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Acta Cryst. (2009). E65, o734-o735    [ doi:10.1107/S160053680900806X ]

Methyl 3-hydroxy-4-(3-methylbut-2-enyloxy)benzoate

M. Wei, Z. Liu, X. Zhang, C. Shao and C. Wang

Abstract top

The title compound, C13H16O4, was isolated from culture extracts of the endophytic fungus Cephalosporium sp. The ester and ether substituents are twisted only slightly out of the benzene ring plane, making dihedral angles of 2.16 (2) and 3.63 (5)°, respectively. The non-H atoms of all three substituents are almost coplanar with the benzene ring, with an r.m.s. deviation of 0.0284 Å from the mean plane through all non-H atoms in the structure. A weak intramolecular O-H...O hydrogen bond contributes to this conformation. In the crystal structure, molecules are linked into a one-dimensional chain by intermolecular O-H...O hydrogen bonds. Weak non-classical C-H...[pi] contacts are also observed in the structure.

Comment top

Marine fungi have proven to be a rich source of novel structural compounds with interesting biological activities and a high level of biodiversity. As a continuation of our previous investigations aimed at finding new bioactive compounds, we found that an unidentified endophytic strain B60 isolated from the mangrove tree can produce new metabolites (Shao et al. 2007; Shao et al. 2008).

Although the structure of the title compound was previously elucidated on the basis of spectroscopic analysis (Shao et al. 2008), we have now determined its solid state structure, Fig. 1, which is reported here. All bond lengths and angles in the molecule are in good agreement with those reported in a related structure by Huang et al. (2005). In the title compound, the most striking feature is the interesting arrangement of the molecules, which linked to form a one-dimensional chain by intermolecular O—H···O hydrogen bonds, Table 1, Fig. 2. Further, weak non-classical C—H···π contacts, similar to those previously reported (Nangia, 2002; Umezawa et al. 1999) are also observed, in which C9—H9B and C13—H13B act as donors with the benzene ring as the acceptor.

Related literature top

For structures with C—H···O and C—H···π contacts, see: Nangia (2002); Umezawa et al. (1999). For new bioactive secondary metabolites from the endophytic strain B60, see: Shao et al. (2007, 2008). For an investigation of the endophytic fungus, see: Shao et al. (2008). For a related structure, see: Huang et al. (2005). Cg1 is the centroid of the C3–C8 ring.

Experimental top

An unidentified fungus (No. B60) was deposited in the School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, People's Republic of China. Strain No. B60 was cultivated without shaking in GYT medium (10 g of glucose, 2 g of peptone /L, 1 g of yeast extract /L, 2.5 g of NaCl, 1L of water) at 298 K for 4 weeks. The cultures (120 L) were filtered through cheesecloth. The filtrate was concentrated to 3 L below 323 K, then extracted five times by shaking with an equal volume of ethyl acetate. The extract was evaporated under reduced pressure below 323 K. The combined organic extracts were subjected to silica-gel column chromatography, eluting with petroleum ether/ethyl acetate (9:1, v:v), to yield the title compound, which was confirmed by spectral data including NMR and EI—MS. Crystals of the title compound were obtained by evaporation of an ethyl acetate solution.

Refinement top

All H atoms were positioned geometrically and treated as riding, with C—H bonding lengths constrained to 0.93 (aromatic CH), 0.96 Å (methyl CH3), 0.97 Å (methylene CH2), and O—H = 0.84 Å, and with Uĩso~(H) = 1.2Ueq(CH) or Uĩso~(H) = 1.5Ueq(CH3, methylene C or OH).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level.
[Figure 2] Fig. 2. Crystal packing of (I) viewed down the b axis with hydrogen bonds drawn as dashed lines.
Methyl 3-hydroxy-4-(3-methylbut-2-enyloxy)benzoate top
Crystal data top
C13H16O4Z = 2
Mr = 236.26F(000) = 252
Triclinic, P1Dx = 1.255 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8401 (16) ÅCell parameters from 4817 reflections
b = 8.3899 (17) Åθ = 1.9–26.0°
c = 11.099 (2) ŵ = 0.09 mm−1
α = 100.655 (3)°T = 291 K
β = 98.771 (3)°Block, colorless
γ = 115.456 (3)°0.40 × 0.38 × 0.35 mm
V = 625.3 (2) Å3
Data collection top
Bruker APEXII CCD
diffractometer		2420 independent reflections
Radiation source: fine-focus sealed tube2058 reflections with I > 2σ(I)
graphiteRint = 0.014
φ and ω scansθmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.964, Tmax = 0.968k = −10→10
4817 measured reflectionsl = −13→13
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.1024P)2 + 0.0667P]
where P = (Fo2 + 2Fc2)/3
2420 reflections(Δ/σ)max < 0.001
158 parametersΔρmax = 0.23 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C13H16O4γ = 115.456 (3)°
Mr = 236.26V = 625.3 (2) Å3
Triclinic, P1Z = 2
a = 7.8401 (16) ÅMo Kα radiation
b = 8.3899 (17) ŵ = 0.09 mm−1
c = 11.099 (2) ÅT = 291 K
α = 100.655 (3)°0.40 × 0.38 × 0.35 mm
β = 98.771 (3)°
Data collection top
Bruker APEXII CCD
diffractometer		2420 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2058 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.968Rint = 0.014
4817 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.161Δρmax = 0.23 e Å−3
S = 1.05Δρmin = −0.25 e Å−3
2420 reflectionsAbsolute structure: ?
158 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1−0.4408 (3)0.2951 (3)0.50642 (16)0.0716 (5)
H1A−0.36970.34580.59440.107*
H1B−0.46810.16920.47840.107*
H1C−0.56160.30090.49600.107*
C2−0.4029 (2)0.34671 (19)0.30738 (14)0.0490 (4)
C3−0.2748 (2)0.46837 (17)0.24198 (13)0.0453 (3)
C4−0.0924 (2)0.61796 (19)0.30835 (13)0.0481 (4)
H4A−0.04740.64100.39550.058*
C50.02077 (19)0.73115 (19)0.24510 (13)0.0457 (3)
C6−0.04479 (19)0.69490 (18)0.11391 (13)0.0452 (3)
C7−0.2253 (2)0.5465 (2)0.04830 (14)0.0558 (4)
H7A−0.27020.5224−0.03890.067*
C8−0.3388 (2)0.4343 (2)0.11268 (14)0.0544 (4)
H8A−0.45970.33460.06820.065*
C90.0269 (2)0.7902 (2)−0.07071 (14)0.0557 (4)
H9A−0.08950.8036−0.09420.067*
H9B0.00030.6684−0.11690.067*
C100.1952 (2)0.9336 (2)−0.10072 (15)0.0578 (4)
H10A0.30611.0114−0.03420.069*
C110.1993 (2)0.9589 (2)−0.21421 (14)0.0546 (4)
C120.0315 (3)0.8410 (3)−0.32730 (17)0.0836 (6)
H12A−0.07250.7516−0.30260.125*
H12B0.07240.7793−0.38920.125*
H12C−0.01380.9160−0.36320.125*
C130.3751 (3)1.1067 (3)−0.2368 (2)0.0752 (5)
H13A0.47481.1741−0.15820.113*
H13B0.33871.1889−0.26990.113*
H13C0.42421.0518−0.29680.113*
O1−0.32509 (16)0.39913 (15)0.43211 (10)0.0640 (4)
O2−0.56125 (16)0.21602 (16)0.25485 (12)0.0702 (4)
O30.19557 (16)0.87793 (16)0.31218 (11)0.0663 (4)
H3A0.231 (4)0.943 (4)0.263 (2)0.102 (8)*
O40.08089 (14)0.81567 (13)0.06303 (9)0.0537 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0731 (11)0.0727 (11)0.0615 (10)0.0165 (9)0.0292 (9)0.0378 (9)
C20.0446 (7)0.0438 (7)0.0559 (8)0.0141 (6)0.0170 (6)0.0222 (6)
C30.0414 (7)0.0383 (7)0.0526 (8)0.0122 (6)0.0151 (6)0.0191 (6)
C40.0452 (7)0.0459 (7)0.0446 (7)0.0117 (6)0.0118 (6)0.0186 (6)
C50.0377 (7)0.0407 (7)0.0492 (7)0.0089 (5)0.0108 (5)0.0166 (6)
C60.0434 (7)0.0397 (7)0.0494 (8)0.0127 (6)0.0169 (6)0.0192 (6)
C70.0535 (8)0.0494 (8)0.0451 (7)0.0067 (7)0.0093 (6)0.0177 (6)
C80.0456 (7)0.0441 (7)0.0523 (8)0.0029 (6)0.0078 (6)0.0166 (6)
C90.0579 (9)0.0501 (8)0.0481 (8)0.0119 (7)0.0171 (6)0.0208 (6)
C100.0588 (9)0.0500 (8)0.0534 (8)0.0114 (7)0.0210 (7)0.0205 (7)
C110.0688 (10)0.0527 (8)0.0556 (8)0.0316 (8)0.0311 (7)0.0252 (7)
C120.0918 (14)0.0981 (15)0.0565 (10)0.0370 (12)0.0193 (10)0.0314 (10)
C130.0933 (14)0.0714 (11)0.0806 (12)0.0382 (11)0.0533 (11)0.0417 (10)
O10.0574 (6)0.0626 (7)0.0561 (6)0.0075 (5)0.0189 (5)0.0305 (5)
O20.0530 (7)0.0590 (7)0.0689 (7)−0.0030 (5)0.0148 (5)0.0275 (6)
O30.0486 (6)0.0604 (7)0.0555 (7)−0.0055 (5)0.0056 (5)0.0255 (5)
O40.0496 (6)0.0489 (6)0.0470 (6)0.0055 (5)0.0153 (4)0.0212 (5)
Geometric parameters (Å, °) top
C1—O11.4418 (17)C8—H8A0.9300
C1—H1A0.9600C9—O41.4289 (18)
C1—H1B0.9600C9—C101.489 (2)
C1—H1C0.9600C9—H9A0.9700
C2—O21.2066 (18)C9—H9B0.9700
C2—O11.3300 (18)C10—C111.319 (2)
C2—C31.4808 (18)C10—H10A0.9300
C3—C81.378 (2)C11—C121.484 (3)
C3—C41.399 (2)C11—C131.500 (2)
C4—C51.3763 (18)C12—H12A0.9600
C4—H4A0.9300C12—H12B0.9600
C5—O31.3594 (17)C12—H12C0.9600
C5—C61.397 (2)C13—H13A0.9600
C6—O41.3563 (16)C13—H13B0.9600
C6—C71.386 (2)C13—H13C0.9600
C7—C81.382 (2)O3—H3A0.84 (3)
C7—H7A0.9300
O1—C1—H1A109.5O4—C9—C10106.75 (12)
O1—C1—H1B109.5O4—C9—H9A110.4
H1A—C1—H1B109.5C10—C9—H9A110.4
O1—C1—H1C109.5O4—C9—H9B110.4
H1A—C1—H1C109.5C10—C9—H9B110.4
H1B—C1—H1C109.5H9A—C9—H9B108.6
O2—C2—O1123.26 (13)C11—C10—C9125.11 (15)
O2—C2—C3124.42 (14)C11—C10—H10A117.4
O1—C2—C3112.31 (12)C9—C10—H10A117.4
C8—C3—C4119.39 (13)C10—C11—C12121.92 (15)
C8—C3—C2118.91 (13)C10—C11—C13121.91 (16)
C4—C3—C2121.69 (13)C12—C11—C13116.16 (15)
C5—C4—C3120.19 (13)C11—C12—H12A109.5
C5—C4—H4A119.9C11—C12—H12B109.5
C3—C4—H4A119.9H12A—C12—H12B109.5
O3—C5—C4119.06 (13)C11—C12—H12C109.5
O3—C5—C6120.93 (12)H12A—C12—H12C109.5
C4—C5—C6120.01 (12)H12B—C12—H12C109.5
O4—C6—C7126.11 (13)C11—C13—H13A109.5
O4—C6—C5114.18 (12)C11—C13—H13B109.5
C7—C6—C5119.71 (13)H13A—C13—H13B109.5
C8—C7—C6119.92 (14)C11—C13—H13C109.5
C8—C7—H7A120.0H13A—C13—H13C109.5
C6—C7—H7A120.0H13B—C13—H13C109.5
C3—C8—C7120.78 (13)C2—O1—C1117.18 (12)
C3—C8—H8A119.6C5—O3—H3A105.7 (18)
C7—C8—H8A119.6C6—O4—C9118.40 (11)
O2—C2—C3—C80.9 (2)C5—C6—C7—C8−0.6 (2)
O1—C2—C3—C8−178.13 (12)C4—C3—C8—C7−0.3 (2)
O2—C2—C3—C4−179.95 (14)C2—C3—C8—C7178.79 (13)
O1—C2—C3—C41.0 (2)C6—C7—C8—C30.2 (3)
C8—C3—C4—C50.8 (2)O4—C9—C10—C11−177.76 (15)
C2—C3—C4—C5−178.28 (12)C9—C10—C11—C12−0.9 (3)
C3—C4—C5—O3178.57 (13)C9—C10—C11—C13−179.89 (15)
C3—C4—C5—C6−1.2 (2)O2—C2—O1—C1−1.6 (2)
O3—C5—C6—O40.8 (2)C3—C2—O1—C1177.47 (13)
C4—C5—C6—O4−179.48 (12)C7—C6—O4—C9−0.6 (2)
O3—C5—C6—C7−178.70 (14)C5—C6—O4—C9179.99 (12)
C4—C5—C6—C71.0 (2)C10—C9—O4—C6−176.59 (12)
O4—C6—C7—C8−179.96 (13)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O40.84 (3)2.16 (2)2.6519 (15)117 (2)
O3—H3A···O2i0.84 (3)2.20 (3)2.9111 (16)143 (2)
C9—H9B···Cg1ii0.972.903.7483 (2)146
C13—H13B···Cg1iii0.962.963.688 (3)134
Symmetry codes: (i) x+1, y+1, z; (ii) −x, −y+1, −z; (iii) −x, −y+2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O40.84 (3)2.16 (2)2.6519 (15)117 (2)
O3—H3A···O2i0.84 (3)2.20 (3)2.9111 (16)143 (2)
C9—H9B···Cg1ii0.972.903.7483 (2)146
C13—H13B···Cg1iii0.962.963.688 (3)134
Symmetry codes: (i) x+1, y+1, z; (ii) −x, −y+1, −z; (iii) −x, −y+2, −z.
Acknowledgements top

We wish to acknowledge financial support from the National Natural Science Foundation of China (No. 40776073), the Basic Research Program of Science and Technology, Ministry of Science and Technology of China (No. 2007FY210500), the Youthful Fund of Guangdong Medical College (No. XQ0511), and the doctoral startup fund of Ocean University of China (No. 1404–82421036).

references
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