Crystal structure of the diglycidyl ether of eugenol.

The diep-oxy monomer, C13H16O4 {DGE-Eu; systematic name: 2-[3-meth-oxy-4-(oxiran-2-ylmeth-oxy)benz-yl]oxirane}, was synthesized from eugenol by a three-step reaction. It consists of a 1,2,4-tris-ubstituted benzene ring substituted by diglycidyl ether, a meth-oxy group and a methyl-oxirane group. The three-membered oxirane rings are inclined to the benzene ring by 61.0 (3) and 27.9 (3)°. The methyl-ene C atom of one of the two terminal epoxide rings is positionally disordered [refined occupancy ratio = 0.69 (1):0.31 (1)]. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming layers parallel to the ab plane. The layers are linked by C-H⋯π inter-actions, forming a three-dimensional network.

Chemical context

The past two decades have witnessed an increasing inter­est in the environmental quest for the replacement of petroleum-based chemicals by monomers from renewable resources. Advances in particular in the catalytic conversion of biomass have led to a wide range of useful platform mol­ecules (Besson et al., 2014 ▸). This sustainable approach is also strongly considered in the field of polymer synthesis (Gandini et al., 2016 ▸). In the specific domain of ep­oxy thermosets, numerous studies have been conducted in order to find alternatives to the diglycidyl ether of bis­phenol A (BADGE), which is the main building-block used for formulation resins (Auvergne et al., 2014 ▸). Classically, the synthetic approach is based on the functionalization of bio-sourced mol­ecules by the grafting of glycidyl ether groups. In this context and in our ongoing studies on the chemical modification of bio-based building blocks for material applications (Mhanna et al., 2014 ▸; Bigot et al., 2016 ▸; François et al., 2016 ▸), we report herein on the synthesis and crystal structure of the diglycidyl ether of eugenol (DGE-Eu), prepared from eugenol in a three-step synthesis (Qin et al., 2014 ▸).

Structural commentary

The title compound (DGE-EU), has an asymmetrical structure, which is depicted in Fig. 1 ▸. It is composed of a benzene ring with three oxygenated functional groups: (i) 2-[(λ1-oxidan­yl)meth­yl]oxirane, (ii) meth­oxy and (iii) 2-methyl­oxirane. While atoms O1, O2 and C11 lie in the plane of the benzene ring, the meth­oxy group (O1/C5/C10) is inclined to the benzene ring by 11.2 (3)°. The two oxirane rings (O3/C8/C9 and O4/C12A/C13) are inclined to the benzene ring by 61.0 (3) and 27.9 (3)°, respectively. The mol­ecule shows disorder with an occupation factor equal to 0.69 (1) for the major component of the methyl­ene group (C12A) of the oxirane ring (C11/C12/O3). Such disorder is commonly observed for diglycidyl ether derivatives (CSD; Groom et al., 2016 ▸).

Figure 1

A view of the mol­ecular structure of the title compound (DGE-Eu), with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The major and minor components of atom C12 (C12A/C12B) are shown.

Supra­molecular features

The crystal packing of DGE-Eu viewed along the c-axis is depicted in Fig. 2 ▸. All oxygen atoms of DGE-Eu are involved in C—H⋯O hydrogen bonds with surrounding mol­ecules, forming layers lying parallel to the ab plane (Fig. 2 ▸ and Table 1 ▸). In addition, the layers are linked C—H⋯π inter­actions, with the C7–H7A group positioned almost orthogonally to the benzene ring, so forming a three-dimensional network (Table 1 ▸ and Fig. 3 ▸).

Figure 2

Crystal packing of DGE-Eu viewed along the c axis, showing the layer-like C—H⋯O hydrogen-bonded network (dashed lines; see Table 1 ▸). Only the major component of atom C12 (C12A) is shown. For clarity, only H atoms H7B, H11C, H12A, H13B and H7A have been included.

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the benzene ring (C1–C6).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O4i	0.99	2.53	3.452 (4)	155
C11—H11C⋯O3ii	0.99	2.43	3.413 (4)	170
C13—H13B⋯O1ii	0.99	2.57	3.358 (4)	136
C12A—H12A⋯O3ii	1.00	2.45	3.177 (5)	129
C7—H7A⋯Cg iii	0.99	2.57	3.465 (4)	150

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 3

Crystal packing of DGE-Eu, viewed along the a axis, showing the layer-like C—H⋯O hydrogen-bonded networks linked by C—H⋯π inter­actions (dashed lines and blue arrows, respectively; see Table 1 ▸). For clarity, only H atoms H7B, H11C, H12A, H13B and H7A (grey ball) have been included. Only the major component of atom C12 (C12A) is shown.

Database survey

To date, and to the best of our knowledge, only nine crystallographic structures comprising diglycidyl ether-substituted benzene ring moieties have been deposited in the Cambridge Structural Database (WebCSD v1.1.2, update 2017-04-05; Groom et al., 2016 ▸). They include 2,2-bis­(3,5-di­bromo-4-hy­droxy­benzene)­propane diglycidyl ether (COMNEX: Saf’yanov et al., 1984 ▸), 2,2-bis­[4-(oxiran-2-ylmeth­oxy)-3,5-di­bromo­phen­yl]propane (COMNEY: Cheban et al., 1985 ▸), diglycidyl ether of bis­phenol A (DGEBPA: Flippen-Anderson & Gilardi, 1980 ▸; DGEBPA01: Heinemann et al., 1993 ▸; DGEBPA10: Flippen-Anderson & Gilardi, 1981 ▸), p-di(2,3-ep­oxy­prop­yloxy)benzene (EOXHQE: Saf’yanov et al., 1977 ▸), 2,2′-[1,3-phenyl­ene-bis­(oxymethyl­ene)]bis­(oxirane) (FITWOU: Bocelli & Grenier-Loustalot, 1987 ▸), 2-(4-{4-[4-(oxiran-2-ylmeth­oxy)phen­oxy]phen­yl}phen­oxy­meth­yl)oxir­ane (LAQTII: Song et al., 2012 ▸) and 10-[2,5-bis­(2,3-ep­oxy-1-prop­oxy)phen­yl]-9-oxa-10-phosphaphenanthren-10-one (LIPSOS: Cho et al., 1999 ▸). In some of these compounds, an ep­oxy ring is disordered, which is also observed for the title compound DGE-Eu. In terms of application, these compounds are used as precursors of thermosetting resins. The polymerization process involving the ep­oxy rings occurs in the presence of amines and acid anhydrides and leads to cross-linked rigid materials.

Synthesis and crystallization

The title compound was prepared from a commercial source of eugenol (Sigma–Aldrich), according to a three-step procedure previously reported in the literature (Qin et al., 2014 ▸). The details of the synthesis of the title compound are summarized in Fig. 4 ▸. Following purification by silica gel column chromatography, colourless prismatic crystals were obtained by slow evaporation of an ethyl acetate solution, and were finally characterized as DGE-Eu.

Figure 4

Reagents and conditions for the synthesis of DGE-Eu from eugenol (Qin et al., 2014 ▸): (i) acetic anhydride, 358 K; (ii) m-chloro­per­oxy­benzoic acid, CH2Cl2, room temperature; (iii) epi­chloro­hydrin, NaOH, C2H5OH, 358 K.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atoms were placed at calculated positions and refined using a riding model: C—H = 0.95–1.00 Å with U iso(H) = 1.5U eq(C-meth­yl) and 1.2U eq(C) for other H atoms. Atom C12 atom of the ep­oxy­propane (oxirane) group (C11/C12/O3) was found to be disordered over two positions with a refined occupancy ratio of 0.69 (1): 0.31 (1) for atoms C12A:C12B.

Table 2

Experimental details

Crystal data
Chemical formula	C13H16O4
M r	236.26
Crystal system, space group	Monoclinic, C c
Temperature (K)	115
a, b, c (Å)	9.8262 (5), 13.4434 (7), 9.4251 (8)
β (°)	109.897 (2)
V (Å3)	1170.71 (13)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.10
Crystal size (mm)	0.4 × 0.35 × 0.3
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.700, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	18897, 2680, 2586
R int	0.021
(sin θ/λ)max (Å−1)	0.650
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.044, 0.121, 1.07
No. of reflections	2680
No. of parameters	160
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.69, −0.28
Absolute structure	Flack x determined using 1234 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	0.20 (18)

Computer programs: APEX2 and SAINT (Bruker, 2014 ▸), SHELXT2015 (Sheldrick, 2015a ▸), SHELXL2015 (Sheldrick, 2015b ▸), OLEX2 (Dolomanov et al., 2009 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017005370/su5360sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017005370/su5360Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989017005370/su5360Isup3.cml

CCDC reference: 1543288

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

C13H16O4	F(000) = 504
Mr = 236.26	Dx = 1.340 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 9992 reflections
a = 9.8262 (5) Å	θ = 2.7–33.0°
b = 13.4434 (7) Å	µ = 0.10 mm−1
c = 9.4251 (8) Å	T = 115 K
β = 109.897 (2)°	Prism, colourless
V = 1170.71 (13) Å3	0.4 × 0.35 × 0.3 mm
Z = 4

Bruker APEXII CCD diffractometer	2680 independent reflections
Radiation source: X-ray tube, Siemens KFF Mo 2K-180	2586 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −12→12
Tmin = 0.700, Tmax = 0.747	k = −17→17
18897 measured reflections	l = −12→12

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)] = 0.044	H-atom parameters constrained
wR(F2) = 0.121	w = 1/[σ2(Fo2) + (0.0641P)2 + 1.3035P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
2680 reflections	Δρmax = 0.69 e Å−3
160 parameters	Δρmin = −0.28 e Å−3
2 restraints	Absolute structure: Flack x determined using 1234 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.20 (18)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.3186 (2)	0.75130 (14)	0.4046 (2)	0.0215 (4)
O2	0.3043 (2)	0.59282 (15)	0.5548 (2)	0.0221 (4)
O3	0.0296 (3)	0.4884 (2)	0.5717 (4)	0.0511 (9)
O4	0.8644 (3)	0.79876 (18)	0.4484 (3)	0.0406 (7)
C1	0.6472 (3)	0.6219 (2)	0.3926 (3)	0.0204 (6)
C2	0.6394 (3)	0.5387 (2)	0.4744 (3)	0.0203 (5)
H2	0.7121	0.4890	0.4925	0.024*
C3	0.5262 (3)	0.5260 (2)	0.5313 (3)	0.0204 (6)
H3	0.5220	0.4677	0.5867	0.025*
C4	0.4203 (3)	0.5984 (2)	0.5068 (3)	0.0169 (5)
C5	0.4272 (3)	0.6842 (2)	0.4242 (3)	0.0171 (5)
C6	0.5397 (3)	0.6949 (2)	0.3680 (3)	0.0187 (5)
H6	0.5441	0.7527	0.3119	0.022*
C7	0.2935 (3)	0.5033 (3)	0.6333 (4)	0.0287 (7)
H7A	0.3828	0.4935	0.7213	0.034*
H7B	0.2807	0.4452	0.5655	0.034*
C8	0.1678 (4)	0.5132 (3)	0.6838 (5)	0.0382 (8)
H8	0.1691	0.5701	0.7526	0.046*
C9	0.0890 (4)	0.4237 (4)	0.6998 (5)	0.0522 (12)
H9A	0.1274	0.3584	0.6826	0.063*
H9B	0.0428	0.4238	0.7782	0.063*
C10	0.3084 (3)	0.8287 (2)	0.2985 (4)	0.0269 (6)
H10A	0.3053	0.7997	0.2020	0.040*
H10B	0.3929	0.8724	0.3366	0.040*
H10C	0.2201	0.8674	0.2839	0.040*
C11	0.7701 (3)	0.6367 (3)	0.3324 (4)	0.0278 (7)
H11A	0.8071	0.5708	0.3159	0.033*	0.690 (11)
H11B	0.7323	0.6706	0.2334	0.033*	0.690 (11)
H11C	0.8536	0.5974	0.3965	0.033*	0.310 (11)
H11D	0.7401	0.6074	0.2299	0.033*	0.310 (11)
C13	0.9712 (4)	0.7691 (2)	0.3826 (4)	0.0324 (7)
H13A	0.9471	0.7781	0.2725	0.039*	0.690 (11)
H13B	1.0745	0.7788	0.4434	0.039*	0.690 (11)
H13C	1.0477	0.7222	0.4401	0.039*	0.310 (11)
H13D	1.0014	0.8187	0.3216	0.039*	0.310 (11)
C12A	0.8911 (4)	0.6954 (3)	0.4331 (5)	0.0203 (11)	0.690 (11)
H12A	0.9476	0.6614	0.5295	0.024*	0.690 (11)
C12B	0.8184 (12)	0.7317 (8)	0.3230 (12)	0.032 (3)*	0.310 (11)
H12B	0.7600	0.7658	0.2274	0.038*	0.310 (11)

	U11	U22	U33	U12	U13	U23
O1	0.0200 (9)	0.0204 (9)	0.0264 (10)	0.0043 (7)	0.0107 (7)	0.0072 (8)
O2	0.0216 (10)	0.0238 (10)	0.0222 (9)	−0.0004 (8)	0.0089 (8)	0.0056 (8)
O3	0.0229 (12)	0.0500 (17)	0.070 (2)	−0.0009 (11)	0.0028 (12)	0.0306 (16)
O4	0.0437 (14)	0.0246 (12)	0.0679 (18)	−0.0074 (10)	0.0379 (13)	−0.0174 (12)
C1	0.0174 (12)	0.0230 (13)	0.0210 (13)	−0.0033 (11)	0.0067 (10)	−0.0078 (11)
C2	0.0186 (12)	0.0202 (12)	0.0194 (12)	0.0029 (10)	0.0029 (10)	−0.0036 (10)
C3	0.0226 (13)	0.0187 (12)	0.0168 (12)	−0.0001 (10)	0.0026 (10)	0.0014 (9)
C4	0.0165 (12)	0.0195 (13)	0.0129 (11)	−0.0036 (9)	0.0026 (10)	0.0003 (9)
C5	0.0160 (11)	0.0170 (12)	0.0167 (11)	0.0005 (9)	0.0035 (9)	−0.0010 (9)
C6	0.0191 (12)	0.0175 (12)	0.0198 (12)	−0.0019 (9)	0.0068 (10)	−0.0008 (9)
C7	0.0218 (14)	0.0326 (16)	0.0299 (15)	0.0008 (12)	0.0067 (11)	0.0146 (13)
C8	0.0330 (17)	0.042 (2)	0.0429 (19)	0.0016 (15)	0.0170 (15)	0.0098 (16)
C9	0.0247 (16)	0.056 (2)	0.075 (3)	0.0001 (16)	0.0159 (18)	0.040 (2)
C10	0.0292 (15)	0.0234 (14)	0.0304 (15)	0.0051 (12)	0.0133 (12)	0.0108 (12)
C11	0.0215 (13)	0.0314 (16)	0.0346 (16)	−0.0047 (12)	0.0146 (12)	−0.0140 (12)
C13	0.0323 (16)	0.0259 (14)	0.049 (2)	−0.0044 (13)	0.0267 (15)	−0.0069 (14)
C12A	0.021 (2)	0.020 (2)	0.023 (2)	0.0008 (15)	0.0118 (16)	−0.0013 (15)

O1—C5	1.361 (3)	C8—H8	1.0000
O1—C10	1.423 (3)	C8—C9	1.467 (5)
O2—C4	1.364 (3)	C9—H9A	0.9900
O2—C7	1.435 (3)	C9—H9B	0.9900
O3—C8	1.447 (5)	C10—H10A	0.9800
O3—C9	1.441 (4)	C10—H10B	0.9800
O4—C13	1.444 (4)	C10—H10C	0.9800
O4—C12A	1.430 (4)	C11—H11A	0.9900
O4—C12B	1.432 (11)	C11—H11B	0.9900
C1—C2	1.374 (4)	C11—H11C	0.9900
C1—C6	1.402 (4)	C11—H11D	0.9900
C1—C11	1.513 (4)	C11—C12A	1.473 (5)
C2—H2	0.9500	C11—C12B	1.375 (12)
C2—C3	1.400 (4)	C13—H13A	0.9900
C3—H3	0.9500	C13—H13B	0.9900
C3—C4	1.386 (4)	C13—H13C	0.9900
C4—C5	1.406 (4)	C13—H13D	0.9900
C5—C6	1.386 (4)	C13—C12A	1.443 (5)
C6—H6	0.9500	C13—C12B	1.499 (12)
C7—H7A	0.9900	C12A—H12A	1.0000
C7—H7B	0.9900	C12B—H12B	1.0000
C7—C8	1.473 (5)
C5—O1—C10	116.4 (2)	O1—C10—H10B	109.5
C4—O2—C7	115.7 (2)	O1—C10—H10C	109.5
C9—O3—C8	61.1 (2)	H10A—C10—H10B	109.5
C12A—O4—C13	60.3 (2)	H10A—C10—H10C	109.5
C12B—O4—C13	62.8 (5)	H10B—C10—H10C	109.5
C2—C1—C6	118.7 (3)	C1—C11—H11A	108.8
C2—C1—C11	121.4 (3)	C1—C11—H11B	108.8
C6—C1—C11	119.9 (3)	C1—C11—H11C	107.6
C1—C2—H2	119.4	C1—C11—H11D	107.6
C1—C2—C3	121.1 (3)	H11A—C11—H11B	107.7
C3—C2—H2	119.4	H11C—C11—H11D	107.0
C2—C3—H3	120.0	C12A—C11—C1	113.6 (3)
C4—C3—C2	120.0 (2)	C12A—C11—H11A	108.8
C4—C3—H3	120.0	C12A—C11—H11B	108.8
O2—C4—C3	124.8 (2)	C12B—C11—C1	118.9 (5)
O2—C4—C5	115.6 (2)	C12B—C11—H11C	107.6
C3—C4—C5	119.6 (2)	C12B—C11—H11D	107.6
O1—C5—C4	115.8 (2)	O4—C13—H13A	117.8
O1—C5—C6	124.7 (2)	O4—C13—H13B	117.8
C6—C5—C4	119.5 (2)	O4—C13—H13C	118.0
C1—C6—H6	119.4	O4—C13—H13D	118.0
C5—C6—C1	121.2 (2)	O4—C13—C12B	58.2 (5)
C5—C6—H6	119.4	H13A—C13—H13B	115.0
O2—C7—H7A	110.1	H13C—C13—H13D	115.1
O2—C7—H7B	110.1	C12A—C13—O4	59.4 (2)
O2—C7—C8	108.0 (3)	C12A—C13—H13A	117.8
H7A—C7—H7B	108.4	C12A—C13—H13B	117.8
C8—C7—H7A	110.1	C12B—C13—H13C	118.0
C8—C7—H7B	110.1	C12B—C13—H13D	118.0
O3—C8—C7	115.2 (3)	O4—C12A—C11	116.8 (3)
O3—C8—H8	116.8	O4—C12A—C13	60.4 (2)
O3—C8—C9	59.3 (2)	O4—C12A—H12A	114.7
C7—C8—H8	116.8	C11—C12A—H12A	114.7
C9—C8—C7	119.3 (4)	C13—C12A—C11	124.5 (4)
C9—C8—H8	116.8	C13—C12A—H12A	114.7
O3—C9—C8	59.7 (2)	O4—C12B—C13	59.0 (5)
O3—C9—H9A	117.8	O4—C12B—H12B	112.2
O3—C9—H9B	117.8	C11—C12B—O4	123.4 (8)
C8—C9—H9A	117.8	C11—C12B—C13	127.6 (8)
C8—C9—H9B	117.8	C11—C12B—H12B	112.2
H9A—C9—H9B	114.9	C13—C12B—H12B	112.2
O1—C10—H10A	109.5
O1—C5—C6—C1	−179.6 (3)	C3—C4—C5—O1	179.6 (2)
O2—C4—C5—O1	0.9 (3)	C3—C4—C5—C6	0.2 (4)
O2—C4—C5—C6	−178.5 (2)	C4—O2—C7—C8	176.7 (3)
O2—C7—C8—O3	83.5 (4)	C4—C5—C6—C1	−0.2 (4)
O2—C7—C8—C9	150.9 (4)	C6—C1—C2—C3	0.6 (4)
O4—C13—C12A—C11	103.8 (4)	C6—C1—C11—C12A	84.8 (4)
O4—C13—C12B—C11	−110.4 (10)	C6—C1—C11—C12B	31.8 (7)
C1—C2—C3—C4	−0.7 (4)	C7—O2—C4—C3	−1.3 (4)
C1—C11—C12A—O4	−69.5 (4)	C7—O2—C4—C5	177.3 (2)
C1—C11—C12A—C13	−140.5 (3)	C7—C8—C9—O3	−103.5 (4)
C1—C11—C12B—O4	54.5 (11)	C9—O3—C8—C7	110.4 (4)
C1—C11—C12B—C13	128.8 (8)	C10—O1—C5—C4	−168.6 (2)
C2—C1—C6—C5	−0.1 (4)	C10—O1—C5—C6	10.8 (4)
C2—C1—C11—C12A	−93.8 (4)	C11—C1—C2—C3	179.3 (2)
C2—C1—C11—C12B	−146.8 (6)	C11—C1—C6—C5	−178.8 (2)
C2—C3—C4—O2	178.8 (2)	C13—O4—C12A—C11	−116.3 (4)
C2—C3—C4—C5	0.3 (4)	C13—O4—C12B—C11	117.2 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O4i	0.99	2.53	3.452 (4)	155
C11—H11C···O3ii	0.99	2.43	3.413 (4)	170
C13—H13B···O1ii	0.99	2.57	3.358 (4)	136
C12A—H12A···O3ii	1.00	2.45	3.177 (5)	129
C7—H7A···Cgiii	0.99	2.57	3.465 (4)	150