Neoaustin: a meroterpene produced by Penicillium sp.

Zukerman-Schpector, J.; Maganhi, S.H.; Fill, T.P.; Rodrigues-Fo, E.; Caracelli, I.

doi:10.1107/S1600536809006618

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o612

doi:10.1107/S1600536809006618

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Neoaustin: a meroterpene produced by Penicillium sp.

Julio Zukerman-Schpector,^a ^* Stella H. Maganhi,^a Taicia Pacheco Fill,^a Edson Rodrigues-Fo ^a and Ignez Caracelli ^b

^aDepartment of Chemistry, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, and ^bPhysics Department, Universidade Estadual Paulista, "Júlio de Mesquita Filho", UNESP, 17033-360 Bauru, SP, Brazil
^*Correspondence e-mail: julio@power.ufscar.br

(Received 15 February 2009; accepted 23 February 2009; online 25 February 2009)

The title meroterpene neoaustin {systematic name: (1′S,2′R,3S,7′R,9′S,11′S,12′R)-11′-hydroxy-2,2,2′,9′,12′-pentamethyl-6′,15′-dimethylene-2,6-dihydro-13′-oxaspiro[pyran-3,5′-tetracyclo[7.5.1.0^1,11.0^2,7]pentadecane]-6,10′,14′-trione}, C₂₅H₃₀O₆, comprises five rings, three six-membered and two five-membered. The absolute configuration was established based on [α_D] = +166.91° (c 1.21, CH₂Cl₂). In the crystal, the molecules are connected into a supramolecular helical chain via O—H⋯O hydrogen bonds reinforced by C—H⋯O contacts.

Related literature

For related literature, see: dos Santos & Rodrigues-Fo (2002 , 2003 ); Maganhi et al. 2009 . For ring conformation analysis, see: Cremer & Pople (1975 ); Iulek & Zukerman-Schpector (1997 ).

Experimental

Crystal data

C₂₅H₃₀O₆
M_r = 426.49
Orthorhombic, P 2₁ 2₁ 2₁
a = 11.2152 (4) Å
b = 13.2870 (5) Å
c = 14.3914 (7) Å
V = 2144.55 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 290 K
0.49 × 0.39 × 0.21 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: none
18157 measured reflections
2622 independent reflections
2453 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.106
S = 1.07
2622 reflections
286 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1O4⋯O2ⁱ	0.82	2.06	2.852 (3)	162
C5—H5⋯O3ⁱⁱ	0.93	2.63	3.386 (3)	139
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ .

Data collection: APEX2, COSMO and BIS (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006618/tk2374sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006618/tk2374Isup2.hkl

checkCIF report

Comment top

Endophytic fungi live in very intimate association with plant tissue and can produce compounds similar and sometimes identical to those produced by the host plant. Thus, fungi have been a rich source of important biologically active secondary metabolites, such as meroterpenoids, a class of complex metabolites derived from a mixed terpenoid-polyketide biosynthetic pathway. During an on-going study of substances produced by endophytic fungi, the title compound (I) was isolated and its structure postulated based on APCIMS (Atmospheric Pressure Chemical Ionization Mass Spectrometry) and a variety of NMR studies (dos Santos and Rodrigues-Fo, 2003). As suitable crystals were subsequently obtained, a crystal structure determination of (I) was undertaken, Fig. 1. The three six-membered rings are in different distorted conformations. Referring to the labels in Scheme 1, ring A is in a highly distorted half-boat conformation, ring B in a slightly distorted chair, and ring C is in a chair distorted towards a half-chair conformation. The five membered rings, D and E, are in a highly distorted envelope and a distorted twist conformation, respectively. The ring-puckering parameters (Cremer & Pople, 1975; Iulek & Zukerman-Schpector, 1997) in the order for A, B, C, D and E (when applicable) are: q₂ = 0.434 (2), 0.044 (2), 0.161 (2), 0.562 (2), 0.284 (2) Å, q₃ = 0.241 (2), 0.552 (2), -0.650 (2) Å, Q = 0.496 (2), 0.554 (2), 0.669 (2)°, ϕ₂ =-73.0 (3), -36 (3), 146.7 (7), -154.3 (3), 25.1 (5)°, and θ₂ = 60.9 (3), 4.5 (2), 166.1 (2)°. The absolute configuration was established based on the [α_D] = +166.914.97° (c 1.21, CH₂Cl₂) and the results reported in dos Santos and Rodrigues-Fo (2003). The molecules are linked via O-H···O hydrogen bonds, Fig. 2. which extend into a supramolecular helical chain which is reinforced via C-H···O contacts (Table 1).

Related literature top

For related literature, see: dos Santos & Rodrigues-Fo (2002, 2003); Maganhi et al. 2009. For structural analysis, see: Cremer & Pople (1975); Iulek & Zukerman-Schpector (1997).

Experimental top

Compound (I), Neoaustin, was produced during cultivation of the fungus Penicillum sp over sterilized rice, and isolated from the methanol extract of the culture. Suitable crystals were obtained, by slow evaporation, from a mixture of dichloromethane, methanol and water.

Computing details top

Data collection: APEX2, COSMO and BIS (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of (I) showing atom labelling scheme and displacement ellipsoids at the 30% probability level (arbitrary spheres for the H atoms).
	Fig. 2. Detail of the hydrogen bonding in (I). Hydrogen bonds are shown as hollow dashed bonds. See Table 1 for symmetry operations.

(1'S,2'R,3S,7'R,9'S,11'S, 12'R)-11'-hydroxy-2,2,2',9',12'-pentamethyl-6',15'-dimethylene-2,6- dihydro-13'-oxaspiro[pyran-3,5'-tetracyclo[7.5.1.0^1,11.0^2,7]pentadecane]- 6,10',14'-trione top

Crystal data top

C₂₅H₃₀O₆	F(000) = 912
M_r = 426.49	D_x = 1.321 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 33851 reflections
a = 11.2152 (4) Å	θ = 1.0–27.4°
b = 13.2870 (5) Å	µ = 0.09 mm⁻¹
c = 14.3914 (7) Å	T = 290 K
V = 2144.55 (15) Å³	Prism, colorless
Z = 4	0.49 × 0.39 × 0.21 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2453 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Graphite monochromator	θ_max = 27.0°, θ_min = 3.2°
ϕ and ω scans	h = −14→14
18157 measured reflections	k = −15→16
2622 independent reflections	l = −17→18

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0607P)² + 0.3107P] where P = (F_o² + 2F_c²)/3
2622 reflections	(Δ/σ)_max < 0.001
286 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₅H₃₀O₆	V = 2144.55 (15) Å³
M_r = 426.49	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 11.2152 (4) Å	µ = 0.09 mm⁻¹
b = 13.2870 (5) Å	T = 290 K
c = 14.3914 (7) Å	0.49 × 0.39 × 0.21 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2453 reflections with I > 2σ(I)
18157 measured reflections	R_int = 0.048
2622 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.07	Δρ_max = 0.17 e Å⁻³
2622 reflections	Δρ_min = −0.13 e Å⁻³
286 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
C1'	0.32891 (19)	0.90837 (15)	0.67021 (13)	0.0371 (4)
C2'	0.45203 (19)	0.93770 (16)	0.71346 (13)	0.0380 (4)
C2	0.74745 (19)	0.93484 (17)	0.92112 (15)	0.0425 (5)
C3'	0.5381 (2)	0.84818 (18)	0.71741 (15)	0.0462 (5)
H3'A	0.5613	0.8301	0.6546	0.055*
H3'B	0.4973	0.7909	0.7444	0.055*
C4'	0.6507 (2)	0.8705 (2)	0.77441 (16)	0.0485 (5)
H4'A	0.6980	0.9201	0.7415	0.058*
H4'B	0.6977	0.8094	0.7788	0.058*
C4	0.5674 (2)	0.82925 (17)	0.93270 (16)	0.0436 (5)
H4	0.5162	0.7834	0.9046	0.052*
C5	0.5873 (2)	0.82231 (18)	1.02291 (17)	0.0493 (5)
H5	0.5532	0.7698	1.0564	0.059*
C5'	0.62593 (18)	0.90991 (16)	0.87378 (14)	0.0378 (4)
C6	0.66206 (19)	0.89585 (17)	1.07096 (15)	0.0431 (5)
C6'	0.53593 (18)	0.99769 (15)	0.86945 (13)	0.0361 (4)
C7'	0.42380 (18)	0.97177 (15)	0.81504 (13)	0.0346 (4)
H7'	0.3896	0.9127	0.8459	0.041*
C8'	0.32623 (19)	1.05317 (15)	0.81811 (14)	0.0375 (4)
H8'A	0.3586	1.1156	0.7940	0.045*
H8'B	0.3035	1.0647	0.8823	0.045*
C9'	0.21293 (19)	1.02470 (16)	0.76119 (14)	0.0385 (4)
C10'	0.18022 (19)	0.91858 (16)	0.79257 (14)	0.0405 (4)
C11'	0.24352 (19)	0.84332 (16)	0.72965 (14)	0.0402 (5)
C12'	0.1604 (2)	0.79507 (18)	0.65534 (17)	0.0523 (6)
H12'	0.1481	0.7246	0.6731	0.063*
C14'	0.3301 (2)	0.85332 (18)	0.57786 (15)	0.0493 (5)
C15'	0.2536 (2)	1.00412 (16)	0.66311 (14)	0.0385 (4)
C16	0.8344 (2)	0.8465 (2)	0.9222 (2)	0.0571 (6)
H16A	0.7958	0.7885	0.9482	0.086*
H16B	0.9027	0.8636	0.9593	0.086*
H16C	0.8596	0.8319	0.8599	0.086*
C17	0.8129 (2)	1.0257 (2)	0.8822 (2)	0.0573 (6)
H17A	0.8738	1.0463	0.9250	0.086*
H17B	0.7575	1.0799	0.8732	0.086*
H17C	0.8487	1.0083	0.8238	0.086*
C18	0.5105 (2)	1.0233 (2)	0.65818 (16)	0.0507 (5)
H18A	0.5192	1.0033	0.5944	0.076*
H18B	0.5875	1.0379	0.6840	0.076*
H18C	0.4613	1.0823	0.6615	0.076*
C19	0.5471 (2)	1.08493 (18)	0.91461 (17)	0.0516 (5)
H19A	0.4854	1.1317	0.9133	0.062*
H19B	0.6166	1.0990	0.9474	0.062*
C20	0.1151 (2)	1.10233 (19)	0.77492 (17)	0.0498 (5)
H20A	0.0473	1.0847	0.7375	0.075*
H20B	0.1439	1.1674	0.7567	0.075*
H20C	0.0922	1.1039	0.8392	0.075*
C21	0.0390 (3)	0.8406 (2)	0.6378 (2)	0.0641 (7)
H21A	−0.0015	0.8026	0.5906	0.096*
H21B	0.0481	0.9090	0.6176	0.096*
H21C	−0.0069	0.8391	0.6941	0.096*
C22	0.2290 (3)	1.05608 (19)	0.58737 (17)	0.0557 (6)
H22A	0.1811	1.1131	0.5910	0.067*
H22B	0.2596	1.0357	0.5303	0.067*
O1	0.72595 (13)	0.95988 (11)	1.02022 (10)	0.0418 (3)
O2	0.66745 (17)	0.90141 (15)	1.15505 (11)	0.0577 (4)
O3	0.11959 (17)	0.89618 (14)	0.85870 (12)	0.0583 (5)
O4	0.30164 (16)	0.76719 (12)	0.78090 (12)	0.0516 (4)
H1O4	0.2520	0.7281	0.8019	0.062*
O5	0.23077 (19)	0.79543 (15)	0.57041 (12)	0.0613 (5)
O6	0.4016 (2)	0.85761 (16)	0.51643 (11)	0.0659 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1'	0.0436 (10)	0.0378 (9)	0.0299 (8)	−0.0005 (9)	0.0004 (9)	0.0024 (7)
C2'	0.0402 (10)	0.0421 (10)	0.0317 (9)	0.0003 (9)	0.0038 (8)	−0.0007 (8)
C2	0.0336 (10)	0.0503 (12)	0.0435 (11)	0.0003 (9)	0.0020 (9)	0.0028 (9)
C3'	0.0464 (12)	0.0499 (12)	0.0422 (11)	0.0090 (10)	0.0022 (10)	−0.0110 (9)
C4'	0.0429 (11)	0.0544 (12)	0.0482 (12)	0.0104 (10)	0.0038 (10)	−0.0104 (10)
C4	0.0383 (10)	0.0390 (10)	0.0535 (12)	−0.0006 (9)	−0.0035 (10)	0.0038 (9)
C5	0.0471 (12)	0.0477 (12)	0.0531 (12)	−0.0053 (10)	−0.0009 (11)	0.0148 (10)
C5'	0.0334 (9)	0.0408 (10)	0.0393 (10)	0.0018 (8)	0.0004 (8)	0.0023 (8)
C6	0.0386 (10)	0.0461 (11)	0.0445 (11)	0.0052 (9)	−0.0007 (9)	0.0082 (9)
C6'	0.0365 (9)	0.0385 (10)	0.0332 (9)	0.0030 (8)	0.0015 (8)	0.0028 (7)
C7'	0.0360 (9)	0.0357 (9)	0.0320 (9)	0.0027 (8)	0.0024 (7)	0.0013 (7)
C8'	0.0384 (10)	0.0386 (10)	0.0356 (9)	0.0036 (9)	0.0000 (8)	−0.0013 (7)
C9'	0.0373 (10)	0.0412 (10)	0.0369 (9)	0.0012 (8)	−0.0006 (8)	0.0029 (8)
C10'	0.0387 (10)	0.0460 (11)	0.0368 (10)	−0.0025 (9)	−0.0023 (9)	0.0045 (9)
C11'	0.0440 (11)	0.0361 (10)	0.0405 (10)	−0.0009 (9)	−0.0015 (9)	0.0073 (8)
C12'	0.0624 (14)	0.0418 (11)	0.0526 (12)	−0.0092 (11)	−0.0059 (12)	−0.0023 (10)
C14'	0.0629 (14)	0.0479 (12)	0.0372 (10)	0.0058 (11)	−0.0052 (11)	−0.0036 (9)
C15'	0.0431 (10)	0.0366 (10)	0.0358 (9)	−0.0009 (8)	−0.0033 (9)	0.0025 (8)
C16	0.0382 (11)	0.0655 (15)	0.0676 (15)	0.0106 (11)	−0.0022 (12)	−0.0038 (13)
C17	0.0458 (12)	0.0654 (15)	0.0607 (14)	−0.0140 (12)	0.0047 (12)	0.0108 (12)
C18	0.0514 (12)	0.0591 (13)	0.0416 (11)	−0.0083 (11)	0.0096 (11)	0.0053 (10)
C19	0.0544 (13)	0.0462 (12)	0.0543 (12)	0.0071 (11)	−0.0140 (11)	−0.0064 (10)
C20	0.0426 (11)	0.0535 (13)	0.0533 (12)	0.0095 (11)	−0.0022 (11)	0.0008 (10)
C21	0.0595 (15)	0.0670 (16)	0.0657 (16)	−0.0123 (14)	−0.0194 (13)	−0.0019 (13)
C22	0.0767 (17)	0.0485 (12)	0.0418 (11)	0.0053 (12)	−0.0051 (12)	0.0092 (10)
O1	0.0388 (7)	0.0459 (8)	0.0405 (7)	−0.0034 (7)	−0.0043 (6)	0.0034 (6)
O2	0.0596 (10)	0.0723 (11)	0.0413 (8)	0.0051 (10)	0.0001 (8)	0.0080 (8)
O3	0.0566 (10)	0.0651 (11)	0.0531 (9)	−0.0069 (9)	0.0156 (9)	0.0095 (8)
O4	0.0579 (9)	0.0399 (8)	0.0569 (9)	−0.0017 (7)	−0.0022 (8)	0.0156 (7)
O5	0.0738 (12)	0.0619 (10)	0.0482 (9)	−0.0079 (10)	−0.0056 (9)	−0.0151 (8)
O6	0.0809 (13)	0.0804 (13)	0.0363 (8)	0.0021 (11)	0.0085 (9)	−0.0096 (8)

Geometric parameters (Å, º) top

C1'—C14'	1.517 (3)	C9'—C20	1.519 (3)
C1'—C15'	1.530 (3)	C9'—C10'	1.525 (3)
C1'—C11'	1.548 (3)	C10'—O3	1.207 (3)
C1'—C2'	1.564 (3)	C10'—C11'	1.524 (3)
C2'—C3'	1.533 (3)	C11'—O4	1.411 (3)
C2'—C18	1.535 (3)	C11'—C12'	1.557 (3)
C2'—C7'	1.563 (3)	C12'—O5	1.455 (3)
C2—O1	1.484 (3)	C12'—C21	1.511 (4)
C2—C17	1.520 (3)	C12'—H12'	0.9800
C2—C16	1.526 (3)	C14'—O6	1.195 (3)
C2—C5'	1.559 (3)	C14'—O5	1.358 (3)
C3'—C4'	1.534 (3)	C15'—C22	1.319 (3)
C3'—H3'A	0.9700	C16—H16A	0.9600
C3'—H3'B	0.9700	C16—H16B	0.9600
C4'—C5'	1.548 (3)	C16—H16C	0.9600
C4'—H4'A	0.9700	C17—H17A	0.9600
C4'—H4'B	0.9700	C17—H17B	0.9600
C4—C5	1.321 (3)	C17—H17C	0.9600
C4—C5'	1.516 (3)	C18—H18A	0.9600
C4—H4	0.9300	C18—H18B	0.9600
C5—C6	1.461 (3)	C18—H18C	0.9600
C5—H5	0.9300	C19—H19A	0.9300
C5'—C6'	1.544 (3)	C19—H19B	0.9300
C6—O2	1.214 (3)	C20—H20A	0.9600
C6—O1	1.331 (3)	C20—H20B	0.9600
C6'—C19	1.335 (3)	C20—H20C	0.9600
C6'—C7'	1.521 (3)	C21—H21A	0.9600
C7'—C8'	1.539 (3)	C21—H21B	0.9600
C7'—H7'	0.9800	C21—H21C	0.9600
C8'—C9'	1.558 (3)	C22—H22A	0.9300
C8'—H8'A	0.9700	C22—H22B	0.9300
C8'—H8'B	0.9700	O4—H1O4	0.8200
C9'—C15'	1.508 (3)

C14'—C1'—C15'	110.33 (17)	C15'—C9'—C8'	106.81 (17)
C14'—C1'—C11'	102.75 (18)	C20—C9'—C8'	110.84 (17)
C15'—C1'—C11'	99.19 (16)	C10'—C9'—C8'	105.36 (16)
C14'—C1'—C2'	117.43 (19)	O3—C10'—C11'	124.7 (2)
C15'—C1'—C2'	107.85 (16)	O3—C10'—C9'	126.7 (2)
C11'—C1'—C2'	117.74 (16)	C11'—C10'—C9'	108.57 (16)
C3'—C2'—C18	108.96 (18)	O4—C11'—C10'	112.01 (17)
C3'—C2'—C7'	108.52 (16)	O4—C11'—C1'	113.78 (18)
C18—C2'—C7'	110.90 (17)	C10'—C11'—C1'	104.48 (16)
C3'—C2'—C1'	112.18 (17)	O4—C11'—C12'	109.90 (18)
C18—C2'—C1'	110.82 (17)	C10'—C11'—C12'	113.54 (18)
C7'—C2'—C1'	105.40 (16)	C1'—C11'—C12'	102.76 (17)
O1—C2—C17	104.74 (19)	O5—C12'—C21	110.3 (2)
O1—C2—C16	105.43 (18)	O5—C12'—C11'	104.53 (18)
C17—C2—C16	107.8 (2)	C21—C12'—C11'	119.3 (2)
O1—C2—C5'	108.99 (16)	O5—C12'—H12'	107.4
C17—C2—C5'	115.45 (19)	C21—C12'—H12'	107.4
C16—C2—C5'	113.58 (19)	C11'—C12'—H12'	107.4
C2'—C3'—C4'	112.83 (18)	O6—C14'—O5	121.3 (2)
C2'—C3'—H3'A	109.0	O6—C14'—C1'	129.2 (2)
C4'—C3'—H3'A	109.0	O5—C14'—C1'	109.5 (2)
C2'—C3'—H3'B	109.0	C22—C15'—C9'	127.9 (2)
C4'—C3'—H3'B	109.0	C22—C15'—C1'	127.3 (2)
H3'A—C3'—H3'B	107.8	C9'—C15'—C1'	104.78 (16)
C3'—C4'—C5'	114.33 (18)	C2—C16—H16A	109.5
C3'—C4'—H4'A	108.7	C2—C16—H16B	109.5
C5'—C4'—H4'A	108.7	H16A—C16—H16B	109.5
C3'—C4'—H4'B	108.7	C2—C16—H16C	109.5
C5'—C4'—H4'B	108.7	H16A—C16—H16C	109.5
H4'A—C4'—H4'B	107.6	H16B—C16—H16C	109.5
C5—C4—C5'	121.8 (2)	C2—C17—H17A	109.5
C5—C4—H4	119.1	C2—C17—H17B	109.5
C5'—C4—H4	119.1	H17A—C17—H17B	109.5
C4—C5—C6	121.0 (2)	C2—C17—H17C	109.5
C4—C5—H5	119.5	H17A—C17—H17C	109.5
C6—C5—H5	119.5	H17B—C17—H17C	109.5
C4—C5'—C6'	105.89 (16)	C2'—C18—H18A	109.5
C4—C5'—C4'	110.80 (19)	C2'—C18—H18B	109.5
C6'—C5'—C4'	109.60 (16)	H18A—C18—H18B	109.5
C4—C5'—C2	106.50 (17)	C2'—C18—H18C	109.5
C6'—C5'—C2	115.38 (18)	H18A—C18—H18C	109.5
C4'—C5'—C2	108.59 (17)	H18B—C18—H18C	109.5
O2—C6—O1	118.8 (2)	C6'—C19—H19A	120.0
O2—C6—C5	122.7 (2)	C6'—C19—H19B	120.0
O1—C6—C5	118.5 (2)	H19A—C19—H19B	120.0
C19—C6'—C7'	121.66 (19)	C9'—C20—H20A	109.5
C19—C6'—C5'	125.1 (2)	C9'—C20—H20B	109.5
C7'—C6'—C5'	112.97 (16)	H20A—C20—H20B	109.5
C6'—C7'—C8'	114.45 (16)	C9'—C20—H20C	109.5
C6'—C7'—C2'	112.31 (16)	H20A—C20—H20C	109.5
C8'—C7'—C2'	111.99 (15)	H20B—C20—H20C	109.5
C6'—C7'—H7'	105.8	C12'—C21—H21A	109.5
C8'—C7'—H7'	105.8	C12'—C21—H21B	109.5
C2'—C7'—H7'	105.8	H21A—C21—H21B	109.5
C7'—C8'—C9'	113.20 (16)	C12'—C21—H21C	109.5
C7'—C8'—H8'A	108.9	H21A—C21—H21C	109.5
C9'—C8'—H8'A	108.9	H21B—C21—H21C	109.5
C7'—C8'—H8'B	108.9	C15'—C22—H22A	120.0
C9'—C8'—H8'B	108.9	C15'—C22—H22B	120.0
H8'A—C8'—H8'B	107.8	H22A—C22—H22B	120.0
C15'—C9'—C20	117.60 (18)	C6—O1—C2	118.14 (18)
C15'—C9'—C10'	100.50 (17)	C11'—O4—H1O4	109.5
C20—C9'—C10'	114.55 (18)	C14'—O5—C12'	112.37 (17)

C14'—C1'—C2'—C3'	−50.6 (2)	C20—C9'—C10'—O3	−36.0 (3)
C15'—C1'—C2'—C3'	−175.97 (16)	C8'—C9'—C10'—O3	86.1 (3)
C11'—C1'—C2'—C3'	73.0 (2)	C15'—C9'—C10'—C11'	20.4 (2)
C14'—C1'—C2'—C18	71.4 (2)	C20—C9'—C10'—C11'	147.45 (18)
C15'—C1'—C2'—C18	−53.9 (2)	C8'—C9'—C10'—C11'	−90.46 (18)
C11'—C1'—C2'—C18	−164.97 (19)	O3—C10'—C11'—O4	−44.7 (3)
C14'—C1'—C2'—C7'	−168.55 (17)	C9'—C10'—C11'—O4	131.88 (18)
C15'—C1'—C2'—C7'	66.12 (19)	O3—C10'—C11'—C1'	−168.3 (2)
C11'—C1'—C2'—C7'	−44.9 (2)	C9'—C10'—C11'—C1'	8.3 (2)
C18—C2'—C3'—C4'	66.8 (2)	O3—C10'—C11'—C12'	80.5 (3)
C7'—C2'—C3'—C4'	−54.1 (2)	C9'—C10'—C11'—C12'	−102.9 (2)
C1'—C2'—C3'—C4'	−170.11 (17)	C14'—C1'—C11'—O4	91.2 (2)
C2'—C3'—C4'—C5'	53.4 (3)	C15'—C1'—C11'—O4	−155.36 (17)
C5'—C4—C5—C6	3.3 (4)	C2'—C1'—C11'—O4	−39.5 (3)
C5—C4—C5'—C6'	−94.1 (3)	C14'—C1'—C11'—C10'	−146.31 (17)
C5—C4—C5'—C4'	147.1 (2)	C15'—C1'—C11'—C10'	−32.90 (19)
C5—C4—C5'—C2	29.2 (3)	C2'—C1'—C11'—C10'	83.0 (2)
C3'—C4'—C5'—C4	66.5 (2)	C14'—C1'—C11'—C12'	−27.5 (2)
C3'—C4'—C5'—C6'	−50.0 (3)	C15'—C1'—C11'—C12'	85.88 (19)
C3'—C4'—C5'—C2	−176.87 (19)	C2'—C1'—C11'—C12'	−158.27 (17)
O1—C2—C5'—C4	−53.3 (2)	O4—C11'—C12'—O5	−96.7 (2)
C17—C2—C5'—C4	−170.8 (2)	C10'—C11'—C12'—O5	137.02 (18)
C16—C2—C5'—C4	63.9 (2)	C1'—C11'—C12'—O5	24.8 (2)
O1—C2—C5'—C6'	63.9 (2)	O4—C11'—C12'—C21	139.5 (2)
C17—C2—C5'—C6'	−53.6 (3)	C10'—C11'—C12'—C21	13.2 (3)
C16—C2—C5'—C6'	−178.92 (18)	C1'—C11'—C12'—C21	−99.0 (2)
O1—C2—C5'—C4'	−172.67 (17)	C15'—C1'—C14'—O6	94.9 (3)
C17—C2—C5'—C4'	69.8 (3)	C11'—C1'—C14'—O6	−160.1 (3)
C16—C2—C5'—C4'	−55.5 (2)	C2'—C1'—C14'—O6	−29.2 (4)
C4—C5—C6—O2	168.2 (2)	C15'—C1'—C14'—O5	−83.3 (2)
C4—C5—C6—O1	−11.2 (3)	C11'—C1'—C14'—O5	21.7 (2)
C4—C5'—C6'—C19	106.6 (2)	C2'—C1'—C14'—O5	152.63 (18)
C4'—C5'—C6'—C19	−133.8 (2)	C20—C9'—C15'—C22	11.9 (4)
C2—C5'—C6'—C19	−10.9 (3)	C10'—C9'—C15'—C22	136.9 (3)
C4—C5'—C6'—C7'	−67.6 (2)	C8'—C9'—C15'—C22	−113.4 (3)
C4'—C5'—C6'—C7'	51.9 (2)	C20—C9'—C15'—C1'	−167.42 (19)
C2—C5'—C6'—C7'	174.84 (16)	C10'—C9'—C15'—C1'	−42.4 (2)
C19—C6'—C7'—C8'	−0.8 (3)	C8'—C9'—C15'—C1'	67.3 (2)
C5'—C6'—C7'—C8'	173.68 (16)	C14'—C1'—C15'—C22	−24.3 (3)
C19—C6'—C7'—C2'	128.4 (2)	C11'—C1'—C15'—C22	−131.7 (3)
C5'—C6'—C7'—C2'	−57.2 (2)	C2'—C1'—C15'—C22	105.1 (3)
C3'—C2'—C7'—C6'	56.4 (2)	C14'—C1'—C15'—C9'	154.94 (19)
C18—C2'—C7'—C6'	−63.2 (2)	C11'—C1'—C15'—C9'	47.58 (19)
C1'—C2'—C7'—C6'	176.80 (16)	C2'—C1'—C15'—C9'	−75.61 (19)
C3'—C2'—C7'—C8'	−173.15 (17)	O2—C6—O1—C2	162.3 (2)
C18—C2'—C7'—C8'	67.2 (2)	C5—C6—O1—C2	−18.3 (3)
C1'—C2'—C7'—C8'	−52.8 (2)	C17—C2—O1—C6	175.49 (19)
C6'—C7'—C8'—C9'	179.61 (16)	C16—C2—O1—C6	−70.9 (2)
C2'—C7'—C8'—C9'	50.3 (2)	C5'—C2—O1—C6	51.4 (2)
C7'—C8'—C9'—C15'	−56.7 (2)	O6—C14'—O5—C12'	175.7 (2)
C7'—C8'—C9'—C20	174.05 (17)	C1'—C14'—O5—C12'	−6.0 (3)
C7'—C8'—C9'—C10'	49.6 (2)	C21—C12'—O5—C14'	117.0 (2)
C15'—C9'—C10'—O3	−163.1 (2)	C11'—C12'—O5—C14'	−12.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O2ⁱ	0.82	2.06	2.852 (3)	162
C5—H5···O3ⁱⁱ	0.93	2.63	3.386 (3)	139

Symmetry codes: (i) x−1/2, −y+3/2, −z+2; (ii) x+1/2, −y+3/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₅H₃₀O₆
M_r	426.49
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	290
a, b, c (Å)	11.2152 (4), 13.2870 (5), 14.3914 (7)
V (Å³)	2144.55 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.49 × 0.39 × 0.21

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18157, 2622, 2453
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.106, 1.07
No. of reflections	2622
No. of parameters	286
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.13

Computer programs: APEX2, COSMO and BIS (Bruker, 2006), SAINT (Bruker, 2006), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O2ⁱ	0.82	2.06	2.852 (3)	162
C5—H5···O3ⁱⁱ	0.93	2.63	3.386 (3)	139

Symmetry codes: (i) x−1/2, −y+3/2, −z+2; (ii) x+1/2, −y+3/2, −z+2.

Acknowledgements

We thank FAPESP, CNPq and CAPES for financial support. Publication costs were met by FAPESP (Proc. 2008/02531–5). Professor R. A. Burrow of the Federal University of Santa Maria is gratefully acknowledged for helping with the collection of the intensity data.

References

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