0.5266	0.081*
H4	−1.1405	0.6140	−0.5046	0.081*
H5	−0.9745	0.6126	−0.5082	0.081*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0496 (5)	0.0386 (4)	0.0516 (5)	0.0099 (4)	0.0354 (5)	0.0108 (4)
O2	0.0629 (6)	0.0488 (5)	0.0639 (6)	0.0099 (4)	0.0490 (6)	0.0171 (4)
O3	0.0443 (4)	0.0400 (4)	0.0390 (4)	0.0081 (3)	0.0286 (4)	0.0109 (3)
O4	0.0449 (4)	0.0384 (4)	0.0283 (4)	−0.0018 (3)	0.0200 (4)	0.0060 (3)
C1	0.0387 (5)	0.0340 (5)	0.0365 (6)	0.0004 (4)	0.0237 (5)	0.0012 (4)
C2	0.0342 (5)	0.0336 (5)	0.0318 (5)	−0.0002 (4)	0.0207 (5)	0.0015 (4)
C3	0.0350 (5)	0.0391 (6)	0.0418 (6)	0.0050 (4)	0.0265 (5)	0.0048 (5)
C4	0.0398 (6)	0.0429 (6)	0.0419 (6)	0.0015 (5)	0.0301 (5)	0.0058 (5)
C5	0.0337 (5)	0.0334 (5)	0.0279 (5)	−0.0001 (4)	0.0184 (4)	0.0018 (4)
C6	0.0493 (6)	0.0420 (6)	0.0451 (6)	0.0120 (5)	0.0359 (6)	0.0090 (5)
C7	0.0505 (7)	0.0439 (6)	0.0438 (6)	0.0073 (5)	0.0362 (6)	0.0085 (5)
C8	0.0412 (6)	0.0407 (6)	0.0307 (5)	0.0063 (5)	0.0227 (5)	0.0054 (4)
C9	0.0435 (6)	0.0361 (6)	0.0325 (5)	0.0030 (5)	0.0220 (5)	0.0029 (4)
C10	0.0472 (6)	0.0412 (6)	0.0331 (6)	−0.0003 (5)	0.0220 (5)	0.0096 (5)
C11	0.0531 (7)	0.0315 (6)	0.0506 (7)	0.0063 (5)	0.0333 (6)	0.0033 (5)
C12	0.0563 (8)	0.0441 (7)	0.0519 (8)	0.0086 (6)	0.0320 (7)	0.0073 (6)

Geometric parameters (Å, º)

O1—C1	1.3428 (14)	C6—H6A	0.9300
O1—C11	1.4573 (15)	C7—H7A	0.9300
O2—C1	1.2072 (14)	C8—C9	1.4978 (16)
O3—C5	1.3650 (13)	C8—H8A	0.9700
O3—C8	1.4327 (14)	C8—H8B	0.9700
O4—C10	1.4140 (13)	C9—H9A	0.9700
O4—C9	1.4199 (14)	C9—H9B	0.9700
C1—C2	1.4821 (15)	C10—C10i	1.506 (3)
C2—C7	1.3886 (16)	C10—H10A	0.9700
C2—C3	1.3912 (16)	C10—H10B	0.9700
C3—C4	1.3800 (16)	C11—C12	1.497 (2)
C3—H3A	0.9300	C11—H1	0.9700
C4—C5	1.3939 (16)	C11—H2	0.9700
C4—H4A	0.9300	C12—H3	0.9600
C5—C6	1.3856 (15)	C12—H4	0.9600
C6—C7	1.3896 (17)	C12—H5	0.9600
C1—O1—C11	116.75 (10)	O3—C8—H8B	110.1
C5—O3—C8	118.36 (9)	C9—C8—H8B	110.1
C10—O4—C9	111.23 (9)	H8A—C8—H8B	108.4
O2—C1—O1	123.13 (11)	O4—C9—C8	109.14 (10)
O2—C1—C2	124.26 (11)	O4—C9—H9A	109.9
O1—C1—C2	112.62 (10)	C8—C9—H9A	109.9
C7—C2—C3	118.97 (10)	O4—C9—H9B	109.9
C7—C2—C1	118.80 (10)	C8—C9—H9B	109.9
C3—C2—C1	122.19 (10)	H9A—C9—H9B	108.3
C4—C3—C2	120.53 (10)	O4—C10—C10i	107.61 (12)
C4—C3—H3A	119.7	O4—C10—H10A	110.2
C2—C3—H3A	119.7	C10i—C10—H10A	110.2
C3—C4—C5	120.15 (10)	O4—C10—H10B	110.2
C3—C4—H4A	119.9	C10i—C10—H10B	110.2
C5—C4—H4A	119.9	H10A—C10—H10B	108.5
O3—C5—C6	124.56 (10)	O1—C11—C12	111.23 (11)
O3—C5—C4	115.59 (9)	O1—C11—H1	109.4
C6—C5—C4	119.85 (10)	C12—C11—H1	109.4
C5—C6—C7	119.55 (10)	O1—C11—H2	109.4
C5—C6—H6A	120.2	C12—C11—H2	109.4
C7—C6—H6A	120.2	H1—C11—H2	108.0
C2—C7—C6	120.93 (10)	C11—C12—H3	109.5
C2—C7—H7A	119.5	C11—C12—H4	109.5
C6—C7—H7A	119.5	H3—C12—H4	109.5
O3—C8—C9	108.14 (9)	C11—C12—H5	109.5
O3—C8—H8A	110.1	H3—C12—H5	109.5
C9—C8—H8A	110.1	H4—C12—H5	109.5
C11—O1—C1—O2	−2.72 (18)	C3—C4—C5—C6	−0.70 (18)
C11—O1—C1—C2	177.11 (10)	O3—C5—C6—C7	−178.83 (11)
O2—C1—C2—C7	−6.63 (18)	C4—C5—C6—C7	1.60 (19)
O1—C1—C2—C7	173.54 (10)	C3—C2—C7—C6	0.10 (19)
O2—C1—C2—C3	171.16 (12)	C1—C2—C7—C6	177.96 (11)
O1—C1—C2—C3	−8.67 (16)	C5—C6—C7—C2	−1.3 (2)
C7—C2—C3—C4	0.82 (18)	C5—O3—C8—C9	175.32 (9)
C1—C2—C3—C4	−176.96 (11)	C10—O4—C9—C8	−178.60 (10)
C2—C3—C4—C5	−0.53 (18)	O3—C8—C9—O4	−74.22 (12)
C8—O3—C5—C6	5.50 (17)	C9—O4—C10—C10i	177.97 (13)
C8—O3—C5—C4	−174.91 (10)	C1—O1—C11—C12	83.70 (14)
C3—C4—C5—O3	179.70 (10)

Symmetry code: (i) −x, −y, −z+1.