6,8-Dihydr­oxy-3-methyl­isocoumarin

Shao, C.; Han, L.; Li, C.; Liu, Z.; Wang, C.

doi:10.1107/S1600536809008083

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o736

doi:10.1107/S1600536809008083

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6,8-Dihydroxy-3-methylisocoumarin

Chang-lun Shao,^a Lei Han,^a Chun-yuan Li,^b Zhen Liu ^c and Chang-yun Wang ^a ^*

^aSchool of Medicine and Pharmacy, Ocean University of China, Qingdao, Shandong 266003, People's Republic of China, ^bCollege of Science, South China Agricultural University, Guangzhou, Guangdong 510642, People's Republic of China, and ^cCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, Henan 471022, People's Republic of China
^*Correspondence e-mail: changyun@ouc.edu.cn

(Received 4 February 2009; accepted 5 March 2009; online 11 March 2009)

The title compound, C₁₀H₈O₄, was isolated from the fermentation culture of the endophytic fungus Cephalosporium sp. In the crystal structure, molecules are connected into a one-dimensional chain along [101] by intermolecular O—H⋯O hydrogen bonds involving the hydroxyl and carbonyl functionalities. The chains are linked by non-classical C—H⋯O interactions, forming extended two-dimensional layers approximately parallel to (11 $[\overline{2}]$ ).

Related literature

For new bioactive secondary metabolites from marine fungi, see: Shao et al. (2007 ). For the investigation of an endophytic strain Cephalosporium sp., see: Wei et al. (2008 ); Hemingway et al. (1977 ); Kendall et al. (1989 ). For crystal structures with non-classical C—H⋯O interactions, see: Nangia (2002 ).

Experimental

Crystal data

C₁₀H₈O₄
M_r = 192.16
Monoclinic, P 2₁ /c
a = 3.8201 (7) Å
b = 15.710 (3) Å
c = 14.196 (2) Å
β = 92.668 (2)°
V = 851.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 291 K
0.27 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.969, T_max = 0.978
4781 measured reflections
1586 independent reflections
1272 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.094
S = 1.04
1586 reflections
131 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2ⁱ	0.82	1.96	2.7225 (15)	155
C5—H5⋯O4ⁱⁱ	0.93	2.60	3.4659 (19)	155
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x-1, -y+1, -z+1.

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); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008083/bh2219sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008083/bh2219Isup2.hkl

checkCIF report

Comment top

Endophytic fungi have proven to be a rich source of novel structural compounds with interesting biological activities and a high level of biodiversity. In the course of our search for new or bioactive secondary metabolites from the marine fungi (Shao et al., 2007). we have investigated an endophytic strain Cephalosporium sp. (Wei et al., 2008). The title compound was previously isolated from the organic extracts of the fungus Ceratocystis minor (Hemingway et al., 1977), and elucidated on the basic of spectroscopic analysis (Kendall et al., 1989). Herein, the title compound was isolated from the fermentation culture of the endophytic fungus Cephalosporium sp., and its crystal structure is reported.

The asymmetric unit of the title compound contains one independent molecule (Fig. 1), in which the bond lengths and angles are within the expected ranges. The structural analysis reveals that the most relevant feature is the arrangement of the molecules, which are connected to form a one-dimensional chain along the [101] direction, by the formation of intermolecular O—H···O hydrogen bonds. Furthermore, weak non-conventional intermolecular C—H···O interactions are observed (Nangia, 2002), in which C5—H5 is a donor and O4 is an acceptor. These interactions consolidate the crystal packing. Details of hydrogen bonds are given in Table 1.

Related literature top

For new bioactive secondary metabolites from marine fungi, see: Shao et al. (2007). For the investigation of an endophytic strain Cephalosporium sp., see: Wei et al. (2008); Hemingway et al. (1977); Kendall et al. (1989). For crystal structures with non-conventional C—H···O interactions, see: Nangia (2002).

Experimental top

A strain of fungus Cephalosporium sp. (No. 2090) was deposited in the School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou, People's Republic of China. Culture conditions: GYT medium (glucose 10 g/L, peptone 2 g/L, yeast extract 1 g/L, NaCl 2.5 g/L) and incubation at 298 K for 4 weeks. The cultures (70 L) were filtered through cheesecloth. The filtrate was concentrated to 3 L below 323 K, 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 chromatographed on silica-gel, eluting with petroleum ether/ethyl acetate, to yield the title compound. Crystals were obtained by evaporation of an ethyl acetate solution.

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); software used to prepare material for publication: SHELXTL (Sheldrick 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title molecule with atom numbering scheme and 30% probability displacement ellipsoids for non-hydrogen atoms.
	Fig. 2. View of the 2D layers formed by intermolecular O—H···O hydrogen bonds and weak non-conventional intermolecular C—H···O interactions.

6,8-Dihydroxy-3-methylisocoumarin top

Crystal data top

C₁₀H₈O₄	F(000) = 400
M_r = 192.16	D_x = 1.500 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1738 reflections
a = 3.8201 (7) Å	θ = 2.6–25.5°
b = 15.710 (3) Å	µ = 0.12 mm⁻¹
c = 14.196 (2) Å	T = 291 K
β = 92.668 (2)°	Block, yellow
V = 851.1 (3) Å³	0.27 × 0.20 × 0.19 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1586 independent reflections
Radiation source: fine-focus sealed tube	1272 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.969, T_max = 0.978	k = −19→13
4781 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0441P)² + 0.1957P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1586 reflections	Δρ_max = 0.18 e Å⁻³
131 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.015 (3)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₀H₈O₄	V = 851.1 (3) Å³
M_r = 192.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8201 (7) Å	µ = 0.12 mm⁻¹
b = 15.710 (3) Å	T = 291 K
c = 14.196 (2) Å	0.27 × 0.20 × 0.19 mm
β = 92.668 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1586 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1272 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.978	R_int = 0.021
4781 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.04	Δρ_max = 0.18 e Å⁻³
1586 reflections	Δρ_min = −0.14 e Å⁻³
131 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.3482 (3)	0.32453 (7)	0.81217 (7)	0.0451 (3)
O2	0.3544 (3)	0.19366 (7)	0.75748 (8)	0.0572 (4)
O3	0.0718 (3)	0.15766 (7)	0.58873 (8)	0.0552 (4)
H3	0.1709	0.1476	0.6400	0.083*
O4	−0.4021 (3)	0.39231 (7)	0.41364 (7)	0.0487 (3)
H4	−0.4514	0.3541	0.3759	0.073*
C1	0.3853 (4)	0.45742 (12)	0.89102 (11)	0.0516 (4)
H1A	0.3148	0.5160	0.8859	0.077*
H1B	0.6359	0.4542	0.8987	0.077*
H1C	0.2819	0.4321	0.9446	0.077*
C2	0.2659 (4)	0.41080 (10)	0.80372 (10)	0.0395 (4)
C3	0.1028 (4)	0.44079 (10)	0.72629 (10)	0.0379 (4)
H3A	0.0505	0.4985	0.7224	0.046*
C4	0.0042 (3)	0.38590 (9)	0.64774 (9)	0.0318 (3)
C5	−0.1641 (4)	0.41528 (9)	0.56587 (10)	0.0355 (3)
H5	−0.2230	0.4725	0.5598	0.043*
C6	−0.2453 (4)	0.35866 (10)	0.49244 (10)	0.0354 (3)
C7	−0.1659 (4)	0.27235 (9)	0.50066 (10)	0.0378 (4)
H7	−0.2235	0.2354	0.4512	0.045*
C8	−0.0016 (4)	0.24192 (9)	0.58233 (10)	0.0368 (3)
C9	0.0880 (4)	0.29837 (9)	0.65755 (9)	0.0337 (3)
C10	0.2651 (4)	0.26818 (10)	0.74166 (10)	0.0401 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0531 (7)	0.0503 (7)	0.0308 (5)	0.0018 (5)	−0.0102 (5)	−0.0008 (5)
O2	0.0802 (9)	0.0448 (7)	0.0447 (7)	0.0086 (6)	−0.0182 (6)	0.0060 (5)
O3	0.0804 (9)	0.0330 (6)	0.0503 (7)	0.0065 (5)	−0.0162 (6)	−0.0011 (5)
O4	0.0677 (8)	0.0425 (6)	0.0342 (6)	0.0033 (5)	−0.0174 (5)	−0.0004 (5)
C1	0.0488 (10)	0.0661 (11)	0.0390 (9)	−0.0024 (8)	−0.0060 (7)	−0.0131 (8)
C2	0.0382 (8)	0.0459 (9)	0.0344 (8)	−0.0026 (7)	0.0008 (6)	−0.0058 (6)
C3	0.0414 (8)	0.0372 (8)	0.0350 (8)	−0.0021 (6)	0.0002 (6)	−0.0034 (6)
C4	0.0311 (7)	0.0354 (8)	0.0291 (7)	−0.0033 (6)	0.0016 (6)	−0.0006 (6)
C5	0.0405 (8)	0.0314 (8)	0.0344 (7)	0.0001 (6)	−0.0011 (6)	0.0009 (6)
C6	0.0354 (8)	0.0407 (8)	0.0297 (7)	−0.0013 (6)	−0.0037 (6)	0.0029 (6)
C7	0.0437 (8)	0.0379 (9)	0.0312 (7)	−0.0045 (6)	−0.0047 (6)	−0.0053 (6)
C8	0.0412 (8)	0.0318 (8)	0.0370 (8)	−0.0010 (6)	−0.0011 (6)	−0.0003 (6)
C9	0.0344 (8)	0.0364 (8)	0.0301 (7)	−0.0011 (6)	−0.0005 (6)	0.0019 (6)
C10	0.0436 (9)	0.0422 (9)	0.0339 (8)	0.0007 (7)	−0.0030 (6)	0.0033 (6)

Geometric parameters (Å, º) top

O1—C10	1.3626 (18)	C3—C4	1.4457 (19)
O1—C2	1.3951 (19)	C3—H3A	0.9300
O2—C10	1.2370 (18)	C4—C5	1.3813 (19)
O3—C8	1.3553 (18)	C4—C9	1.417 (2)
O3—H3	0.8200	C5—C6	1.394 (2)
O4—C6	1.3518 (17)	C5—H5	0.9300
O4—H4	0.8200	C6—C7	1.393 (2)
C1—C2	1.493 (2)	C7—C8	1.378 (2)
C1—H1A	0.9600	C7—H7	0.9300
C1—H1B	0.9600	C8—C9	1.418 (2)
C1—H1C	0.9600	C9—C10	1.426 (2)
C2—C3	1.325 (2)

C10—O1—C2	121.61 (11)	C4—C5—C6	119.64 (13)
C8—O3—H3	109.5	C4—C5—H5	120.2
C6—O4—H4	109.5	C6—C5—H5	120.2
C2—C1—H1A	109.5	O4—C6—C7	122.43 (13)
C2—C1—H1B	109.5	O4—C6—C5	116.35 (13)
H1A—C1—H1B	109.5	C7—C6—C5	121.22 (13)
C2—C1—H1C	109.5	C8—C7—C6	119.81 (13)
H1A—C1—H1C	109.5	C8—C7—H7	120.1
H1B—C1—H1C	109.5	C6—C7—H7	120.1
C3—C2—O1	120.81 (13)	O3—C8—C7	118.69 (13)
C3—C2—C1	128.92 (15)	O3—C8—C9	121.23 (13)
O1—C2—C1	110.27 (13)	C7—C8—C9	120.08 (13)
C2—C3—C4	121.57 (14)	C4—C9—C8	119.18 (12)
C2—C3—H3A	119.2	C4—C9—C10	120.08 (13)
C4—C3—H3A	119.2	C8—C9—C10	120.74 (13)
C5—C4—C9	120.07 (12)	O2—C10—O1	115.39 (13)
C5—C4—C3	122.96 (13)	O2—C10—C9	125.66 (14)
C9—C4—C3	116.96 (12)	O1—C10—C9	118.96 (13)

C10—O1—C2—C3	0.1 (2)	C5—C4—C9—C8	0.3 (2)
C10—O1—C2—C1	179.78 (13)	C3—C4—C9—C8	−179.69 (13)
O1—C2—C3—C4	−0.1 (2)	C5—C4—C9—C10	179.32 (13)
C1—C2—C3—C4	−179.74 (14)	C3—C4—C9—C10	−0.66 (19)
C2—C3—C4—C5	−179.60 (14)	O3—C8—C9—C4	−179.69 (13)
C2—C3—C4—C9	0.4 (2)	C7—C8—C9—C4	0.5 (2)
C9—C4—C5—C6	−1.1 (2)	O3—C8—C9—C10	1.3 (2)
C3—C4—C5—C6	178.85 (13)	C7—C8—C9—C10	−178.57 (13)
C4—C5—C6—O4	−178.42 (12)	C2—O1—C10—O2	179.49 (13)
C4—C5—C6—C7	1.3 (2)	C2—O1—C10—C9	−0.4 (2)
O4—C6—C7—C8	179.14 (14)	C4—C9—C10—O2	−179.17 (15)
C5—C6—C7—C8	−0.5 (2)	C8—C9—C10—O2	−0.2 (2)
C6—C7—C8—O3	179.79 (14)	C4—C9—C10—O1	0.7 (2)
C6—C7—C8—C9	−0.3 (2)	C8—C9—C10—O1	179.67 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.92	2.6426 (16)	146
O4—H4···O2ⁱ	0.82	1.96	2.7225 (15)	155
C5—H5···O4ⁱⁱ	0.93	2.60	3.4659 (19)	155

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x−1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₈O₄
M_r	192.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	3.8201 (7), 15.710 (3), 14.196 (2)
β (°)	92.668 (2)
V (Å³)	851.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.27 × 0.20 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.969, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	4781, 1586, 1272
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.094, 1.04
No. of reflections	1586
No. of parameters	131
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.14

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick 2008), SHELXTL (Sheldrick 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.82	1.96	2.7225 (15)	155.3
C5—H5···O4ⁱⁱ	0.93	2.60	3.4659 (19)	155

Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) −x−1, −y+1, −z+1.

Acknowledgements

The authors 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) and the Youthful Fund of Guangdong Medical College (No. XQ0511).

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