Methyl 5a-acetoxy­methyl-3-isopropyl-8-methyl-1,2,3,3a,4,5,5a,6,7,10,10a,10b-dodeca­hydro-7,10-endo-epidioxy­cylohepta­[e]indene-3a-carboxyl­ate

Brito, I.; Bórquez, J.; Loyola, L.A.; Cárdenas, A.; López-Rodríguez, M.

doi:10.1107/S1600536808016474

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1209

doi:10.1107/S1600536808016474

Open

access

Methyl 5a-acetoxymethyl-3-isopropyl-8-methyl-1,2,3,3a,4,5,5a,6,7,10,10a,10b-dodecahydro-7,10-endo-epidioxycylohepta[e]indene-3a-carboxylate

Iván Brito,^a ^* Jorge Bórquez,^a Luis Alberto Loyola,^a Alejandro Cárdenas ^b and Matías López-Rodríguez ^c

^aDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, ^bDepartamento de Física, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, and ^cInstituto de Bio-Orgánica `Antonio González', Universidad de La Laguna, Astrofísico Francisco Sánchez No. 2, La Laguna, Tenerife, Spain
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 27 May 2008; accepted 29 May 2008; online 7 June 2008)

The molecule of the title compound, C₂₃H₃₄O₆, is built up from three fused carbocycles, one five-membered, one six-membered and one seven-membered. The five-membered ring has an envelope conformation, whereas the six-membered ring has a perfect chair conformation and the seven-membered ring has a boat conformation. Intramolecular C—H⋯O hydrogen bonds together with van der Waals interactions stabilize the molecular conformation.

Related literature

For related literature, see: Araya et al. (2003 ); Cremer & Pople (1975 ); Loyola et al. (1990 , 2004 ); Munizaga & Gunkel (1958 ).

Experimental

Crystal data

C₂₃H₃₄O₆
M_r = 406.5
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.7014 (1) Å
b = 12.1234 (3) Å
c = 23.2773 (6) Å
V = 2173.34 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 (2) K
0.24 × 0.24 × 0.02 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: none
5538 measured reflections
3052 independent reflections
2499 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.127
S = 1.08
3052 reflections
269 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5B⋯O3	0.97	2.39	2.877 (3)	110
C10A—H10A⋯O3	0.98	2.33	2.848 (3)	112
C10B—H10B⋯O1	0.98	2.43	2.778 (3)	101

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808016474/bt2719sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808016474/bt2719Isup2.hkl

checkCIF report

Comment top

The title compound was obtained from a methylation reaction over the acid group of 17-acetoxymulinic acid, which was previously isolated from Mulinum crassifolium (Apiaceae). Mulinum crassifolium is a 15 cm small shrub, which grows in the north of Chile at altitudes above 4000 m. This plant, commonly known as chuquican, susurco or espinilla is used in the folk medicine, principally against diabetes, and bronchial (caught) and intestinal disorders (Munizaga et al., 1958). Mulinane diterpenes exhibits antiplasmodial (Loyola et al., 2004) and anti-Tripanosomacruzi (Araya et al., 2003) activities.We have undertaken the X-ray crystal-structure determination of (I) in order to establish its molecular conformation and relative stereochemistry. We are not able to determine the absolute stereochemistry by X-ray methods and the configuration shown here was chosen to be in accord with that reported in previous chemical studies (Loyola et al., 1990). The structure consists of a mulinic acid skeleton and the isopropyl, acetyloxymethyl and carboxylate groups at C3, C5a and C3 are β-oriented respectively, whereas the endo-peroxide group is α-oriented. The cyclopentane (A), cyclohexane (B) and cycloheptene (C) rings are in an envelope, chair and boat conformation, respectively [Q₂= 0.424 (3) Å, ϕ₂= 107.2 (4)° for ring A; Q_T= 0.553 (3) Å, θ = 159.6 (3)°, ϕ=189.2 (8)° for ring B; Q_T= 1.123 (3) Å, ϕ₂=179.9 (2)°, for ring C] (Cremer & Pople, 1975). The A and B and B and C rings are trans and cis-fused respectively. The molecular conformation of the title compound, is stabilized by three strong intramolecular hydrogen bonds, Fig.2.

Related literature top

For related literature, see: Araya et al. (2003); Cremer & Pople (1975); Loyola et al. (1990, 2004); Munizaga & Gunkel (1958).

Experimental top

Dried and finely powdered aerial parts of Mulinum crassifolium (1530 g) were extracted with petroleum ether at room temperature. The solvent was evaporated in vacuum yielding a gum (40 g). The concentrated petrol ether extract was fractionated on silica gel column with hexane-ethyl acetate mixtures of increasing polarity as elution solvents. The fraction (0.867 g) eluted was further separated and purified by silica gel chromatography to give 120.5 mg of 17-acetoxymulinic acid which was methylated with diazomethane using ethyl ether as solvent at room temperature to give 110 mg de (I). Recrystallization from hexane-ethyl acetate (7:3) at room temperature afforded colourless crystals suitable for X-ray diffraction analysis.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of the molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Intramolecular C—H···O interactions (dashed lines) in the title compound.

Methyl 5a-acetoxymethyl-3-isopropyl-8-methyl- 1,2,3,3a,4,5,5a,6,7,10,10a,10b-dodecahydro-7,10-endo- epidioxycylohepta[e]indene-3a-carboxylate top

Crystal data top

C₂₃H₃₄O₆	F(000) = 880
M_r = 406.5	D_x = 1.242 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4314 reflections
a = 7.7014 (1) Å	θ = 6.5–28.5°
b = 12.1234 (3) Å	µ = 0.09 mm⁻¹
c = 23.2773 (6) Å	T = 298 K
V = 2173.34 (8) Å³	Block, colourless
Z = 4	0.24 × 0.24 × 0.02 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	2499 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 28.7°, θ_min = 6.5°
ϕ scans, and ω scans with κ offsets	h = 0→9
5538 measured reflections	k = 0→16
3052 independent reflections	l = −31→31

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.059	w = 1/[σ²(F_o²) + (0.0421P)² + 0.8253P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.127	(Δ/σ)_max = 0.007
S = 1.08	Δρ_max = 0.22 e Å⁻³
3052 reflections	Δρ_min = −0.16 e Å⁻³
269 parameters

Crystal data top

C₂₃H₃₄O₆	V = 2173.34 (8) Å³
M_r = 406.5	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.7014 (1) Å	µ = 0.09 mm⁻¹
b = 12.1234 (3) Å	T = 298 K
c = 23.2773 (6) Å	0.24 × 0.24 × 0.02 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	2499 reflections with I > 2σ(I)
5538 measured reflections	R_int = 0.031
3052 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.08	Δρ_max = 0.22 e Å⁻³
3052 reflections	Δρ_min = −0.16 e Å⁻³
269 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	−0.2384 (3)	0.1347 (2)	0.68889 (10)	0.0639 (7)
O2	−0.1528 (4)	0.2323 (2)	0.71350 (11)	0.0687 (7)
O3	0.3065 (3)	−0.10383 (17)	0.68850 (9)	0.0518 (5)
O4	0.5474 (3)	−0.1354 (2)	0.73855 (15)	0.0867 (9)
O5	0.0901 (3)	−0.14722 (16)	0.55258 (10)	0.0552 (6)
O6	0.3186 (3)	−0.06177 (16)	0.51523 (9)	0.0487 (5)
C1	−0.2121 (4)	0.0030 (3)	0.57004 (13)	0.0535 (8)
H1A	−0.3169	0.039	0.5835	0.052 (2)*
H1B	−0.2162	−0.0742	0.5808	0.052 (2)*
C2	−0.1933 (4)	0.0156 (3)	0.50447 (14)	0.0591 (8)
H2A	−0.2915	0.0558	0.4889	0.052 (2)*
H2B	−0.1885	−0.0563	0.4863	0.052 (2)*
C3	−0.0234 (4)	0.0795 (2)	0.49338 (12)	0.0473 (7)
H3	−0.0524	0.1582	0.4954	0.052 (2)*
C3A	0.0889 (3)	0.0529 (2)	0.54768 (11)	0.0343 (5)
C4	0.2315 (4)	0.1336 (2)	0.56491 (12)	0.0398 (6)
H4A	0.3203	0.136	0.5354	0.052 (2)*
H4B	0.1834	0.2071	0.5692	0.052 (2)*
C5	0.3105 (4)	0.0957 (2)	0.62158 (12)	0.0415 (6)
H5A	0.3964	0.1499	0.6331	0.052 (2)*
H5B	0.3717	0.0271	0.6146	0.052 (2)*
C5A	0.1856 (3)	0.0774 (2)	0.67296 (11)	0.0347 (5)
C6	0.1561 (4)	0.1917 (2)	0.70137 (13)	0.0468 (7)
H6A	0.2622	0.2115	0.7213	0.052 (2)*
H6B	0.1402	0.2451	0.6708	0.052 (2)*
C7	0.0054 (5)	0.2063 (3)	0.74379 (14)	0.0525 (8)
H7	0.0334	0.2706	0.7676	0.052 (2)*
C8	−0.0245 (4)	0.1123 (3)	0.78396 (13)	0.0508 (8)
C9	−0.0977 (4)	0.0257 (3)	0.75995 (13)	0.0520 (8)
H9	−0.1209	−0.038	0.7808	0.052 (2)*
C10	−0.1419 (4)	0.0345 (3)	0.69763 (13)	0.0470 (7)
H10	−0.2224	−0.0261	0.6894	0.052 (2)*
C10A	0.0111 (3)	0.0217 (2)	0.65466 (11)	0.0337 (5)
H10A	0.0347	−0.0575	0.6517	0.052 (2)*
C10B	−0.0497 (3)	0.0591 (2)	0.59511 (11)	0.0356 (6)
H10B	−0.0792	0.1373	0.599	0.052 (2)*
C11	0.0302 (6)	0.1227 (4)	0.84575 (14)	0.0737 (11)
H11A	−0.0064	0.0584	0.8666	0.105 (4)*
H11B	−0.0224	0.1871	0.8623	0.105 (4)*
H11C	0.1543	0.1292	0.8478	0.105 (4)*
C12	0.2888 (4)	0.0041 (3)	0.71470 (13)	0.0462 (7)
H12A	0.4025	0.0358	0.7218	0.052 (2)*
H12B	0.228	−0.0019	0.7511	0.052 (2)*
C13	0.4416 (4)	−0.1652 (3)	0.70431 (15)	0.0500 (8)
C14	0.4426 (5)	−0.2734 (3)	0.67401 (19)	0.0705 (10)
H14A	0.5582	−0.2896	0.6611	0.105 (4)*
H14B	0.3658	−0.2702	0.6416	0.105 (4)*
H14C	0.4046	−0.3302	0.6998	0.105 (4)*
C15	0.1611 (3)	−0.0632 (2)	0.53996 (11)	0.0355 (5)
C16	0.3949 (5)	−0.1677 (3)	0.50295 (16)	0.0618 (9)
H16A	0.4036	−0.2097	0.5378	0.105 (4)*
H16B	0.5087	−0.1574	0.4869	0.105 (4)*
H16C	0.3234	−0.2066	0.4759	0.105 (4)*
C17	0.0546 (5)	0.0591 (3)	0.43302 (13)	0.0569 (8)
H17	0.0958	−0.0174	0.4319	0.052 (2)*
C18	0.2077 (7)	0.1326 (4)	0.41986 (16)	0.0870 (14)
H18A	0.1763	0.2081	0.4267	0.105 (4)*
H18B	0.2407	0.1236	0.3804	0.105 (4)*
H18C	0.3034	0.1129	0.4442	0.105 (4)*
C19	−0.0846 (7)	0.0713 (4)	0.38666 (15)	0.0855 (14)
H19A	−0.1338	0.144	0.3886	0.105 (4)*
H19B	−0.1741	0.0175	0.3928	0.105 (4)*
H19C	−0.0333	0.0602	0.3495	0.105 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0484 (12)	0.0844 (17)	0.0589 (13)	0.0207 (13)	0.0003 (11)	−0.0204 (13)
O2	0.0731 (16)	0.0593 (15)	0.0738 (16)	0.0192 (14)	0.0024 (14)	0.0054 (13)
O3	0.0489 (12)	0.0487 (11)	0.0579 (12)	0.0085 (10)	−0.0136 (11)	−0.0031 (10)
O4	0.0587 (16)	0.0741 (18)	0.127 (2)	0.0043 (14)	−0.0425 (18)	0.0106 (17)
O5	0.0608 (13)	0.0319 (10)	0.0730 (15)	−0.0098 (10)	0.0136 (12)	−0.0067 (10)
O6	0.0469 (11)	0.0377 (10)	0.0617 (12)	0.0068 (10)	0.0138 (10)	−0.0047 (10)
C1	0.0323 (15)	0.074 (2)	0.0541 (17)	−0.0029 (15)	−0.0033 (13)	−0.0075 (16)
C2	0.0488 (17)	0.076 (2)	0.0520 (17)	0.0034 (17)	−0.0165 (15)	−0.0075 (17)
C3	0.0612 (18)	0.0406 (15)	0.0401 (14)	0.0098 (14)	−0.0074 (14)	−0.0016 (12)
C3A	0.0391 (13)	0.0287 (12)	0.0351 (12)	0.0006 (11)	0.0014 (11)	−0.0003 (10)
C4	0.0450 (15)	0.0311 (13)	0.0435 (14)	−0.0062 (12)	0.0101 (12)	−0.0040 (11)
C5	0.0326 (13)	0.0429 (15)	0.0490 (15)	−0.0102 (12)	0.0035 (12)	−0.0077 (12)
C5A	0.0335 (12)	0.0346 (13)	0.0360 (12)	−0.0055 (11)	−0.0015 (11)	−0.0061 (11)
C6	0.0563 (18)	0.0379 (15)	0.0461 (16)	−0.0087 (14)	0.0008 (14)	−0.0086 (13)
C7	0.070 (2)	0.0420 (16)	0.0460 (16)	−0.0030 (17)	0.0046 (16)	−0.0103 (13)
C8	0.0541 (17)	0.0584 (19)	0.0400 (15)	0.0037 (16)	0.0076 (14)	−0.0049 (14)
C9	0.0612 (19)	0.0476 (16)	0.0471 (16)	−0.0007 (16)	0.0176 (15)	0.0010 (13)
C10	0.0398 (14)	0.0531 (17)	0.0482 (16)	−0.0100 (13)	0.0097 (13)	−0.0049 (14)
C10A	0.0288 (11)	0.0343 (12)	0.0379 (13)	−0.0026 (11)	0.0014 (10)	−0.0047 (10)
C10B	0.0298 (12)	0.0363 (13)	0.0408 (13)	0.0032 (11)	0.0004 (10)	−0.0040 (11)
C11	0.080 (3)	0.097 (3)	0.0439 (18)	0.003 (2)	−0.0008 (19)	−0.0052 (19)
C12	0.0418 (15)	0.0522 (17)	0.0447 (15)	0.0055 (14)	−0.0078 (13)	−0.0073 (13)
C13	0.0363 (15)	0.0521 (18)	0.0615 (19)	0.0016 (13)	0.0014 (14)	0.0189 (15)
C14	0.067 (2)	0.054 (2)	0.090 (3)	0.0167 (19)	0.006 (2)	0.0085 (19)
C15	0.0399 (13)	0.0326 (12)	0.0342 (12)	−0.0005 (12)	−0.0027 (11)	−0.0035 (11)
C16	0.067 (2)	0.0506 (18)	0.068 (2)	0.0200 (17)	0.0143 (19)	−0.0075 (16)
C17	0.084 (2)	0.0468 (16)	0.0399 (15)	0.0123 (19)	−0.0024 (16)	0.0003 (14)
C18	0.123 (4)	0.088 (3)	0.0499 (19)	−0.016 (3)	0.020 (2)	0.005 (2)
C19	0.128 (4)	0.083 (3)	0.0457 (18)	0.032 (3)	−0.021 (2)	−0.0038 (19)

Geometric parameters (Å, º) top

O1—C10	1.438 (4)	C6—H6B	0.97
O1—O2	1.470 (4)	C7—C8	1.492 (5)
O2—C7	1.443 (5)	C7—H7	0.98
O3—C13	1.331 (4)	C8—C9	1.316 (5)
O3—C12	1.450 (4)	C8—C11	1.504 (5)
O4—C13	1.196 (4)	C9—C10	1.494 (5)
O5—C15	1.193 (3)	C9—H9	0.93
O6—C15	1.342 (3)	C10—C10A	1.554 (4)
O6—C16	1.441 (4)	C10—H10	0.98
C1—C10B	1.538 (4)	C10A—C10B	1.532 (4)
C1—C2	1.541 (5)	C10A—H10A	0.98
C1—H1A	0.97	C10B—H10B	0.98
C1—H1B	0.97	C11—H11A	0.96
C2—C3	1.542 (5)	C11—H11B	0.96
C2—H2A	0.97	C11—H11C	0.96
C2—H2B	0.97	C12—H12A	0.97
C3—C17	1.548 (4)	C12—H12B	0.97
C3—C3A	1.565 (4)	C13—C14	1.490 (5)
C3—H3	0.98	C14—H14A	0.96
C3A—C4	1.524 (4)	C14—H14B	0.96
C3A—C15	1.525 (4)	C14—H14C	0.96
C3A—C10B	1.538 (4)	C16—H16A	0.96
C4—C5	1.523 (4)	C16—H16B	0.96
C4—H4A	0.97	C16—H16C	0.96
C4—H4B	0.97	C17—C18	1.510 (6)
C5—C5A	1.551 (4)	C17—C19	1.528 (5)
C5—H5A	0.97	C17—H17	0.98
C5—H5B	0.97	C18—H18A	0.96
C5A—C12	1.538 (4)	C18—H18B	0.96
C5A—C6	1.553 (4)	C18—H18C	0.96
C5A—C10A	1.563 (3)	C19—H19A	0.96
C6—C7	1.534 (5)	C19—H19B	0.96
C6—H6A	0.97	C19—H19C	0.96

C10—O1—O2	113.1 (2)	O1—C10—C10A	112.7 (2)
C7—O2—O1	113.1 (2)	C9—C10—C10A	116.4 (2)
C13—O3—C12	117.5 (2)	O1—C10—H10	106.2
C15—O6—C16	116.2 (2)	C9—C10—H10	106.2
C10B—C1—C2	104.8 (3)	C10A—C10—H10	106.2
C10B—C1—H1A	110.8	C10B—C10A—C10	108.7 (2)
C2—C1—H1A	110.8	C10B—C10A—C5A	112.5 (2)
C10B—C1—H1B	110.8	C10—C10A—C5A	115.7 (2)
C2—C1—H1B	110.8	C10B—C10A—H10A	106.5
H1A—C1—H1B	108.9	C10—C10A—H10A	106.5
C1—C2—C3	107.2 (2)	C5A—C10A—H10A	106.5
C1—C2—H2A	110.3	C10A—C10B—C3A	115.0 (2)
C3—C2—H2A	110.3	C10A—C10B—C1	117.5 (2)
C1—C2—H2B	110.3	C3A—C10B—C1	105.7 (2)
C3—C2—H2B	110.3	C10A—C10B—H10B	105.9
H2A—C2—H2B	108.5	C3A—C10B—H10B	105.9
C2—C3—C17	113.6 (3)	C1—C10B—H10B	105.9
C2—C3—C3A	103.3 (2)	C8—C11—H11A	109.5
C17—C3—C3A	119.0 (3)	C8—C11—H11B	109.5
C2—C3—H3	106.7	H11A—C11—H11B	109.5
C17—C3—H3	106.7	C8—C11—H11C	109.5
C3A—C3—H3	106.7	H11A—C11—H11C	109.5
C4—C3A—C15	111.2 (2)	H11B—C11—H11C	109.5
C4—C3A—C10B	106.3 (2)	O3—C12—C5A	107.7 (2)
C15—C3A—C10B	112.5 (2)	O3—C12—H12A	110.2
C4—C3A—C3	118.6 (2)	C5A—C12—H12A	110.2
C15—C3A—C3	107.3 (2)	O3—C12—H12B	110.2
C10B—C3A—C3	100.7 (2)	C5A—C12—H12B	110.2
C5—C4—C3A	108.8 (2)	H12A—C12—H12B	108.5
C5—C4—H4A	109.9	O4—C13—O3	123.3 (3)
C3A—C4—H4A	109.9	O4—C13—C14	125.3 (3)
C5—C4—H4B	109.9	O3—C13—C14	111.4 (3)
C3A—C4—H4B	109.9	C13—C14—H14A	109.5
H4A—C4—H4B	108.3	C13—C14—H14B	109.5
C4—C5—C5A	117.6 (2)	H14A—C14—H14B	109.5
C4—C5—H5A	107.9	C13—C14—H14C	109.5
C5A—C5—H5A	107.9	H14A—C14—H14C	109.5
C4—C5—H5B	107.9	H14B—C14—H14C	109.5
C5A—C5—H5B	107.9	O5—C15—O6	122.1 (3)
H5A—C5—H5B	107.2	O5—C15—C3A	126.3 (2)
C12—C5A—C5	104.5 (2)	O6—C15—C3A	111.6 (2)
C12—C5A—C6	108.8 (2)	O6—C16—H16A	109.5
C5—C5A—C6	106.9 (2)	O6—C16—H16B	109.5
C12—C5A—C10A	111.5 (2)	H16A—C16—H16B	109.5
C5—C5A—C10A	112.6 (2)	O6—C16—H16C	109.5
C6—C5A—C10A	112.1 (2)	H16A—C16—H16C	109.5
C7—C6—C5A	119.2 (2)	H16B—C16—H16C	109.5
C7—C6—H6A	107.5	C18—C17—C19	110.3 (3)
C5A—C6—H6A	107.5	C18—C17—C3	113.1 (3)
C7—C6—H6B	107.5	C19—C17—C3	110.7 (3)
C5A—C6—H6B	107.5	C18—C17—H17	107.5
H6A—C6—H6B	107	C19—C17—H17	107.5
O2—C7—C8	110.1 (3)	C3—C17—H17	107.5
O2—C7—C6	110.4 (2)	C17—C18—H18A	109.5
C8—C7—C6	115.6 (3)	C17—C18—H18B	109.5
O2—C7—H7	106.7	H18A—C18—H18B	109.5
C8—C7—H7	106.7	C17—C18—H18C	109.5
C6—C7—H7	106.7	H18A—C18—H18C	109.5
C9—C8—C7	114.1 (3)	H18B—C18—H18C	109.5
C9—C8—C11	126.4 (3)	C17—C19—H19A	109.5
C7—C8—C11	119.5 (3)	C17—C19—H19B	109.5
C8—C9—C10	117.0 (3)	H19A—C19—H19B	109.5
C8—C9—H9	121.5	C17—C19—H19C	109.5
C10—C9—H9	121.5	H19A—C19—H19C	109.5
O1—C10—C9	108.4 (2)	H19B—C19—H19C	109.5

C10—O1—O2—C7	−3.0 (3)	C9—C10—C10A—C5A	−39.5 (4)
C10B—C1—C2—C3	−0.8 (4)	C12—C5A—C10A—C10B	−152.2 (2)
C1—C2—C3—C17	156.3 (3)	C5—C5A—C10A—C10B	−35.1 (3)
C1—C2—C3—C3A	25.9 (3)	C6—C5A—C10A—C10B	85.5 (3)
C2—C3—C3A—C4	−155.8 (2)	C12—C5A—C10A—C10	82.1 (3)
C17—C3—C3A—C4	77.2 (3)	C5—C5A—C10A—C10	−160.9 (2)
C2—C3—C3A—C15	77.4 (3)	C6—C5A—C10A—C10	−40.2 (3)
C17—C3—C3A—C15	−49.7 (3)	C10—C10A—C10B—C3A	179.1 (2)
C2—C3—C3A—C10B	−40.4 (3)	C5A—C10A—C10B—C3A	49.7 (3)
C17—C3—C3A—C10B	−167.5 (3)	C10—C10A—C10B—C1	−55.4 (3)
C15—C3A—C4—C5	−60.2 (3)	C5A—C10A—C10B—C1	175.1 (2)
C10B—C3A—C4—C5	62.4 (3)	C4—C3A—C10B—C10A	−63.6 (3)
C3—C3A—C4—C5	174.8 (2)	C15—C3A—C10B—C10A	58.3 (3)
C3A—C4—C5—C5A	−54.7 (3)	C3—C3A—C10B—C10A	172.2 (2)
C4—C5—C5A—C12	161.1 (2)	C4—C3A—C10B—C1	165.1 (2)
C4—C5—C5A—C6	−83.6 (3)	C15—C3A—C10B—C1	−73.0 (3)
C4—C5—C5A—C10A	39.9 (3)	C3—C3A—C10B—C1	40.9 (3)
C12—C5A—C6—C7	−82.6 (3)	C2—C1—C10B—C10A	−155.3 (3)
C5—C5A—C6—C7	165.1 (3)	C2—C1—C10B—C3A	−25.3 (3)
C10A—C5A—C6—C7	41.2 (4)	C13—O3—C12—C5A	154.3 (2)
O1—O2—C7—C8	−48.3 (3)	C5—C5A—C12—O3	−69.1 (3)
O1—O2—C7—C6	80.6 (3)	C6—C5A—C12—O3	177.0 (2)
C5A—C6—C7—O2	−85.8 (3)	C10A—C5A—C12—O3	52.8 (3)
C5A—C6—C7—C8	40.0 (4)	C12—O3—C13—O4	−0.2 (5)
O2—C7—C8—C9	51.4 (4)	C12—O3—C13—C14	179.9 (3)
C6—C7—C8—C9	−74.6 (4)	C16—O6—C15—O5	2.0 (4)
O2—C7—C8—C11	−129.2 (3)	C16—O6—C15—C3A	−176.7 (3)
C6—C7—C8—C11	104.8 (4)	C4—C3A—C15—O5	143.0 (3)
C7—C8—C9—C10	−1.0 (4)	C10B—C3A—C15—O5	23.9 (4)
C11—C8—C9—C10	179.7 (3)	C3—C3A—C15—O5	−85.9 (3)
O2—O1—C10—C9	51.2 (3)	C4—C3A—C15—O6	−38.5 (3)
O2—O1—C10—C10A	−79.1 (3)	C10B—C3A—C15—O6	−157.5 (2)
C8—C9—C10—O1	−50.8 (4)	C3—C3A—C15—O6	92.6 (3)
C8—C9—C10—C10A	77.4 (4)	C2—C3—C17—C18	172.8 (3)
O1—C10—C10A—C10B	−41.0 (3)	C3A—C3—C17—C18	−65.2 (4)
C9—C10—C10A—C10B	−167.1 (3)	C2—C3—C17—C19	48.4 (4)
O1—C10—C10A—C5A	86.6 (3)	C3A—C3—C17—C19	170.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O3	0.97	2.39	2.877 (3)	110
C10A—H10A···O3	0.98	2.33	2.848 (3)	112
C10B—H10B···O1	0.98	2.43	2.778 (3)	101

Experimental details

Crystal data
Chemical formula	C₂₃H₃₄O₆
M_r	406.5
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.7014 (1), 12.1234 (3), 23.2773 (6)
V (Å³)	2173.34 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.24 × 0.24 × 0.02

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5538, 3052, 2499
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.127, 1.08
No. of reflections	3052
No. of parameters	269
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.16

Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···O3	0.97	2.39	2.877 (3)	110
C10A—H10A···O3	0.98	2.33	2.848 (3)	112
C10B—H10B···O1	0.98	2.43	2.778 (3)	101

Acknowledgements

LAL thanks the Fondo Nacional de Desarrollo Científico y Tecnológico de Chile for grant No. 1060339. The authors thank the Spanish Research Council (CSIC) for the provision of a free-of-charge licence for use of the Cambridge Structural Database.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Araya, J. E., Neira, I., da Silva, S., Mortara, R. A., Manque, P., Cordero, E., Sagua, H., Loyola, A., Bórquez, J., Morales, G. & González, J. (2003). Mem. Inst. Oswaldo Cruz Rio de Janeiro, 98, 413–418. CrossRef CAS Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Loyola, L. A., Bórquez, J., Morales, G., San-Martín, A., Darias, J., Flores, N. & Giménez, A. (2004). Phytochemistry, 65, 1931–1935. Web of Science CrossRef PubMed CAS Google Scholar
Loyola, L. A., Morales, G., Perales, A. & Rodríguez, B. (1990). Tetrahedron, 46, 5413–5420. CSD CrossRef CAS Web of Science Google Scholar
Munizaga, C. & Gunkel, H. (1958). Notas etnobotánicas del pueblo de Socaire. Publicación No. 5. Universidad de Chile. Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1209

doi:10.1107/S1600536808016474

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Methyl 5a-acet­oxy­methyl-3-iso­propyl-8-methyl-1,2,3,3a,4,5,5a,6,7,10,10a,10b-dodeca­hydro-7,10-endo-epi­dioxy­cylohepta­[e]indene-3a-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Methyl 5a-acetoxymethyl-3-isopropyl-8-methyl-1,2,3,3a,4,5,5a,6,7,10,10a,10b-dodecahydro-7,10-endo-epidioxycylohepta[e]indene-3a-carboxylate