Crystal structure of (E)-4,4′-(but-2-ene-1,4-di­yl)bis­(2-meth­oxy­phenol)

Abstract

The title compound, C₁₈H₂₀O₄, was synthesized via the ruthenium-catalyzed alkene methathesis dimerization of eugenol. The whole mol­ecule is generated by inversion symmetry; the center of inversion being located at the mid-point of the trans C=C bond. The phenol ring is inclined to the mean plane of the central C—C=C—C unit (r.m.s. deviation = 0.014 Å) by 68.83 (16)°. In the crystal, mol­ecules are linked via O—H⋯O hydrogen bonds, involving the hy­droxy and meth­oxy groups, forming undulating sheets parallel to (010).

Related literature  

For a general review of alkene metathesis catalyzed by ruthenium carbenes, see: Grubbs (2004 ▸). For the second generation Grubbs ruthenium carbene catalyst, see: Scholl et al. (1999 ▸). For the synthesis of the title compound, see: Taber & Frankowski (2006 ▸).

Experimental  

Crystal data  

• C₁₈H₂₀O₄

• M _r = 300.34

• Orthorhombic,

• a = 4.8846 (2) Å

• b = 10.7002 (4) Å

• c = 29.5666 (11) Å

• V = 1545.33 (10) ų

• Z = 4

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 198 K

• 0.6 × 0.55 × 0.2 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.927, T _max = 1.000

• 25610 measured reflections

• 1352 independent reflections

• 1199 reflections with I > 2σ(I)

• R _int = 0.036

Refinement  

• R[F ² > 2σ(F ²)] = 0.033

• wR(F ²) = 0.096

• S = 1.05

• 1352 reflections

• 105 parameters

• H-atom parameters constrained

• Δρ_max = 0.16 e Å⁻³

• Δρ_min = −0.13 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: OLEX2.

Supplementary Material

CCDC reference: 1406832

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O8H8O1i	0.78(2)	2.57(2)	3.1784(13)	136(1)

Symmetry code: (i) .

supplementary crystallographic information

S1. Synthesis and crystallization

The title compound was prepared from eugenol by alkene metathesis dimerization using the second generation Grubbs ruthenium carbene catalyst (Scholl et al., 1999) as described previously (Taber & Frankowski, 2006).

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydroxyl H atom was located in a difference Fourier map and refined with U_iso(H) = 1.2U_eq(O). The C-bound H atoms were positioned geometrically and constrained to ride on their parent atoms: C—H = 0.95 - 1.0 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq (C) for other H atoms.

Figures

Fig. 1.

A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by inversion symmetry (symmetry code: -x + 1, -y + 2, -z).

Fig. 2.

A view along the a axis of the crystal packing of the title compound, with hydrogen bonds shown as dashed lines (see Table 1 for details). C-bound H atoms have been omitted for clarity.

Crystal data

C18H20O4	Dx = 1.291 Mg m−3
Mr = 300.34	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9944 reflections
a = 4.8846 (2) Å	θ = 2.8–24.8°
b = 10.7002 (4) Å	µ = 0.09 mm−1
c = 29.5666 (11) Å	T = 198 K
V = 1545.33 (10) Å3	Plate, colorless
Z = 4	0.6 × 0.55 × 0.2 mm
F(000) = 640

Data collection

Bruker APEXII CCD diffractometer	1199 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
φ and ω scans	θmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
Tmin = 0.927, Tmax = 1.000	k = −12→12
25610 measured reflections	l = −35→35
1352 independent reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.033	H-atom parameters constrained
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0476P)2 + 0.352P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
1352 reflections	Δρmax = 0.16 e Å−3
105 parameters	Δρmin = −0.13 e Å−3
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.009 (3)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.3753 (2)	0.94521 (9)	0.20535 (3)	0.0531 (3)
C1	0.1882 (3)	1.04703 (13)	0.20379 (5)	0.0505 (4)
H1A	0.2599	1.1120	0.1837	0.076*
H1B	0.1646	1.0815	0.2343	0.076*
H1C	0.0111	1.0178	0.1924	0.076*
C2	0.4437 (3)	0.88991 (11)	0.16499 (4)	0.0395 (3)
C3	0.3285 (3)	0.91684 (12)	0.12337 (4)	0.0454 (3)
H3	0.1922	0.9798	0.1211	0.054*
C4	0.4108 (3)	0.85237 (13)	0.08473 (4)	0.0475 (4)
C5	0.2924 (3)	0.88644 (16)	0.03888 (4)	0.0605 (4)
H5A	0.3136	0.8146	0.0181	0.073*
H5B	0.0941	0.9035	0.0422	0.073*
C6	0.4294 (3)	0.99880 (15)	0.01871 (4)	0.0554 (4)
H6	0.4116	1.0754	0.0347	0.066*
C7	0.6459 (3)	0.79875 (11)	0.16851 (4)	0.0419 (3)
O8	0.7636 (2)	0.77137 (10)	0.20946 (3)	0.0556 (3)
H8	0.699 (3)	0.8143 (16)	0.2278 (6)	0.067*
C9	0.6067 (3)	0.76024 (14)	0.08901 (4)	0.0552 (4)
H9	0.6619	0.7143	0.0631	0.066*
C10	0.7244 (3)	0.73365 (14)	0.13057 (5)	0.0536 (4)
H10	0.8598	0.6702	0.1329	0.064*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0688 (7)	0.0527 (6)	0.0378 (5)	0.0162 (5)	−0.0078 (4)	−0.0042 (4)
C1	0.0538 (8)	0.0470 (8)	0.0505 (8)	0.0073 (6)	0.0032 (6)	−0.0004 (6)
C2	0.0455 (7)	0.0381 (6)	0.0349 (6)	−0.0030 (5)	−0.0011 (5)	0.0016 (5)
C3	0.0491 (8)	0.0459 (7)	0.0413 (7)	0.0003 (6)	−0.0055 (5)	0.0057 (6)
C4	0.0534 (8)	0.0541 (8)	0.0349 (7)	−0.0139 (7)	−0.0006 (5)	0.0057 (5)
C5	0.0676 (10)	0.0772 (10)	0.0368 (7)	−0.0170 (8)	−0.0082 (6)	0.0073 (6)
C6	0.0660 (10)	0.0653 (9)	0.0348 (6)	−0.0031 (8)	−0.0081 (6)	0.0054 (6)
C7	0.0456 (7)	0.0415 (7)	0.0386 (6)	−0.0018 (5)	−0.0004 (5)	0.0071 (5)
O8	0.0644 (7)	0.0597 (6)	0.0426 (6)	0.0163 (5)	−0.0077 (5)	0.0057 (4)
C9	0.0643 (9)	0.0621 (9)	0.0393 (7)	−0.0016 (7)	0.0112 (6)	−0.0037 (6)
C10	0.0564 (8)	0.0544 (8)	0.0500 (8)	0.0109 (7)	0.0084 (6)	0.0038 (6)

Geometric parameters (Å, º)

O1—C1	1.4228 (16)	C5—H5A	0.9900
O1—C2	1.3732 (15)	C5—H5B	0.9900
C1—H1A	0.9800	C5—C6	1.500 (2)
C1—H1B	0.9800	C6—C6i	1.304 (3)
C1—H1C	0.9800	C6—H6	0.9500
C2—C3	1.3834 (17)	C7—O8	1.3720 (15)
C2—C7	1.3921 (18)	C7—C10	1.3751 (19)
C3—H3	0.9500	O8—H8	0.777 (17)
C3—C4	1.3938 (18)	C9—H9	0.9500
C4—C5	1.5183 (17)	C9—C10	1.386 (2)
C4—C9	1.380 (2)	C10—H10	0.9500
C2—O1—C1	117.26 (10)	H5A—C5—H5B	107.9
O1—C1—H1A	109.5	C6—C5—C4	112.18 (12)
O1—C1—H1B	109.5	C6—C5—H5A	109.2
O1—C1—H1C	109.5	C6—C5—H5B	109.2
H1A—C1—H1B	109.5	C5—C6—H6	116.9
H1A—C1—H1C	109.5	C6i—C6—C5	126.11 (19)
H1B—C1—H1C	109.5	C6i—C6—H6	116.9
O1—C2—C3	125.76 (12)	O8—C7—C2	120.87 (11)
O1—C2—C7	114.17 (10)	O8—C7—C10	119.65 (12)
C3—C2—C7	120.07 (11)	C10—C7—C2	119.46 (11)
C2—C3—H3	119.7	C7—O8—H8	108.7 (13)
C2—C3—C4	120.59 (13)	C4—C9—H9	119.5
C4—C3—H3	119.7	C4—C9—C10	121.05 (12)
C3—C4—C5	120.21 (13)	C10—C9—H9	119.5
C9—C4—C3	118.58 (12)	C7—C10—C9	120.23 (13)
C9—C4—C5	121.19 (13)	C7—C10—H10	119.9
C4—C5—H5A	109.2	C9—C10—H10	119.9
C4—C5—H5B	109.2
O1—C2—C3—C4	−178.58 (12)	C3—C2—C7—C10	−1.74 (19)
O1—C2—C7—O8	−1.02 (18)	C3—C4—C5—C6	80.50 (17)
O1—C2—C7—C10	177.67 (12)	C3—C4—C9—C10	−1.4 (2)
C1—O1—C2—C3	−6.20 (19)	C4—C5—C6—C6i	116.9 (2)
C1—O1—C2—C7	174.44 (11)	C4—C9—C10—C7	0.4 (2)
C2—C3—C4—C5	−177.32 (12)	C5—C4—C9—C10	176.73 (13)
C2—C3—C4—C9	0.8 (2)	C7—C2—C3—C4	0.75 (19)
C2—C7—C10—C9	1.2 (2)	O8—C7—C10—C9	179.89 (13)
C3—C2—C7—O8	179.57 (12)	C9—C4—C5—C6	−97.55 (17)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O1ii	0.78 (2)	2.57 (2)	3.1784 (13)	136 (1)

Symmetry code: (ii) x+1/2, y, −z+1/2.