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

Abstract

The title compound, C
11
H
14
O
3
, 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.

Full text

data reports
IUCrData (2016). 1, x160936 http://dx.doi.org/10.1107/S2414314616009366 1of2
4-[(E)-4-Hydroxybut-2-en-1-yl]-2-methoxyphenol
Kyle S. Knight* and Michael C. Orick
Department of Chemistry and Physics, The University of Tennessee at Chattanooga, Chattanooga, TN, 37403, USA.
*Correspondence e-mail: kyle-knight@utc.edu
The title compound, C
11
H
14
O
3
, 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.
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).
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
Synthesis and crystallization
The Grubbs second-generation catalyst, tricyclohexylphosphine[1,3-bis-(2,4,6-trimethyl-
phenyl)-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
Received 19 May 2016
Accepted 9 June 2016
Edited by J. Simpson, University of Otago, New
Zealand
Keywords: crystal structure; alkene metathesis;
hydrogen bonding.
CCDC reference:1484314
Structural data:full structural data are available
from iucrdata.iucr.org
ISSN 2414-3146

2of2 Knight and Orick C
11
H
14
O
3
IUCrData (2016). 1, x160936
data reports
form the title compound. The product was mpurified by
column chromatography, and allowed to crystallize from di-
chloromethane at room temperature over the course of 14
days.
Refinement
Crystal data, data collection and structure refinement details
are summarized in Table 2.
Acknowledgements
Acknowledgements are made to the National Science Foun-
dation 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
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. &
Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
Grubbs, R. H. (2004). Tetrahedron,60, 7117–7140.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe,
P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. &
Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.
Masuda, T. & Jitoe, A. (1995). Phytochem. 39, 459–461.
Scholl, M., Ding, S., Lee, C. W. & Grubbs, R. H. (1999). Org. Lett. 1,
953–956.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
Taber, D. F. & Frankowski, K. J. (2006). J. Chem. Educ. 83, 283–284.
Table 1
Hydrogen-bond geometry (A
˚,).
D—HAD—H HADAD—HA
O1—H1O2
i
0.84 1.80 (1) 2.635 (2) 174 (2)
Symmetry code: (i) xþ1;yþ2;zþ1.
Figure 2
Crystal packing of the title compound, viewed along the aaxis with
hydrogen bonds drawn as dashed lines.
Table 2
Experimental details.
Crystal data
Chemical formula C
11
H
14
O
3
M
r
194.22
Crystal system, space group Triclinic, P1
Temperature (K) 200
a,b,c(A
˚) 5.7659 (11), 8.5396 (17), 10.804 (2)
,,() 81.579 (6), 88.020 (6), 71.167 (6)
V(A
˚
3
) 498.03 (17)
Z2
Radiation type Mo K
(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>2(I)] reflections
9408, 1736, 1487
R
int
0.042
(sin /)
max
(A
˚
1
) 0.595
Refinement
R[F
2
>2(F
2
)], wR(F
2
), S0.046, 0.114, 1.07
No. of reflections 1736
No. of parameters 130
H-atom treatment H-atom parameters constrained

max
,
min
(e A
˚
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).
Figure 1
A view of the molecular structure of the title compound, with atom
labelling. Displacement ellipsoids are drawn at the 50% probability level.

data reports
data-1
IUCrData (2016). 1, x160936
full crystallographic data
IUCrData (2016). 1, x160936 [doi:10.1107/S2414314616009366]
4-[(E)-4-Hydroxybut-2-en-1-yl]-2-methoxyphenol
Kyle S. Knight and Michael C. Orick
4-[(E)-4-Hydroxybut-2-en-1-yl]-2-methoxyphenol
Crystal data
C11H14O3
Mr = 194.22
Triclinic, P1
a = 5.7659 (11) Å
b = 8.5396 (17) Å
c = 10.804 (2) Å
α = 81.579 (6)°
β = 88.020 (6)°
γ = 71.167 (6)°
V = 498.03 (17) Å3
Z = 2
F(000) = 208
Dx = 1.295 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3014 reflections
θ = 2.5–24.8°
µ = 0.09 mm−1
T = 200 K
Plate, colorless
0.6 × 0.4 × 0.05 mm
Data collection
Bruker APEXII CCD
diffractometer
Graphite monochromator
φ and ω scans
9408 measured reflections
1736 independent reflections
1487 reflections with I > 2σ(I)
Rint = 0.042
θmax = 25.0°, θmin = 3.0°
h = −6→6
k = −10→10
l = −12→12
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.046
wR(F2) = 0.114
S = 1.07
1736 reflections
130 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.044P)2 + 0.2128P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.49 e Å−3
Δρmin = −0.18 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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
xy z U
iso*/Ueq
O1 0.6301 (2) 0.80940 (16) 0.11536 (11) 0.0390 (4)

data reports
data-2
IUCrData (2016). 1, x160936
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)
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)

data reports
data-3
IUCrData (2016). 1, x160936
Geometric parameters (Å, º)
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)

data reports
data-4
IUCrData (2016). 1, x160936
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)
D—H···AD—H H···AD···AD—H···A
O1—H1···O2i0.84 1.80 (1) 2.635 (2) 174 (2)
Symmetry code: (i) −x+1, −y+2, −z+1.