4-[(E)-4-Hydroxybut-2-en-1-yl]-2-methoxyphenol

Knight, K.S.; Orick, M.C.

doi:10.1107/S2414314616009366

organic compounds

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doi:10.1107/S2414314616009366

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4-[(E)-4-Hydroxybut-2-en-1-yl]-2-methoxyphenol

Kyle S. Knight ^a ^* and Michael C. Orick ^a

^aDepartment of Chemistry and Physics, The University of Tennessee at Chattanooga, Chattanooga, TN, 37403, USA
^*Correspondence e-mail: kyle-knight@utc.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 19 May 2016; accepted 9 June 2016; online 17 June 2016)

The title compound, C₁₁H₁₄O₃, was synthesized by a cross-metathesis reaction. The dihedral angle between the aromatic ring and the butenol side chain is 30.2 (2)°. In the crystal, inversion dimers are formed through O—H⋯O hydrogen bonds and these are linked into chains by additional O—H⋯O contacts. These chains are linked into sheets in the bc plane by C—H⋯O hydrogen bonds.

Keywords: crystal structure; alkene metathesis; hydrogen bonding.

CCDC reference: 1484314

Structure description

The title compound (Fig. 1) was synthesized by the cross-metathesis (Scholl, et al. 1999 ) of eugenol and cis-2-butene-1,4-diol, as previously described (Taber & Frankowski, 2006 ). This compound is a natural product that can also be isolated from the rhizomes of Zingiber cassumunar (Masuda & Jitoe, 1995 ).

Figure 1
A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

The dihedral angle between the aromatic ring and the butenol side chain is 30.2 (2)°. The methyl group of the methoxy-substituent is twisted out of the plane of the aromatic ring by 6.8 (2)°. In the crystal, the unit cell contains inversion dimers connected by hydrogen bonding. Each phenol hydroxyl group acts as a hydrogen-bond donor to the allylic hydroxyl in its dimeric counterpart through O1—H1⋯O2 hydrogen bonds (Table 1 and Fig. 2). The allylic hydroxyl group is a bifurcated donor, forming O2—H2⋯O1 and O2—H2⋯O3 hydrogen bonds that link the dimers into supramolecular chains propagated along the c-axis direction. Chains of dimers are linked by C7–H7⋯O3 hydrogen bonds forming sheets of molecules in the bc plane

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.84	1.80 (1)	2.635 (2)	174 (2)
Symmetry code: (i) -x+1, -y+2, -z+1.

Figure 2
Crystal packing of the title compound, viewed along the a axis with hydrogen bonds drawn as dashed lines.

Synthesis and crystallization

The Grubbs second-generation catalyst, tricyclohexylphosphine[1,3-bis-(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][benzylidene]ruthenium(IV) dichloride (Grubbs, 2004 ), was used to facilitate the cross metathesis of eugenol with cis-1,4-butenediol, to form the title compound. The product was mpurified by column chromatography, and allowed to crystallize from dichloromethane at room temperature over the course of 14 days.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₄O₃
M_r	194.22
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	200
a, b, c (Å)	5.7659 (11), 8.5396 (17), 10.804 (2)
α, β, γ (°)	81.579 (6), 88.020 (6), 71.167 (6)
V (Å³)	498.03 (17)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.6 × 0.4 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	9408, 1736, 1487
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.114, 1.07
No. of reflections	1736
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.18
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1484314

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616009366/sj4039sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616009366/sj4039Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616009366/sj4039Isup3.cdx

Supporting information file. DOI: 10.1107/S2414314616009366/sj4039Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (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 (Dolomanov et al., 2009).

4-[(E)-4-Hydroxybut-2-en-1-yl]-2-methoxyphenol top

Crystal data top

C₁₁H₁₄O₃	Z = 2
M_r = 194.22	F(000) = 208
Triclinic, P1	D_x = 1.295 Mg m⁻³
a = 5.7659 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5396 (17) Å	Cell parameters from 3014 reflections
c = 10.804 (2) Å	θ = 2.5–24.8°
α = 81.579 (6)°	µ = 0.09 mm⁻¹
β = 88.020 (6)°	T = 200 K
γ = 71.167 (6)°	Plate, colorless
V = 498.03 (17) Å³	0.6 × 0.4 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.042
Graphite monochromator	θ_max = 25.0°, θ_min = 3.0°
φ and ω scans	h = −6→6
9408 measured reflections	k = −10→10
1736 independent reflections	l = −12→12
1487 reflections with I > 2σ(I)

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.044P)² + 0.2128P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1736 reflections	Δρ_max = 0.49 e Å⁻³
130 parameters	Δρ_min = −0.18 e Å⁻³

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	0.6301 (2)	0.80940 (16)	0.11536 (11)	0.0390 (4)
H1	0.6644	0.8981	0.1139	0.058*
O2	0.2842 (3)	0.90321 (18)	0.90202 (13)	0.0513 (4)
H2	0.3365	0.8367	0.9679	0.077*
O3	0.3545 (2)	0.62145 (15)	0.11605 (11)	0.0369 (3)
C1	0.5208 (3)	0.7770 (2)	0.22611 (16)	0.0306 (4)
C2	0.5516 (3)	0.8357 (2)	0.33455 (16)	0.0335 (4)
H2A	0.6563	0.9017	0.3353	0.040*
C3	0.4301 (3)	0.7991 (2)	0.44320 (16)	0.0336 (4)
H3	0.4542	0.8394	0.5176	0.040*
C4	0.2748 (3)	0.7049 (2)	0.44395 (16)	0.0304 (4)
C5	0.1392 (3)	0.6612 (2)	0.56028 (16)	0.0356 (4)
H5A	−0.0142	0.6465	0.5337	0.043*
H5B	0.2414	0.5527	0.6055	0.043*
C6	0.0766 (3)	0.7860 (2)	0.64830 (17)	0.0377 (5)
H6	−0.0171	0.8977	0.6168	0.045*
C7	0.1425 (4)	0.7521 (2)	0.76809 (18)	0.0402 (5)
H7	0.2404	0.6412	0.7990	0.048*
C8	0.0739 (4)	0.8755 (3)	0.85676 (19)	0.0467 (5)
H8A	−0.0388	0.9824	0.8144	0.056*
H8B	−0.0137	0.8345	0.9281	0.056*
C9	0.3699 (3)	0.6775 (2)	0.22712 (15)	0.0299 (4)
C10	0.2208 (4)	0.5064 (2)	0.11609 (19)	0.0418 (5)
H10A	0.2849	0.4120	0.1827	0.063*
H10B	0.2388	0.4653	0.0351	0.063*
H10C	0.0470	0.5630	0.1305	0.063*
C11	0.2463 (3)	0.6443 (2)	0.33454 (16)	0.0315 (4)
H11	0.1405	0.5792	0.3337	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0481 (8)	0.0432 (8)	0.0330 (7)	−0.0256 (6)	0.0103 (6)	−0.0055 (6)
O2	0.0763 (11)	0.0483 (9)	0.0362 (8)	−0.0328 (8)	−0.0110 (7)	0.0048 (6)
O3	0.0461 (8)	0.0439 (7)	0.0273 (7)	−0.0233 (6)	0.0004 (5)	−0.0059 (5)
C1	0.0304 (9)	0.0308 (9)	0.0289 (9)	−0.0100 (7)	0.0027 (7)	0.0003 (7)
C2	0.0335 (10)	0.0345 (9)	0.0370 (10)	−0.0173 (8)	0.0014 (8)	−0.0049 (8)
C3	0.0365 (10)	0.0357 (10)	0.0299 (9)	−0.0124 (8)	−0.0010 (7)	−0.0062 (7)
C4	0.0307 (9)	0.0286 (9)	0.0292 (9)	−0.0074 (7)	0.0002 (7)	−0.0005 (7)
C5	0.0383 (10)	0.0371 (10)	0.0311 (10)	−0.0144 (8)	0.0024 (8)	0.0009 (7)
C6	0.0399 (11)	0.0382 (10)	0.0352 (10)	−0.0145 (8)	0.0069 (8)	−0.0029 (8)
C7	0.0421 (11)	0.0381 (10)	0.0419 (11)	−0.0172 (9)	0.0061 (9)	−0.0017 (8)
C8	0.0560 (13)	0.0495 (12)	0.0371 (11)	−0.0218 (10)	0.0066 (9)	−0.0049 (9)
C9	0.0321 (9)	0.0283 (9)	0.0280 (9)	−0.0092 (7)	−0.0023 (7)	−0.0012 (7)
C10	0.0447 (11)	0.0472 (11)	0.0427 (11)	−0.0249 (9)	−0.0008 (9)	−0.0123 (9)
C11	0.0326 (10)	0.0319 (9)	0.0318 (9)	−0.0144 (8)	−0.0004 (7)	−0.0003 (7)

Geometric parameters (Å, º) top

O1—H1	0.8400	C5—H5A	0.9900
O1—C1	1.367 (2)	C5—H5B	0.9900
O2—H2	0.8400	C5—C6	1.481 (3)
O2—C8	1.424 (3)	C6—H6	0.9500
O3—C9	1.371 (2)	C6—C7	1.325 (3)
O3—C10	1.431 (2)	C7—H7	0.9500
C1—C2	1.378 (3)	C7—C8	1.478 (3)
C1—C9	1.397 (2)	C8—H8A	0.9900
C2—H2A	0.9500	C8—H8B	0.9900
C2—C3	1.394 (2)	C9—C11	1.383 (2)
C3—H3	0.9500	C10—H10A	0.9800
C3—C4	1.383 (3)	C10—H10B	0.9800
C4—C5	1.521 (2)	C10—H10C	0.9800
C4—C11	1.392 (2)	C11—H11	0.9500

C1—O1—H1	109.5	C7—C6—H6	117.8
C8—O2—H2	109.5	C6—C7—H7	117.8
C9—O3—C10	116.99 (14)	C6—C7—C8	124.33 (19)
O1—C1—C2	124.05 (16)	C8—C7—H7	117.8
O1—C1—C9	116.82 (15)	O2—C8—C7	111.23 (18)
C2—C1—C9	119.13 (16)	O2—C8—H8A	109.4
C1—C2—H2A	119.8	O2—C8—H8B	109.4
C1—C2—C3	120.46 (16)	C7—C8—H8A	109.4
C3—C2—H2A	119.8	C7—C8—H8B	109.4
C2—C3—H3	119.6	H8A—C8—H8B	108.0
C4—C3—C2	120.74 (16)	O3—C9—C1	115.16 (15)
C4—C3—H3	119.6	O3—C9—C11	124.74 (16)
C3—C4—C5	122.59 (16)	C11—C9—C1	120.09 (16)
C3—C4—C11	118.57 (16)	O3—C10—H10A	109.5
C11—C4—C5	118.82 (15)	O3—C10—H10B	109.5
C4—C5—H5A	108.5	O3—C10—H10C	109.5
C4—C5—H5B	108.5	H10A—C10—H10B	109.5
H5A—C5—H5B	107.5	H10A—C10—H10C	109.5
C6—C5—C4	115.18 (15)	H10B—C10—H10C	109.5
C6—C5—H5A	108.5	C4—C11—H11	119.5
C6—C5—H5B	108.5	C9—C11—C4	120.96 (16)
C5—C6—H6	117.8	C9—C11—H11	119.5
C7—C6—C5	124.35 (18)

O1—C1—C2—C3	178.96 (16)	C3—C4—C5—C6	30.2 (2)
O1—C1—C9—O3	1.3 (2)	C3—C4—C11—C9	−0.1 (3)
O1—C1—C9—C11	−177.74 (15)	C4—C5—C6—C7	−123.8 (2)
O3—C9—C11—C4	179.28 (15)	C5—C4—C11—C9	−178.60 (15)
C1—C2—C3—C4	−0.7 (3)	C5—C6—C7—C8	−178.11 (18)
C1—C9—C11—C4	−1.8 (3)	C6—C7—C8—O2	−116.2 (2)
C2—C1—C9—O3	−178.53 (15)	C9—C1—C2—C3	−1.2 (3)
C2—C1—C9—C11	2.4 (3)	C10—O3—C9—C1	174.23 (15)
C2—C3—C4—C5	179.76 (16)	C10—O3—C9—C11	−6.8 (2)
C2—C3—C4—C11	1.3 (3)	C11—C4—C5—C6	−151.41 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.84	1.80 (1)	2.635 (2)	174 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

Acknowledgements are made to the National Science Foundation MRI Program (CHE-0951711), the Grote Chemistry Fund at the University of Tennessee at Chattanooga, and to Materia Inc. of Pasadena, CA, USA, for their generous support of our work.

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-[(E)-4-Hydroxybut-2-en-1-yl]-2-methoxyphenol

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds