Methyl 3-hydr-oxy-4-(3-methyl-but-2-en-yloxy)benzoate.

The title compound, C(13)H(16)O(4), 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 intra-molecular O-H⋯O hydrogen bond contributes to this conformation. In the crystal structure, mol-ecules are linked into a one-dimensional chain by inter-molecular O-H⋯O hydrogen bonds. Weak non-classical C-H⋯π contacts are also observed in the structure.

Related literature

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 ▶).

Experimental

Crystal data

C13H16O4

M = 236.26

Triclinic,

a = 7.8401 (16) Å

b = 8.3899 (17) Å

c = 11.099 (2) Å

α = 100.655 (3)°

β = 98.771 (3)°

γ = 115.456 (3)°

V = 625.3 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 291 K

0.40 × 0.38 × 0.35 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.964, T max = 0.968

4817 measured reflections

2420 independent reflections

2058 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.161

S = 1.05

2420 reflections

158 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900806X/sj2576sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900806X/sj2576Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C13H16O4	Z = 2
Mr = 236.26	F(000) = 252
Triclinic, P1	Dx = 1.255 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8401 (16) Å	Cell parameters from 4817 reflections
b = 8.3899 (17) Å	θ = 1.9–26.0°
c = 11.099 (2) Å	µ = 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

Bruker APEXII CCD diffractometer	2420 independent reflections
Radiation source: fine-focus sealed tube	2058 reflections with I > 2σ(I)
graphite	Rint = 0.014
φ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.964, Tmax = 0.968	k = −10→10
4817 measured reflections	l = −13→13

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H 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 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	−0.4408 (3)	0.2951 (3)	0.50642 (16)	0.0716 (5)
H1A	−0.3697	0.3458	0.5944	0.107*
H1B	−0.4681	0.1692	0.4784	0.107*
H1C	−0.5616	0.3009	0.4960	0.107*
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	−0.0474	0.6410	0.3955	0.058*
C5	0.02077 (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	−0.2702	0.5224	−0.0389	0.067*
C8	−0.3388 (2)	0.4343 (2)	0.11268 (14)	0.0544 (4)
H8A	−0.4597	0.3346	0.0682	0.065*
C9	0.0269 (2)	0.7902 (2)	−0.07071 (14)	0.0557 (4)
H9A	−0.0895	0.8036	−0.0942	0.067*
H9B	0.0003	0.6684	−0.1169	0.067*
C10	0.1952 (2)	0.9336 (2)	−0.10072 (15)	0.0578 (4)
H10A	0.3061	1.0114	−0.0342	0.069*
C11	0.1993 (2)	0.9589 (2)	−0.21421 (14)	0.0546 (4)
C12	0.0315 (3)	0.8410 (3)	−0.32730 (17)	0.0836 (6)
H12A	−0.0725	0.7516	−0.3026	0.125*
H12B	0.0724	0.7793	−0.3892	0.125*
H12C	−0.0138	0.9160	−0.3632	0.125*
C13	0.3751 (3)	1.1067 (3)	−0.2368 (2)	0.0752 (5)
H13A	0.4748	1.1741	−0.1582	0.113*
H13B	0.3387	1.1889	−0.2699	0.113*
H13C	0.4242	1.0518	−0.2968	0.113*
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)
O3	0.19557 (16)	0.87793 (16)	0.31218 (11)	0.0663 (4)
H3A	0.231 (4)	0.943 (4)	0.263 (2)	0.102 (8)*
O4	0.08089 (14)	0.81567 (13)	0.06303 (9)	0.0537 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0731 (11)	0.0727 (11)	0.0615 (10)	0.0165 (9)	0.0292 (9)	0.0378 (9)
C2	0.0446 (7)	0.0438 (7)	0.0559 (8)	0.0141 (6)	0.0170 (6)	0.0222 (6)
C3	0.0414 (7)	0.0383 (7)	0.0526 (8)	0.0122 (6)	0.0151 (6)	0.0191 (6)
C4	0.0452 (7)	0.0459 (7)	0.0446 (7)	0.0117 (6)	0.0118 (6)	0.0186 (6)
C5	0.0377 (7)	0.0407 (7)	0.0492 (7)	0.0089 (5)	0.0108 (5)	0.0166 (6)
C6	0.0434 (7)	0.0397 (7)	0.0494 (8)	0.0127 (6)	0.0169 (6)	0.0192 (6)
C7	0.0535 (8)	0.0494 (8)	0.0451 (7)	0.0067 (7)	0.0093 (6)	0.0177 (6)
C8	0.0456 (7)	0.0441 (7)	0.0523 (8)	0.0029 (6)	0.0078 (6)	0.0166 (6)
C9	0.0579 (9)	0.0501 (8)	0.0481 (8)	0.0119 (7)	0.0171 (6)	0.0208 (6)
C10	0.0588 (9)	0.0500 (8)	0.0534 (8)	0.0114 (7)	0.0210 (7)	0.0205 (7)
C11	0.0688 (10)	0.0527 (8)	0.0556 (8)	0.0316 (8)	0.0311 (7)	0.0252 (7)
C12	0.0918 (14)	0.0981 (15)	0.0565 (10)	0.0370 (12)	0.0193 (10)	0.0314 (10)
C13	0.0933 (14)	0.0714 (11)	0.0806 (12)	0.0382 (11)	0.0533 (11)	0.0417 (10)
O1	0.0574 (6)	0.0626 (7)	0.0561 (6)	0.0075 (5)	0.0189 (5)	0.0305 (5)
O2	0.0530 (7)	0.0590 (7)	0.0689 (7)	−0.0030 (5)	0.0148 (5)	0.0275 (6)
O3	0.0486 (6)	0.0604 (7)	0.0555 (7)	−0.0055 (5)	0.0056 (5)	0.0255 (5)
O4	0.0496 (6)	0.0489 (6)	0.0470 (6)	0.0055 (5)	0.0153 (4)	0.0212 (5)

C1—O1	1.4418 (17)	C8—H8A	0.9300
C1—H1A	0.9600	C9—O4	1.4289 (18)
C1—H1B	0.9600	C9—C10	1.489 (2)
C1—H1C	0.9600	C9—H9A	0.9700
C2—O2	1.2066 (18)	C9—H9B	0.9700
C2—O1	1.3300 (18)	C10—C11	1.319 (2)
C2—C3	1.4808 (18)	C10—H10A	0.9300
C3—C8	1.378 (2)	C11—C12	1.484 (3)
C3—C4	1.399 (2)	C11—C13	1.500 (2)
C4—C5	1.3763 (18)	C12—H12A	0.9600
C4—H4A	0.9300	C12—H12B	0.9600
C5—O3	1.3594 (17)	C12—H12C	0.9600
C5—C6	1.397 (2)	C13—H13A	0.9600
C6—O4	1.3563 (16)	C13—H13B	0.9600
C6—C7	1.386 (2)	C13—H13C	0.9600
C7—C8	1.382 (2)	O3—H3A	0.84 (3)
C7—H7A	0.9300
O1—C1—H1A	109.5	O4—C9—C10	106.75 (12)
O1—C1—H1B	109.5	O4—C9—H9A	110.4
H1A—C1—H1B	109.5	C10—C9—H9A	110.4
O1—C1—H1C	109.5	O4—C9—H9B	110.4
H1A—C1—H1C	109.5	C10—C9—H9B	110.4
H1B—C1—H1C	109.5	H9A—C9—H9B	108.6
O2—C2—O1	123.26 (13)	C11—C10—C9	125.11 (15)
O2—C2—C3	124.42 (14)	C11—C10—H10A	117.4
O1—C2—C3	112.31 (12)	C9—C10—H10A	117.4
C8—C3—C4	119.39 (13)	C10—C11—C12	121.92 (15)
C8—C3—C2	118.91 (13)	C10—C11—C13	121.91 (16)
C4—C3—C2	121.69 (13)	C12—C11—C13	116.16 (15)
C5—C4—C3	120.19 (13)	C11—C12—H12A	109.5
C5—C4—H4A	119.9	C11—C12—H12B	109.5
C3—C4—H4A	119.9	H12A—C12—H12B	109.5
O3—C5—C4	119.06 (13)	C11—C12—H12C	109.5
O3—C5—C6	120.93 (12)	H12A—C12—H12C	109.5
C4—C5—C6	120.01 (12)	H12B—C12—H12C	109.5
O4—C6—C7	126.11 (13)	C11—C13—H13A	109.5
O4—C6—C5	114.18 (12)	C11—C13—H13B	109.5
C7—C6—C5	119.71 (13)	H13A—C13—H13B	109.5
C8—C7—C6	119.92 (14)	C11—C13—H13C	109.5
C8—C7—H7A	120.0	H13A—C13—H13C	109.5
C6—C7—H7A	120.0	H13B—C13—H13C	109.5
C3—C8—C7	120.78 (13)	C2—O1—C1	117.18 (12)
C3—C8—H8A	119.6	C5—O3—H3A	105.7 (18)
C7—C8—H8A	119.6	C6—O4—C9	118.40 (11)
O2—C2—C3—C8	0.9 (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—C7	178.79 (13)
O1—C2—C3—C4	1.0 (2)	C6—C7—C8—C3	0.2 (3)
C8—C3—C4—C5	0.8 (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—O3	178.57 (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—O4	0.8 (2)	C3—C2—O1—C1	177.47 (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—C9	179.99 (12)
C4—C5—C6—C7	1.0 (2)	C10—C9—O4—C6	−176.59 (12)
O4—C6—C7—C8	−179.96 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4	0.84 (3)	2.16 (2)	2.6519 (15)	117 (2)
O3—H3A···O2i	0.84 (3)	2.20 (3)	2.9111 (16)	143 (2)
C9—H9B···Cg1ii	0.97	2.90	3.7483 (2)	146
C13—H13B···Cg1iii	0.96	2.96	3.688 (3)	134

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O4	0.84 (3)	2.16 (2)	2.6519 (15)	117 (2)
O3—H3A⋯O2i	0.84 (3)	2.20 (3)	2.9111 (16)	143 (2)
C9—H9B⋯Cg1ii	0.97	2.90	3.7483 (2)	146
C13—H13B⋯Cg1iii	0.96	2.96	3.688 (3)	134

Symmetry codes: (i) ; (ii) ; (iii) . Cg1 is the centroid of the C3–C8 ring.