Diethyl 4,4′-[octane-1,8-diylbis(­oxy)]dibenzoate

Khan, S.S.; Howlader, M.B.H.; Miyatake, R.; Sheikh, M.C.; Zangrando, E.

doi:10.1107/S241431462201080X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 11| November 2022| x221080

https://doi.org/10.1107/S241431462201080X

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Diethyl 4,4′-[octane-1,8-diylbis(oxy)]dibenzoate

Sultana Shakila Khan,^a Md. Belayet Hossain Howlader,^a ^* Ryuta Miyatake,^b Md. Chanmiya Sheikh ^c and Ennio Zangrando ^d

^aDepartment of Chemistry, Rajshahi University, Rajshahi-6205, Bangladesh, ^bCenter for Environmental Conservation and Research Safety, University of Toyama, 3190 Gofuku, Toyama, 930-8555, Japan, ^cDepartment of Applied Science, Faculty of Science, Okayama University of Science, Japan, and ^dDepartment of Chemical and Pharmaceutical Science, University of Trieste, Italy
^*Correspondence e-mail: mbhhowlader@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 9 November 2022; accepted 10 November 2022; online 17 November 2022)

The complete molecule of the title compound, C₂₆H₃₄O₆, is generated by a crystallographic centre of symmetry and the central octyl chain adopts an extended conformation. In the extended structure, weak C—H⋯π interactions link the molecules.

Keywords: crystal structure; ester; ether.

CCDC reference: 2210835

Structure description

Alkylbenzoates possess interesting physical properties and applications in industry. For example, 4-hydroxybenzoic acid and its esters are known as parabens (Giordano et al., 1999 ; Yang et al., 2014 ), and alkylbenzoates are used for preparing liquid crystalline compounds (Abser et al., 1993 ), and non-linear optical materials (Perumal et al., 2002 ). As part of our studies in this area, we now describe the synthesis and structure of the title compound, C₂₆H₃₄O₆ (Fig. 1).

Figure 1
ORTEP view (ellipsoids drawn at the 50% probability level) of the title molecule. C1′ and unlabelled atoms are generated by the symmetry operation −x + 2, −y + 2, −z.

The X-ray diffraction analysis revealed that the title molecule is centrosymmmetric with the inversion center located in the middle of the alkyl chain. The mean plane through the non-hydrogen atoms indicates that they are almost coplanar with r.m.s. and maximum deviations of 0.101 and ±0.151 (2) Å (exhibited by atom C6), respectively. The n-octyl alkyl chain exhibits an extended (all anti) conformation. The bond distances agree with those reported in similar compounds (Ma et al., 2011 , 2012 ; Shi et al., 2014 ). The crystal packing shows the molecules connected by C3—H3A⋯π and C12—H12B⋯π interactions with H–ring centroid separations of 2.89 and 2.82 Å, respectively (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯Cg1ⁱ	0.99	2.89	3.728 (2)	143
C12—H12B⋯Cg1ⁱⁱ	0.99	2.82	3.744 (2)	155
Symmetry codes: (i) x+1, y, z; (ii) .

Figure 2
Detail of the crystal packing showing the C—H⋯π interactions.

Synthesis and crystallization

A mixture of ethyl-4-hydroxybenzoate (8.3 g, 50 mmol) and 1,8-dibromo-octane (6.8 g, 25 mmol) in acetone (100 ml) was refluxed for 24 h over anhydrous potassium carbonate (13.8 g, 100 mmol). The solvent was removed under vacuum and the solid mass was dissolved in water and extracted with dichloromethane. Left overnight, a white precipitate formed, which was filtered off and washed with ethanol. The product was recrystallized from hot ethanol solution, resulting in colorless needle-shaped crystals suitable for X-ray diffraction. Yield: 9.6 g (86%), melting point: 372–373 K.

FT–IR (KBr), (cm⁻¹): 1707 ν (C=O_ester), 1606, 1580 ν (C=C_aromatic), 3072, 3052 ν (C—H_aromatic), 2914, 2942, 2874, 2858 ν (C—H_aliphatic).

¹H NMR (CDCl₃, 400 MHz), δ: 7.99 (d, 2 × 2H, J = 8.8 Hz, C-2,6,2^′,6′), 6.90 (d, 2 × 2H, J = 8.8 Hz, C-3,5,3′,5′), 4.35 (q, 2 × 2H, OCH₂CH₃), 4.0 (t, 2 × 2H, J = 7.6 Hz, OCH₂CH₂), 1.81 (p, 2 × 2H, OCH₂CH₂), 1.5 (p, 2 × 2H, OCH₂CH₂CH₂), 1.41 (p, 2 × 2H, OCH₂CH₂CH₂CH₂), 1.40 (t, 2 × 3H, CH₃).

¹³C NMR (CDCl₃, 400 MHz), δ: 14.47 (2 C, CH₃), 26.00 (2 C, OCH₂CH₂CH₂CH₂), 29.17 (2 C, OCH₂CH₂CH₂), 29.33 (2 C, OCH₂CH₂), 60.67 (2 C, OCH₂CH₂), 68.13 (2 C, OCH₂CH₃), 122.78 (2 C, C-4,4′), 163 (2 C, C-1,1′), 114 (2 × 2 C, C-3,5,3′,5′), 131.59 (2 × 2 C, C-2,6,2′,6′), 166.51 (2 C, OCO)

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₆H₃₄O₆
M_r	442.53
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	6.6734 (5), 9.8044 (8), 10.5156 (7)
α, β, γ (°)	65.804 (5), 89.894 (6), 74.736 (5)
V (Å³)	601.03 (8)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.29 × 0.21 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.506, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	5815, 2739, 2065
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.164, 1.10
No. of reflections	2739
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.26
Computer programs: RAPID-AUTO (Rigaku, 2010 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and DIAMOND (Brandenburg & Putz, 1999 ).

Structural data

CCDC reference: 2210835

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431462201080X/hb4419sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462201080X/hb4419Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431462201080X/hb4419Isup3.cml

checkCIF report

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2010); cell refinement: RAPID-AUTO (Rigaku, 2010); data reduction: RAPID-AUTO (Rigaku, 2010); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 1999).

Diethyl 4,4'-[octane-1,8-diylbis(oxy)]dibenzoate top

Crystal data top

C₂₆H₃₄O₆	Z = 1
M_r = 442.53	F(000) = 238
Triclinic, P1	D_x = 1.223 Mg m⁻³
a = 6.6734 (5) Å	Mo Kα radiation, λ = 0.71075 Å
b = 9.8044 (8) Å	Cell parameters from 4497 reflections
c = 10.5156 (7) Å	θ = 2.4–25.9°
α = 65.804 (5)°	µ = 0.09 mm⁻¹
β = 89.894 (6)°	T = 173 K
γ = 74.736 (5)°	Plate, colorless
V = 601.03 (8) Å³	0.29 × 0.21 × 0.06 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2065 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.030
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
T_min = 0.506, T_max = 0.995	k = −12→12
5815 measured reflections	l = −13→12
2739 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.164	w = 1/[σ²(F_o²) + (0.0845P)² + 0.0881P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2739 reflections	Δρ_max = 0.48 e Å⁻³
146 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.50078 (18)	0.61698 (14)	0.26687 (11)	0.0379 (3)
O2	−0.15521 (19)	0.27118 (15)	0.20288 (12)	0.0448 (4)
O3	−0.13007 (18)	0.21468 (14)	0.43290 (12)	0.0373 (3)
C1	0.9557 (3)	0.95272 (19)	0.06471 (16)	0.0340 (4)
H1A	0.875445	1.023516	0.104138	0.041*
H1B	1.073077	0.875112	0.136554	0.041*
C2	0.8136 (2)	0.86753 (19)	0.03467 (16)	0.0331 (4)
H2A	0.696733	0.944785	−0.037757	0.040*
H2B	0.894056	0.795510	−0.003499	0.040*
C3	0.7246 (3)	0.77505 (19)	0.16506 (16)	0.0341 (4)
H3A	0.841692	0.697379	0.237046	0.041*
H3B	0.645698	0.847111	0.203703	0.041*
C4	0.5820 (3)	0.69140 (19)	0.13702 (16)	0.0335 (4)
H4A	0.466187	0.766566	0.062869	0.040*
H4B	0.660781	0.612463	0.105526	0.040*
C5	0.3632 (2)	0.53601 (18)	0.26868 (16)	0.0306 (4)
C6	0.3009 (3)	0.51230 (19)	0.15451 (16)	0.0338 (4)
H6	0.354087	0.554669	0.067383	0.041*
C7	0.1604 (3)	0.42621 (19)	0.16981 (17)	0.0340 (4)
H7	0.118981	0.409221	0.092424	0.041*
C8	0.0786 (2)	0.36409 (18)	0.29588 (16)	0.0301 (4)
C9	0.1424 (2)	0.38832 (19)	0.40981 (16)	0.0319 (4)
H9	0.088819	0.346062	0.496787	0.038*
C10	0.2826 (3)	0.4731 (2)	0.39638 (16)	0.0339 (4)
H10	0.324872	0.489132	0.474169	0.041*
C11	−0.0794 (2)	0.28025 (18)	0.30258 (17)	0.0328 (4)
C12	−0.2826 (3)	0.1275 (2)	0.45125 (18)	0.0373 (4)
H12A	−0.225921	0.035401	0.431134	0.045*
H12B	−0.413088	0.194284	0.387294	0.045*
C13	−0.3244 (3)	0.0773 (2)	0.60203 (19)	0.0454 (5)
H13A	−0.423756	0.015410	0.620866	0.054*
H13B	−0.383525	0.169814	0.619571	0.054*
H13C	−0.193089	0.014077	0.663841	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0408 (7)	0.0495 (7)	0.0316 (6)	−0.0276 (6)	0.0102 (5)	−0.0163 (5)
O2	0.0479 (8)	0.0588 (8)	0.0391 (7)	−0.0288 (6)	0.0045 (5)	−0.0236 (6)
O3	0.0362 (6)	0.0433 (7)	0.0389 (7)	−0.0228 (5)	0.0073 (5)	−0.0170 (5)
C1	0.0341 (9)	0.0348 (8)	0.0357 (9)	−0.0156 (7)	0.0060 (7)	−0.0141 (7)
C2	0.0322 (8)	0.0345 (8)	0.0354 (9)	−0.0159 (7)	0.0063 (6)	−0.0136 (7)
C3	0.0339 (9)	0.0361 (9)	0.0342 (9)	−0.0152 (7)	0.0060 (6)	−0.0137 (7)
C4	0.0327 (8)	0.0369 (9)	0.0330 (9)	−0.0176 (7)	0.0081 (6)	−0.0123 (7)
C5	0.0274 (8)	0.0324 (8)	0.0323 (8)	−0.0106 (6)	0.0023 (6)	−0.0128 (6)
C6	0.0358 (9)	0.0394 (9)	0.0280 (8)	−0.0151 (7)	0.0074 (6)	−0.0135 (7)
C7	0.0330 (9)	0.0394 (9)	0.0334 (9)	−0.0123 (7)	0.0022 (6)	−0.0181 (7)
C8	0.0273 (8)	0.0303 (8)	0.0335 (9)	−0.0096 (6)	0.0021 (6)	−0.0134 (6)
C9	0.0309 (8)	0.0377 (9)	0.0291 (8)	−0.0146 (7)	0.0061 (6)	−0.0131 (6)
C10	0.0331 (8)	0.0438 (9)	0.0300 (8)	−0.0167 (7)	0.0038 (6)	−0.0171 (7)
C11	0.0297 (8)	0.0322 (8)	0.0380 (9)	−0.0095 (7)	0.0039 (6)	−0.0159 (7)
C12	0.0331 (9)	0.0388 (9)	0.0466 (10)	−0.0186 (7)	0.0071 (7)	−0.0196 (7)
C13	0.0458 (11)	0.0490 (11)	0.0504 (11)	−0.0260 (9)	0.0160 (8)	−0.0223 (8)

Geometric parameters (Å, º) top

O1—C5	1.3581 (18)	C5—C6	1.396 (2)
O1—C4	1.4421 (18)	C5—C10	1.402 (2)
O2—C11	1.2105 (19)	C6—C7	1.386 (2)
O3—C11	1.3403 (19)	C6—H6	0.9500
O3—C12	1.4581 (18)	C7—C8	1.392 (2)
C1—C1ⁱ	1.520 (3)	C7—H7	0.9500
C1—C2	1.527 (2)	C8—C9	1.400 (2)
C1—H1A	0.9900	C8—C11	1.484 (2)
C1—H1B	0.9900	C9—C10	1.378 (2)
C2—C3	1.522 (2)	C9—H9	0.9500
C2—H2A	0.9900	C10—H10	0.9500
C2—H2B	0.9900	C12—C13	1.505 (2)
C3—C4	1.508 (2)	C12—H12A	0.9900
C3—H3A	0.9900	C12—H12B	0.9900
C3—H3B	0.9900	C13—H13A	0.9800
C4—H4A	0.9900	C13—H13B	0.9800
C4—H4B	0.9900	C13—H13C	0.9800

C5—O1—C4	118.70 (12)	C7—C6—H6	120.4
C11—O3—C12	116.54 (12)	C5—C6—H6	120.4
C1ⁱ—C1—C2	113.30 (16)	C6—C7—C8	121.54 (14)
C1ⁱ—C1—H1A	108.9	C6—C7—H7	119.2
C2—C1—H1A	108.9	C8—C7—H7	119.2
C1ⁱ—C1—H1B	108.9	C7—C8—C9	118.79 (14)
C2—C1—H1B	108.9	C7—C8—C11	118.64 (14)
H1A—C1—H1B	107.7	C9—C8—C11	122.51 (14)
C3—C2—C1	112.54 (13)	C10—C9—C8	120.34 (14)
C3—C2—H2A	109.1	C10—C9—H9	119.8
C1—C2—H2A	109.1	C8—C9—H9	119.8
C3—C2—H2B	109.1	C9—C10—C5	120.44 (14)
C1—C2—H2B	109.1	C9—C10—H10	119.8
H2A—C2—H2B	107.8	C5—C10—H10	119.8
C4—C3—C2	113.26 (13)	O2—C11—O3	123.23 (15)
C4—C3—H3A	108.9	O2—C11—C8	124.60 (15)
C2—C3—H3A	108.9	O3—C11—C8	112.17 (13)
C4—C3—H3B	108.9	O3—C12—C13	106.08 (14)
C2—C3—H3B	108.9	O3—C12—H12A	110.5
H3A—C3—H3B	107.7	C13—C12—H12A	110.5
O1—C4—C3	107.07 (12)	O3—C12—H12B	110.5
O1—C4—H4A	110.3	C13—C12—H12B	110.5
C3—C4—H4A	110.3	H12A—C12—H12B	108.7
O1—C4—H4B	110.3	C12—C13—H13A	109.5
C3—C4—H4B	110.3	C12—C13—H13B	109.5
H4A—C4—H4B	108.6	H13A—C13—H13B	109.5
O1—C5—C6	124.62 (14)	C12—C13—H13C	109.5
O1—C5—C10	115.71 (13)	H13A—C13—H13C	109.5
C6—C5—C10	119.67 (14)	H13B—C13—H13C	109.5
C7—C6—C5	119.21 (14)

C1ⁱ—C1—C2—C3	−179.35 (16)	C11—C8—C9—C10	−177.00 (15)
C1—C2—C3—C4	179.44 (14)	C8—C9—C10—C5	−0.1 (2)
C5—O1—C4—C3	178.54 (13)	O1—C5—C10—C9	−179.73 (14)
C2—C3—C4—O1	−176.76 (13)	C6—C5—C10—C9	0.0 (2)
C4—O1—C5—C6	3.3 (2)	C12—O3—C11—O2	0.8 (2)
C4—O1—C5—C10	−176.98 (13)	C12—O3—C11—C8	−179.24 (13)
O1—C5—C6—C7	179.46 (15)	C7—C8—C11—O2	−5.7 (2)
C10—C5—C6—C7	−0.2 (2)	C9—C8—C11—O2	171.73 (16)
C5—C6—C7—C8	0.6 (2)	C7—C8—C11—O3	174.33 (13)
C6—C7—C8—C9	−0.7 (2)	C9—C8—C11—O3	−8.2 (2)
C6—C7—C8—C11	176.84 (14)	C11—O3—C12—C13	−175.71 (14)
C7—C8—C9—C10	0.4 (2)

Symmetry code: (i) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···Cg1ⁱⁱ	0.99	2.89	3.728 (2)	143
C12—H12B···Cg1ⁱⁱⁱ	0.99	2.82	3.744 (2)	155

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

Acknowledgements

MBHH and SSK are grateful to the Department of Chemistry, Rajshahi University for the provision of laboratory facilities. MBHH is indebted to Rajshahi University for financial support. MCS and RM acknowledge the Center for Environmental Conservation and Research Safety, University of Toyama, for providing facilities for single-crystal X-ray analyses.

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