Preaustinoid A: a meroterpene produced by Penicillium sp.

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

doi:10.1107/S1600536808043481

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o221

doi:10.1107/S1600536808043481

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Preaustinoid A: a meroterpene produced by Penicillium sp.

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

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

(Received 17 December 2008; accepted 20 December 2008; online 8 January 2009)

The title meroterpene preaustinoid A (systematic name: methyl 15-hydroxy-2,6,6,10,13,15-hexamethyl-17-methylene-7,14,16-trioxotetracyclo[11.3.1.0^2,11.0^5,10]heptadecane-1-carboxylate), C₂₆H₃₆O₆, features a fused four-ring arrangement. Three rings are in different distorted chair conformations and the other is in a distorted boat conformation. The absolute configuration was established based on [α_D] = −4.97° (c = 1.10 g l⁻¹, CH₂Cl₂). In the crystal, the molecules are connected into supramolecular chains via O—H⋯O hydrogen bonds.

Related literature

For related literature, see: dos Santos & Rodrigues-Fo (2002 ). For structure analysis, see: Cremer and Pople (1975 ); Iulek and Zukerman-Schpector (1997 )).

Experimental

Crystal data

C₂₆H₃₆O₆
M_r = 444.55
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.5023 (2) Å
b = 13.5405 (2) Å
c = 19.7127 (4) Å
V = 2269.43 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 290 (2) K
0.37 × 0.28 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: none
27134 measured reflections
2938 independent reflections
2677 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.093
S = 1.03
2938 reflections
297 parameters
H-atom parameters constrained
Δρ_max = 0.22 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
O5—H1O5⋯O3ⁱ	0.82	2.05	2.870 (2)	173
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043481/tk2346sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043481/tk2346Isup2.hkl

checkCIF report

Comment top

Endophytic fungi have been a rich source of important biologically active secondary metabolites, in particular 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), HREIMS (High Resolution Electrospray Mass Spectrometry) and a variety of NMR studies (dos Santos and Rodrigues-Fo, 2002). As suitable crystals were subsequently obtained, a crystal structure determination was undertaken. The four fused rings are in different distorted conformations. Rings A and C are distorted towards a half-chair conformation, ring B is distorted towards a half-boat conformation, and ring D is a boat conformation that is highly distorted towards a half-boat. The ring-puckering parameters (Cremer & Pople, 1975, Iulek & Zukerman-Shpector, 1997) for rings A,B,C, D are: q₂ = 0.062 (2), 0.093 (2), 0.059 (2), 0.582 (2) Å, q₃ = -0.524 (2), 0.577 (2), -0.624 (2), -0.139 (2) Å, Q = 0.528 (2), 0.584 (2), 0.627 (2), 0.599 (2)°, ϕ₂ = 90 (2), 172 (1), -149 (2), -122.4 (2)°, and θ₂ = 173.3 (2), 9.1 (2), 174.6 (2), 103.4 (2)°, respectively. The absolute configuration was established based on the [α_D] = -4.97° (c 1.10 g/L, CH₂Cl₂) and the results reported in dos Santos & Rodrigues-Fo (2002). The molecules are linked into a supramolecular chain via intermolecular O-H···O hydrogen bonds, Table 1.

Related literature top

For related literature, see: dos Santos & Rodrigues-Fo (2002). For structure analysis, see: Cremer and Pople (1975); Iulek and Zukerman-Schpector (1997).

Experimental top

Compound (I), Preaustinoid A, was produced during cultivation of 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).

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).

methyl 15-hydroxy-2,6,6,10,13,15-hexamethyl-17-methylene-7,14,16- trioxotetracyclo[11.3.1.0^2,11.0^5,10]heptadecane-1-carboxylate top

Crystal data top

C₂₆H₃₆O₆	F(000) = 960
M_r = 444.55	D_x = 1.301 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 22936 reflections
a = 8.5023 (2) Å	θ = 1.0–27.5°
b = 13.5405 (2) Å	µ = 0.09 mm⁻¹
c = 19.7127 (4) Å	T = 290 K
V = 2269.43 (8) Å³	Prism, colorless
Z = 4	0.37 × 0.28 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2677 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 27.5°, θ_min = 1.8°
ϕ and ω scans	h = −11→9
27134 measured reflections	k = −17→17
2938 independent reflections	l = −25→25

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0531P)² + 0.3814P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2938 reflections	Δρ_max = 0.22 e Å⁻³
297 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Absolute structure: [α_D] = -4.97° and results in dos Santos & Rodrigues-Fo (2002)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₆H₃₆O₆	V = 2269.43 (8) Å³
M_r = 444.55	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.5023 (2) Å	µ = 0.09 mm⁻¹
b = 13.5405 (2) Å	T = 290 K
c = 19.7127 (4) Å	0.37 × 0.28 × 0.11 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2677 reflections with I > 2σ(I)
27134 measured reflections	R_int = 0.034
2938 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.03	Δρ_max = 0.22 e Å⁻³
2938 reflections	Δρ_min = −0.13 e Å⁻³
297 parameters	Absolute structure: [α_D] = -4.97° and results in dos Santos & Rodrigues-Fo (2002)

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	0.6598 (2)	1.07289 (12)	1.05643 (9)	0.0288 (4)
C2	0.6226 (2)	1.08110 (12)	0.97653 (9)	0.0285 (4)
C3	0.4489 (2)	1.10698 (14)	0.96387 (10)	0.0339 (4)
H3A	0.3835	1.0666	0.9931	0.041*
H3B	0.4314	1.1756	0.9760	0.041*
C4	0.3986 (2)	1.09105 (13)	0.89014 (10)	0.0335 (4)
H4A	0.4588	1.1343	0.8607	0.040*
H4B	0.2882	1.1076	0.8851	0.040*
C5	0.4252 (2)	0.98347 (13)	0.86909 (9)	0.0281 (4)
H5	0.3789	0.9444	0.9059	0.034*
C6	0.3310 (2)	0.95241 (13)	0.80444 (10)	0.0333 (4)
C7	0.3688 (3)	0.84397 (14)	0.78946 (10)	0.0375 (4)
C8	0.5381 (3)	0.81430 (17)	0.79148 (13)	0.0480 (5)
H8A	0.5925	0.8437	0.7532	0.058*
H8B	0.5456	0.7431	0.7871	0.058*
C9	0.6192 (3)	0.84641 (14)	0.85749 (10)	0.0379 (4)
H9A	0.7299	0.8294	0.8551	0.045*
H9B	0.5736	0.8103	0.8952	0.045*
C10	0.6034 (2)	0.95805 (13)	0.87113 (9)	0.0289 (4)
C11	0.6583 (2)	0.97663 (12)	0.94619 (8)	0.0266 (3)
H11	0.5967	0.9304	0.9737	0.032*
C12	0.8309 (2)	0.94807 (15)	0.95867 (10)	0.0346 (4)
H12A	0.8986	0.9948	0.9355	0.041*
H12B	0.8503	0.8833	0.9394	0.041*
C13	0.8741 (2)	0.94642 (14)	1.03528 (10)	0.0338 (4)
C14	0.7714 (3)	0.86428 (14)	1.06479 (10)	0.0372 (4)
C15	0.6277 (3)	0.89190 (13)	1.10736 (9)	0.0346 (4)
C16	0.5554 (2)	0.99228 (14)	1.08868 (9)	0.0322 (4)
C17	0.8335 (2)	1.04648 (13)	1.06521 (9)	0.0317 (4)
C18	0.6196 (2)	1.16872 (13)	1.09524 (10)	0.0341 (4)
C19	0.5811 (3)	1.23338 (17)	1.20486 (12)	0.0498 (6)
H19A	0.4780	1.2564	1.1928	0.075*
H19B	0.6558	1.2858	1.1989	0.075*
H19C	0.5811	1.2126	1.2514	0.075*
C20	0.7279 (3)	1.16296 (14)	0.94607 (10)	0.0392 (5)
H20A	0.7083	1.2241	0.9692	0.059*
H20B	0.7043	1.1706	0.8987	0.059*
H20C	0.8364	1.1450	0.9513	0.059*
C21	0.1540 (3)	0.96145 (17)	0.81845 (13)	0.0475 (5)
H21A	0.1281	0.9253	0.8588	0.071*
H21B	0.0961	0.9349	0.7808	0.071*
H21C	0.1270	1.0297	0.8245	0.071*
C22	0.3678 (3)	1.01321 (16)	0.74011 (10)	0.0448 (5)
H22A	0.3552	1.0822	0.7498	0.067*
H22B	0.2969	0.9944	0.7044	0.067*
H22C	0.4741	1.0008	0.7261	0.067*
C23	0.7051 (2)	1.01368 (17)	0.81888 (10)	0.0409 (5)
H23A	0.7011	0.9798	0.7761	0.061*
H23B	0.8119	1.0163	0.8346	0.061*
H23C	0.6656	1.0796	0.8134	0.061*
C24	1.0483 (3)	0.91813 (19)	1.04234 (13)	0.0496 (6)
H24A	1.0757	0.9149	1.0895	0.074*
H24B	1.1122	0.9669	1.0203	0.074*
H24C	1.0658	0.8549	1.0216	0.074*
C25	0.5021 (3)	0.81210 (15)	1.10693 (14)	0.0515 (6)
H25A	0.4182	0.8306	1.1369	0.077*
H25B	0.5471	0.7508	1.1218	0.077*
H25C	0.4616	0.8045	1.0618	0.077*
C26	0.9386 (3)	1.10751 (16)	1.09100 (11)	0.0429 (5)
H26A	1.0443	1.0901	1.0915	0.051*
H26B	0.9069	1.1680	1.1087	0.051*
O1	0.5918 (2)	1.24745 (10)	1.07174 (8)	0.0472 (4)
O2	0.6234 (2)	1.15134 (10)	1.16213 (7)	0.0466 (4)
O3	0.2674 (2)	0.78454 (11)	0.77637 (9)	0.0544 (4)
O4	0.8037 (2)	0.77818 (11)	1.05593 (10)	0.0617 (5)
O5	0.6898 (2)	0.90860 (11)	1.17396 (7)	0.0485 (4)
H1O5	0.7163	0.8558	1.1907	0.058*
O6	0.41897 (17)	1.00801 (12)	1.10126 (8)	0.0465 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0316 (9)	0.0236 (7)	0.0311 (8)	−0.0013 (7)	−0.0004 (7)	−0.0008 (6)
C2	0.0322 (9)	0.0238 (7)	0.0295 (8)	0.0008 (7)	−0.0008 (7)	0.0006 (6)
C3	0.0352 (10)	0.0299 (8)	0.0365 (9)	0.0057 (8)	−0.0024 (8)	−0.0049 (7)
C4	0.0348 (9)	0.0282 (8)	0.0375 (9)	0.0073 (8)	−0.0057 (8)	−0.0025 (7)
C5	0.0288 (9)	0.0265 (8)	0.0291 (8)	0.0009 (7)	0.0010 (7)	0.0010 (6)
C6	0.0334 (9)	0.0303 (8)	0.0362 (9)	0.0002 (8)	−0.0034 (8)	−0.0013 (7)
C7	0.0468 (12)	0.0338 (9)	0.0319 (9)	−0.0007 (9)	−0.0064 (9)	−0.0024 (7)
C8	0.0513 (13)	0.0410 (11)	0.0516 (13)	0.0118 (10)	−0.0063 (11)	−0.0160 (10)
C9	0.0407 (11)	0.0352 (9)	0.0378 (10)	0.0111 (9)	−0.0046 (9)	−0.0064 (8)
C10	0.0282 (9)	0.0300 (8)	0.0285 (8)	0.0025 (7)	0.0025 (7)	0.0004 (7)
C11	0.0268 (8)	0.0265 (8)	0.0265 (8)	0.0016 (7)	0.0018 (7)	0.0012 (6)
C12	0.0299 (9)	0.0406 (10)	0.0331 (9)	0.0070 (8)	0.0009 (8)	−0.0012 (8)
C13	0.0309 (9)	0.0345 (9)	0.0360 (9)	0.0056 (8)	−0.0044 (8)	−0.0009 (8)
C14	0.0451 (11)	0.0336 (9)	0.0329 (9)	0.0053 (9)	−0.0056 (9)	0.0001 (7)
C15	0.0445 (11)	0.0279 (8)	0.0313 (9)	−0.0043 (8)	−0.0031 (8)	0.0014 (7)
C16	0.0373 (10)	0.0308 (9)	0.0284 (8)	−0.0032 (8)	0.0007 (8)	−0.0023 (7)
C17	0.0331 (9)	0.0318 (8)	0.0302 (8)	0.0006 (8)	−0.0011 (8)	0.0027 (7)
C18	0.0344 (10)	0.0303 (8)	0.0376 (10)	−0.0015 (8)	−0.0026 (8)	−0.0041 (7)
C19	0.0606 (15)	0.0438 (11)	0.0450 (11)	−0.0037 (11)	0.0107 (11)	−0.0153 (10)
C20	0.0450 (12)	0.0331 (9)	0.0396 (10)	−0.0096 (9)	−0.0007 (9)	0.0069 (8)
C21	0.0339 (11)	0.0461 (11)	0.0624 (14)	−0.0015 (9)	−0.0053 (10)	−0.0104 (10)
C22	0.0533 (13)	0.0453 (11)	0.0358 (10)	0.0002 (10)	−0.0068 (10)	0.0038 (9)
C23	0.0356 (10)	0.0544 (12)	0.0328 (9)	−0.0030 (9)	0.0050 (8)	0.0065 (9)
C24	0.0362 (11)	0.0583 (13)	0.0543 (13)	0.0131 (11)	−0.0111 (10)	−0.0098 (11)
C25	0.0584 (14)	0.0319 (10)	0.0642 (14)	−0.0127 (10)	−0.0048 (12)	0.0048 (10)
C26	0.0375 (11)	0.0417 (11)	0.0496 (12)	−0.0050 (9)	−0.0073 (9)	−0.0005 (9)
O1	0.0638 (10)	0.0288 (6)	0.0490 (8)	0.0075 (7)	−0.0084 (8)	−0.0050 (6)
O2	0.0698 (11)	0.0342 (7)	0.0359 (7)	0.0028 (7)	0.0037 (8)	−0.0064 (6)
O3	0.0614 (11)	0.0355 (8)	0.0664 (10)	−0.0091 (8)	−0.0145 (9)	−0.0019 (7)
O4	0.0825 (13)	0.0312 (7)	0.0716 (11)	0.0123 (8)	0.0137 (10)	−0.0002 (7)
O5	0.0746 (12)	0.0382 (7)	0.0327 (7)	0.0031 (8)	−0.0117 (7)	−0.0005 (6)
O6	0.0388 (8)	0.0467 (8)	0.0539 (9)	−0.0008 (7)	0.0106 (7)	0.0049 (7)

Geometric parameters (Å, º) top

C1—C17	1.529 (3)	C13—C24	1.536 (3)
C1—C16	1.544 (3)	C14—O4	1.210 (2)
C1—C18	1.545 (2)	C14—C15	1.529 (3)
C1—C2	1.610 (2)	C15—O5	1.433 (2)
C2—C3	1.538 (3)	C15—C25	1.519 (3)
C2—C20	1.546 (3)	C15—C16	1.536 (3)
C2—C11	1.566 (2)	C16—O6	1.205 (2)
C3—C4	1.530 (3)	C17—C26	1.319 (3)
C3—H3A	0.9700	C18—O1	1.186 (2)
C3—H3B	0.9700	C18—O2	1.340 (2)
C4—C5	1.531 (2)	C19—O2	1.440 (2)
C4—H4A	0.9700	C19—H19A	0.9600
C4—H4B	0.9700	C19—H19B	0.9600
C5—C10	1.554 (2)	C19—H19C	0.9600
C5—C6	1.563 (3)	C20—H20A	0.9600
C5—H5	0.9800	C20—H20B	0.9600
C6—C7	1.532 (3)	C20—H20C	0.9600
C6—C21	1.535 (3)	C21—H21A	0.9600
C6—C22	1.544 (3)	C21—H21B	0.9600
C7—O3	1.207 (3)	C21—H21C	0.9600
C7—C8	1.495 (3)	C22—H22A	0.9600
C8—C9	1.536 (3)	C22—H22B	0.9600
C8—H8A	0.9700	C22—H22C	0.9600
C8—H8B	0.9700	C23—H23A	0.9600
C9—C10	1.541 (2)	C23—H23B	0.9600
C9—H9A	0.9700	C23—H23C	0.9600
C9—H9B	0.9700	C24—H24A	0.9600
C10—C23	1.541 (3)	C24—H24B	0.9600
C10—C11	1.572 (2)	C24—H24C	0.9600
C11—C12	1.538 (3)	C25—H25A	0.9600
C11—H11	0.9800	C25—H25B	0.9600
C12—C13	1.554 (3)	C25—H25C	0.9600
C12—H12A	0.9700	C26—H26A	0.9300
C12—H12B	0.9700	C26—H26B	0.9300
C13—C17	1.518 (3)	O5—H1O5	0.8200
C13—C14	1.529 (3)

C17—C1—C16	110.07 (14)	C17—C13—C24	114.00 (17)
C17—C1—C18	110.75 (15)	C14—C13—C24	109.54 (17)
C16—C1—C18	105.22 (15)	C17—C13—C12	108.14 (15)
C17—C1—C2	108.47 (15)	C14—C13—C12	104.21 (16)
C16—C1—C2	109.79 (14)	C24—C13—C12	108.61 (17)
C18—C1—C2	112.51 (14)	O4—C14—C13	121.1 (2)
C3—C2—C20	109.24 (15)	O4—C14—C15	119.7 (2)
C3—C2—C11	109.27 (15)	C13—C14—C15	119.16 (16)
C20—C2—C11	112.77 (15)	O5—C15—C25	112.11 (17)
C3—C2—C1	111.30 (15)	O5—C15—C14	104.29 (17)
C20—C2—C1	108.39 (14)	C25—C15—C14	112.63 (17)
C11—C2—C1	105.86 (13)	O5—C15—C16	103.14 (14)
C4—C3—C2	112.98 (16)	C25—C15—C16	110.30 (17)
C4—C3—H3A	109.0	C14—C15—C16	113.86 (16)
C2—C3—H3A	109.0	O6—C16—C15	119.46 (18)
C4—C3—H3B	109.0	O6—C16—C1	120.88 (18)
C2—C3—H3B	109.0	C15—C16—C1	119.63 (17)
H3A—C3—H3B	107.8	C26—C17—C13	123.72 (19)
C3—C4—C5	110.50 (15)	C26—C17—C1	123.45 (18)
C3—C4—H4A	109.6	C13—C17—C1	112.61 (16)
C5—C4—H4A	109.6	O1—C18—O2	123.17 (17)
C3—C4—H4B	109.6	O1—C18—C1	127.27 (18)
C5—C4—H4B	109.6	O2—C18—C1	109.54 (15)
H4A—C4—H4B	108.1	O2—C19—H19A	109.5
C4—C5—C10	110.34 (15)	O2—C19—H19B	109.5
C4—C5—C6	113.65 (15)	H19A—C19—H19B	109.5
C10—C5—C6	117.46 (15)	O2—C19—H19C	109.5
C4—C5—H5	104.6	H19A—C19—H19C	109.5
C10—C5—H5	104.6	H19B—C19—H19C	109.5
C6—C5—H5	104.6	C2—C20—H20A	109.5
C7—C6—C21	108.47 (17)	C2—C20—H20B	109.5
C7—C6—C22	108.08 (17)	H20A—C20—H20B	109.5
C21—C6—C22	107.68 (18)	C2—C20—H20C	109.5
C7—C6—C5	107.91 (15)	H20A—C20—H20C	109.5
C21—C6—C5	109.53 (17)	H20B—C20—H20C	109.5
C22—C6—C5	114.99 (16)	C6—C21—H21A	109.5
O3—C7—C8	120.95 (19)	C6—C21—H21B	109.5
O3—C7—C6	122.0 (2)	H21A—C21—H21B	109.5
C8—C7—C6	117.03 (18)	C6—C21—H21C	109.5
C7—C8—C9	112.26 (18)	H21A—C21—H21C	109.5
C7—C8—H8A	109.2	H21B—C21—H21C	109.5
C9—C8—H8A	109.2	C6—C22—H22A	109.5
C7—C8—H8B	109.2	C6—C22—H22B	109.5
C9—C8—H8B	109.2	H22A—C22—H22B	109.5
H8A—C8—H8B	107.9	C6—C22—H22C	109.5
C8—C9—C10	112.73 (17)	H22A—C22—H22C	109.5
C8—C9—H9A	109.0	H22B—C22—H22C	109.5
C10—C9—H9A	109.0	C10—C23—H23A	109.5
C8—C9—H9B	109.0	C10—C23—H23B	109.5
C10—C9—H9B	109.0	H23A—C23—H23B	109.5
H9A—C9—H9B	107.8	C10—C23—H23C	109.5
C23—C10—C9	108.29 (16)	H23A—C23—H23C	109.5
C23—C10—C5	114.92 (15)	H23B—C23—H23C	109.5
C9—C10—C5	107.32 (16)	C13—C24—H24A	109.5
C23—C10—C11	112.61 (16)	C13—C24—H24B	109.5
C9—C10—C11	107.17 (14)	H24A—C24—H24B	109.5
C5—C10—C11	106.16 (14)	C13—C24—H24C	109.5
C12—C11—C2	110.55 (15)	H24A—C24—H24C	109.5
C12—C11—C10	113.19 (15)	H24B—C24—H24C	109.5
C2—C11—C10	116.54 (14)	C15—C25—H25A	109.5
C12—C11—H11	105.1	C15—C25—H25B	109.5
C2—C11—H11	105.1	H25A—C25—H25B	109.5
C10—C11—H11	105.1	C15—C25—H25C	109.5
C11—C12—C13	112.61 (15)	H25A—C25—H25C	109.5
C11—C12—H12A	109.1	H25B—C25—H25C	109.5
C13—C12—H12A	109.1	C17—C26—H26A	120.0
C11—C12—H12B	109.1	C17—C26—H26B	120.0
C13—C12—H12B	109.1	H26A—C26—H26B	120.0
H12A—C12—H12B	107.8	C18—O2—C19	115.72 (16)
C17—C13—C14	111.82 (16)	C15—O5—H1O5	109.5

C17—C1—C2—C3	179.65 (14)	C5—C10—C11—C2	−54.13 (19)
C16—C1—C2—C3	59.35 (19)	C2—C11—C12—C13	58.8 (2)
C18—C1—C2—C3	−57.47 (19)	C10—C11—C12—C13	−168.36 (15)
C17—C1—C2—C20	−60.19 (18)	C11—C12—C13—C17	−55.3 (2)
C16—C1—C2—C20	179.50 (15)	C11—C12—C13—C14	63.8 (2)
C18—C1—C2—C20	62.69 (19)	C11—C12—C13—C24	−179.52 (17)
C17—C1—C2—C11	61.04 (17)	C17—C13—C14—O4	−167.3 (2)
C16—C1—C2—C11	−59.27 (18)	C24—C13—C14—O4	−40.0 (3)
C18—C1—C2—C11	−176.09 (15)	C12—C13—C14—O4	76.1 (2)
C20—C2—C3—C4	74.34 (19)	C17—C13—C14—C15	11.4 (2)
C11—C2—C3—C4	−49.46 (19)	C24—C13—C14—C15	138.78 (18)
C1—C2—C3—C4	−166.01 (14)	C12—C13—C14—C15	−105.16 (19)
C2—C3—C4—C5	58.4 (2)	O4—C14—C15—O5	95.3 (2)
C3—C4—C5—C10	−63.8 (2)	C13—C14—C15—O5	−83.44 (19)
C3—C4—C5—C6	161.82 (16)	O4—C14—C15—C25	−26.5 (3)
C4—C5—C6—C7	179.97 (16)	C13—C14—C15—C25	154.76 (18)
C10—C5—C6—C7	49.0 (2)	O4—C14—C15—C16	−153.0 (2)
C4—C5—C6—C21	−62.1 (2)	C13—C14—C15—C16	28.2 (2)
C10—C5—C6—C21	166.93 (17)	O5—C15—C16—O6	−91.8 (2)
C4—C5—C6—C22	59.3 (2)	C25—C15—C16—O6	28.1 (3)
C10—C5—C6—C22	−71.7 (2)	C14—C15—C16—O6	155.85 (18)
C21—C6—C7—O3	15.0 (3)	O5—C15—C16—C1	86.0 (2)
C22—C6—C7—O3	−101.4 (2)	C25—C15—C16—C1	−154.06 (18)
C5—C6—C7—O3	133.6 (2)	C14—C15—C16—C1	−26.3 (2)
C21—C6—C7—C8	−165.2 (2)	C17—C1—C16—O6	163.11 (18)
C22—C6—C7—C8	78.4 (2)	C18—C1—C16—O6	43.8 (2)
C5—C6—C7—C8	−46.6 (2)	C2—C1—C16—O6	−77.6 (2)
O3—C7—C8—C9	−128.7 (2)	C17—C1—C16—C15	−14.7 (2)
C6—C7—C8—C9	51.5 (3)	C18—C1—C16—C15	−134.06 (16)
C7—C8—C9—C10	−55.0 (3)	C2—C1—C16—C15	104.64 (18)
C8—C9—C10—C23	−70.2 (2)	C14—C13—C17—C26	129.3 (2)
C8—C9—C10—C5	54.4 (2)	C24—C13—C17—C26	4.4 (3)
C8—C9—C10—C11	168.11 (17)	C12—C13—C17—C26	−116.5 (2)
C4—C5—C10—C23	−65.9 (2)	C14—C13—C17—C1	−55.9 (2)
C6—C5—C10—C23	66.6 (2)	C24—C13—C17—C1	179.19 (18)
C4—C5—C10—C9	173.62 (15)	C12—C13—C17—C1	58.3 (2)
C6—C5—C10—C9	−53.9 (2)	C16—C1—C17—C26	−128.2 (2)
C4—C5—C10—C11	59.28 (18)	C18—C1—C17—C26	−12.3 (3)
C6—C5—C10—C11	−168.29 (14)	C2—C1—C17—C26	111.7 (2)
C3—C2—C11—C12	−179.43 (15)	C16—C1—C17—C13	57.01 (19)
C20—C2—C11—C12	58.88 (19)	C18—C1—C17—C13	172.94 (15)
C1—C2—C11—C12	−59.47 (17)	C2—C1—C17—C13	−63.13 (18)
C3—C2—C11—C10	49.48 (19)	C17—C1—C18—O1	108.2 (2)
C20—C2—C11—C10	−72.2 (2)	C16—C1—C18—O1	−132.9 (2)
C1—C2—C11—C10	169.43 (14)	C2—C1—C18—O1	−13.4 (3)
C23—C10—C11—C12	−57.4 (2)	C17—C1—C18—O2	−70.5 (2)
C9—C10—C11—C12	61.6 (2)	C16—C1—C18—O2	48.4 (2)
C5—C10—C11—C12	176.01 (14)	C2—C1—C18—O2	167.95 (16)
C23—C10—C11—C2	72.4 (2)	O1—C18—O2—C19	4.0 (3)
C9—C10—C11—C2	−168.58 (16)	C1—C18—O2—C19	−177.29 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1O5···O3ⁱ	0.82	2.05	2.870 (2)	173
C23—H23A···O5ⁱⁱ	0.96	2.68	3.173 (2)	112

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

Experimental details

Crystal data
Chemical formula	C₂₆H₃₆O₆
M_r	444.55
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	290
a, b, c (Å)	8.5023 (2), 13.5405 (2), 19.7127 (4)
V (Å³)	2269.43 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.37 × 0.28 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	27134, 2938, 2677
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.093, 1.03
No. of reflections	2938
No. of parameters	297
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.13
Absolute structure	[α_D] = -4.97° and results in dos Santos & Rodrigues-Fo (2002)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1O5···O3ⁱ	0.82	2.05	2.870 (2)	173

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

Acknowledgements

We thank FAPESP, CNPq and CAPES for financial support. 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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