Oosporein from Tremella fuciformis

He, G.; Yan, J.; Wu, X.-Y.; Gou, X.-J.; Li, W.-C.

doi:10.1107/S1600536812012950

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1231

doi:10.1107/S1600536812012950

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Oosporein from Tremella fuciformis

Gang He,^a Jun Yan,^b Xiao-Yong Wu,^b Xiao-Jun Gou ^b and Wan-Chen Li ^a ^*

^aMaize Research Institute, Sichuan Agricultural University, Chengdu 611130, People's Republic of China, and ^bThe Key Laboratory of Medicinal and Edible Plants Resources Development of Sichuan Education Commission, Chengdu University, Chengdu 610106, People's Republic of China
^*Correspondence e-mail: lwc0011@yahoo.cn

(Received 16 March 2012; accepted 24 March 2012; online 31 March 2012)

The title compound [systematic name: 3,3′,6,6′-tetrahydroxy-4,4′-dimethyl-1,1′-bi(cyclohexa-3,6-diene)-2,2′,5,5′-tetraone], C₁₄H₁₀O₈, was isolated from Tremella fuciformis. The molecule has 2 symmetry, with the mid-point of the C—C bond linking the cyclohexadienedione rings located on a twofold rotation axis. In the molecule, the ring is approximately planar, with an r.m.s. deviation of 0.0093 Å, and the two rings make a dihedral angle of 67.89 (5)°. Intermolecular O—H⋯O hydrogen bonding occurs in the crystal structure.

Related literature

For general background to the title compound, see: Takeshita & Anchel (1965 ). For the chemical structure of the title compound established from NMR data, see: Richard et al. (1974 ).

Experimental

Crystal data

C₁₄H₁₀O₈
M_r = 306.22
Monoclinic, C 2/c
a = 11.9983 (9) Å
b = 8.2981 (6) Å
c = 13.7634 (11) Å
β = 105.994 (7)°
V = 1317.28 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
2848 measured reflections
1342 independent reflections
937 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.118
S = 1.06
1342 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4ⁱ	0.82	2.03	2.770 (2)	150
O3—H3⋯O1ⁱⁱ	0.82	2.03	2.7658 (19)	150
Symmetry codes: (i) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812012950/xu5486sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012950/xu5486Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812012950/xu5486Isup3.cml

checkCIF report

Comment top

The oosporein was previously isolated from Phlebia mellea (Takeshita & Anchel, 1965), and its structure was established from the spectroscopic data (Richard et al., 1974). In our recent investigation, it was isolated from Tremella fuciformis for the first time, and its structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. The molecule of the title compound contains two plane six-membered rings which assumes a screw-plane conformation, and there is a dihedral angle between the two planes.

The crystal structure contains intermolecular O—H···O hydrogen bonding between the hydroxy group and the aldehyde atom (Table 1).

Related literature top

For general background to the title compound, see: Takeshita & Anchel (1965). For the chemical structure of the title compound established from NMR data, see: Richard et al. (1974).

Experimental top

Tremella fuciformis was a culture collection of our laboratory, the stock culture was maintained on potato dextrose agar (PDA) slants and subcultured once a month. It was used in submerged culture. Agar, slants containing potato–dextrose–agar were inoculated with mycelia and incubated at 25 °C for 5 days, and then used as inoculums for seed culture. The seed culture was grown in 250 ml shake flasks containing 50 ml for 2 days at initial pH 6.8–7.0, 25 °C, and 150 rpm with a medium containing 20 g.l^-1 glucose, 2 g.l^-1 soybean meal leaching solution, 1.0 g.l^-1 MgSO₄, 1.0 g.l^-1 KH₂PO₄ and 0.46 g.l^-1 K₂HPO₄. Submerged fermentation was the same as the seed culture medium. All media were sterilized at 115 °C for 20 min. Fermentation liquid centrifugal (10000 rpm) and then rotary evaporation at 50 °C. Fermented liquid was concentrated by rotating evaporation at 50°C and add 4 times the volume of the anhydrous alcohol, 4 °C for the night precipitation, 10000 rmp centrifugal remove polysaccharides and protein. Rotated evaporation and concentration, concentrate on D101 macroporous resin adsorption, first washed with distilled water, then elution with 95% ethanol elution, eluent was saved at 4°C, to obtain crud crystals, crud crystals washing was 95% ethanol, and then recrystallized in 95% ethanol solution.

Structure description top

The crystal structure contains intermolecular O—H···O hydrogen bonding between the hydroxy group and the aldehyde atom (Table 1).

For general background to the title compound, see: Takeshita & Anchel (1965). For the chemical structure of the title compound established from NMR data, see: Richard et al. (1974).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms.

3,3',6,6'-tetrahydroxy-4,4'-dimethyl-1,1'-bi(cyclohexa-3,6-diene)-2,2',5,5'- tetraone top

Crystal data top

C₁₄H₁₀O₈	F(000) = 632
M_r = 306.22	D_x = 1.544 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9983 (9) Å	Cell parameters from 884 reflections
b = 8.2981 (6) Å	θ = 3.0–28.7°
c = 13.7634 (11) Å	µ = 0.13 mm⁻¹
β = 105.994 (7)°	T = 293 K
V = 1317.28 (17) Å³	Block, colorless
Z = 4	0.25 × 0.20 × 0.20 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	937 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 26.4°, θ_min = 3.0°
Detector resolution: 10.0 pixels mm^-1	h = −14→11
ω scans	k = −9→10
2848 measured reflections	l = −17→13
1342 independent reflections

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0491P)² + 0.4579P] where P = (F_o² + 2F_c²)/3
1342 reflections	(Δ/σ)_max < 0.001
103 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₄H₁₀O₈	V = 1317.28 (17) Å³
M_r = 306.22	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.9983 (9) Å	µ = 0.13 mm⁻¹
b = 8.2981 (6) Å	T = 293 K
c = 13.7634 (11) Å	0.25 × 0.20 × 0.20 mm
β = 105.994 (7)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	937 reflections with I > 2σ(I)
2848 measured reflections	R_int = 0.022
1342 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
1342 reflections	Δρ_min = −0.17 e Å⁻³
103 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.82546 (12)	0.06885 (18)	0.65807 (11)	0.0380 (4)
O2	0.79548 (13)	0.0605 (2)	0.45935 (11)	0.0434 (5)
H2	0.7623	0.0135	0.4958	0.065*
O3	1.16014 (12)	0.3820 (2)	0.71051 (11)	0.0402 (5)
H3	1.1965	0.4229	0.6744	0.060*
O4	1.12577 (13)	0.3814 (2)	0.51152 (12)	0.0454 (5)
C1	0.95888 (17)	0.2202 (2)	0.47435 (15)	0.0275 (5)
C2	0.88498 (16)	0.1437 (2)	0.51643 (15)	0.0274 (5)
C3	0.89706 (16)	0.1438 (2)	0.62776 (15)	0.0259 (5)
C4	0.99324 (15)	0.2298 (2)	0.69505 (14)	0.0232 (5)
C5	1.06929 (16)	0.3034 (2)	0.65361 (15)	0.0267 (5)
C6	1.05442 (17)	0.3056 (2)	0.54165 (16)	0.0284 (5)
C7	0.9473 (2)	0.2204 (3)	0.36334 (16)	0.0399 (6)
H7A	0.9064	0.1254	0.3332	0.060*
H7B	1.0229	0.2215	0.3525	0.060*
H7C	0.9050	0.3144	0.3331	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0323 (8)	0.0499 (10)	0.0336 (9)	−0.0172 (7)	0.0120 (7)	0.0003 (7)
O2	0.0398 (9)	0.0616 (12)	0.0274 (9)	−0.0259 (8)	0.0069 (7)	−0.0044 (8)
O3	0.0339 (9)	0.0544 (11)	0.0309 (9)	−0.0219 (7)	0.0066 (7)	−0.0014 (8)
O4	0.0416 (9)	0.0618 (11)	0.0351 (10)	−0.0259 (8)	0.0146 (7)	−0.0008 (8)
C1	0.0264 (10)	0.0320 (12)	0.0243 (11)	−0.0007 (9)	0.0074 (8)	−0.0006 (9)
C2	0.0236 (10)	0.0315 (12)	0.0259 (12)	−0.0045 (9)	0.0047 (8)	−0.0013 (9)
C3	0.0227 (10)	0.0269 (11)	0.0286 (12)	0.0003 (8)	0.0080 (8)	0.0034 (8)
C4	0.0223 (10)	0.0247 (11)	0.0227 (11)	0.0019 (8)	0.0064 (8)	0.0009 (8)
C5	0.0220 (10)	0.0289 (11)	0.0274 (12)	−0.0033 (8)	0.0040 (8)	−0.0019 (9)
C6	0.0260 (11)	0.0299 (12)	0.0313 (12)	−0.0024 (9)	0.0112 (9)	0.0018 (9)
C7	0.0424 (13)	0.0499 (15)	0.0291 (13)	−0.0063 (11)	0.0125 (10)	−0.0024 (11)

Geometric parameters (Å, º) top

O1—C3	1.223 (2)	C2—C3	1.499 (3)
O2—C2	1.335 (2)	C3—C4	1.452 (3)
O2—H2	0.8200	C4—C5	1.348 (3)
O3—C5	1.325 (2)	C4—C4ⁱ	1.476 (4)
O3—H3	0.8200	C5—C6	1.502 (3)
O4—C6	1.223 (2)	C7—H7A	0.9600
C1—C2	1.344 (3)	C7—H7B	0.9600
C1—C6	1.445 (3)	C7—H7C	0.9600
C1—C7	1.496 (3)

C2—O2—H2	109.5	C3—C4—C4ⁱ	119.81 (18)
C5—O3—H3	109.5	O3—C5—C4	121.01 (18)
C2—C1—C6	117.14 (18)	O3—C5—C6	116.50 (17)
C2—C1—C7	123.62 (18)	C4—C5—C6	122.46 (17)
C6—C1—C7	119.24 (18)	O4—C6—C1	122.71 (19)
O2—C2—C1	120.65 (18)	O4—C6—C5	117.24 (18)
O2—C2—C3	115.94 (16)	C1—C6—C5	120.04 (17)
C1—C2—C3	123.41 (17)	C1—C7—H7A	109.5
O1—C3—C4	122.79 (19)	C1—C7—H7B	109.5
O1—C3—C2	117.97 (17)	H7A—C7—H7B	109.5
C4—C3—C2	119.23 (17)	C1—C7—H7C	109.5
C5—C4—C3	117.65 (18)	H7A—C7—H7C	109.5
C5—C4—C4ⁱ	122.51 (19)	H7B—C7—H7C	109.5

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4ⁱⁱ	0.82	2.03	2.770 (2)	150
O3—H3···O1ⁱⁱⁱ	0.82	2.03	2.7658 (19)	150

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀O₈
M_r	306.22
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	11.9983 (9), 8.2981 (6), 13.7634 (11)
β (°)	105.994 (7)
V (Å³)	1317.28 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2848, 1342, 937
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.118, 1.06
No. of reflections	1342
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.17

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4ⁱ	0.82	2.03	2.770 (2)	149.7
O3—H3···O1ⁱⁱ	0.82	2.03	2.7658 (19)	149.9

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

Acknowledgements

This project was supported by the Chengdu University Research Fund (No. 2010XJZ23).

References

Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Richard, J. C., Jerry, W. K., Horace, G. C. & Elemer, E. D. (1974). J. Agric. Food Chem, 22, 517–520. PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takeshita, H. & Anchel, M. (1965). Science, 147, 152–153. CrossRef PubMed CAS Web of Science Google Scholar