(–)-(5S,8S,9R,10S,13R,14R)-15,16-Dide­oxy-16,17-epoxy-16-oxospongian-15-yl acetate

Blake, A.J.; González, M.A.; Gil-Gimeno, M.J.

doi:10.1107/S0108270106006366

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 62| Part 4| April 2006| Pages o208-o210

doi:10.1107/S0108270106006366

(–)-(5S,8S,9R,10S,13R,14R)-15,16-Dideoxy-16,17-epoxy-16-oxospongian-15-yl acetate

Alexander J. Blake,^a ^* Miguel A. González ^b ^* and Maria J. Gil-Gimeno ^b

^aSchool of Chemistry, The University of Nottingham, University Park, Nottingham NG7 2RD, England, and ^bDepartamento de Química Orgánica/Instituto de Ciencia Molecular (ICMOL), Universidad de Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain
^*Correspondence e-mail: a.j.blake@nottingham.ac.uk, miguel.a.gonzalez@uv.es

(Received 13 February 2006; accepted 20 February 2006; online 18 March 2006)

The title compound (aplyroseol-14), C₂₂H₃₄O₄, exhibits a lactone-based structure that is novel for spongian-type diterpenoids. The structure, which features a six-membered lactone ring, was proposed by Arnó, González & Zaragozá [J. Org. Chem. (2003), 68, 1242–1251] on the basis of spectroscopic data and chemical correlations. This assignment has been confirmed, and it is shown that the molecule contains a trans–anti–trans 6/6/6 tricyclic hydrocarbon system and that the acetoxymethyl group lies in an equatorial position. Pairs of near-linear C—H⋯O interactions link molecules into extended chains.

Comment

Spongian diterpenoids are bioactive natural products isolated exclusively from sponges and shell-less molluscs (nudibranchs), which are believed to be capable of sequestering the spongian-derived metabolites from the sponges on which they feed. Most of these compounds play a key role as eco-physiological mediators and are of interest as potential therapeutic agents (Arnó, Betancur-Galvis et al., 2003 ).

The carbon skeleton (I), named `spongian' in accordance with IUPAC recommendations (Kazlauskas et al., 1979 ), was chosen as the fundamental parent structure for this family of natural compounds, with the numbering depicted. Thus, spongians typically exhibit the hydrocarbon ring system (I), consisting of a steroid-like ABCD ring system containing an oxygenated group, such as a tetrahydrofuran ring, and with varying oxidation patterns on rings A–D.

The title compound, (1b), was isolated from the sponge Aplysilla rosea Barrois by Taylor & Toth (1997 ), and the structure (1a), in which ring D is usually a five-membered lactone typical of other members of the spongian family (Cimino et al., 1974 ; Karuso & Taylor, 1986 ; Miyamoto et al., 1996 ), was assigned from one- and two-dimensional ¹H NMR data, high-resolution mass spectrometry, and IR spectroscopy. Following our studies directed towards the synthesis of C-17-functionalized spongians (Arnó et al., 2001 ), we selected (1a) as a potential target compound and we readily synthesized

a compound (Arnó, González & Zaragozá, 2003

) whose spectroscopic data were in apparently good agreement with those reported for natural aplyroseol-14. However, a careful study of the spectroscopic data, in particular the IR and NMR spectra, indicated that the molecule contained the six-membered lactone (1b)

instead of the expected five-membered one seen, for example, in (5R*,7S*,8S*,9S*,10R*,13S*,14S*)-16-oxospongian-7,17-diyl diacetate (Karuso & Taylor, 1986

) or 7α-hydroxyspongian-16-one (Miyamoto et al., 1996

). We supported our assignment by synthesizing the proposed structure (1a)

for aplyroseol-14 and making comparisons with the published data. As expected, the synthetic compound (1a)

gave spectroscopic data that, although generally similar to those reported for natural (1b)

, were nevertheless clearly different. Owing to the uniqueness of the carbon skeleton of (1b)

, together with apparent disagreement in some reported data (IR bands), a single-crystal X-ray study was carried out on synthetic (1b)

in order to confirm the structural assignment. The ¹H NMR spectra of synthetic (1b)

and natural (1b)

were found to be in excellent agreement.

A perspective view of the molecule is shown in Fig. 1. Both the chemical connectivity and the relative stereochemistry are in full agreement with those proposed by Arnó, González & Zaragozá (2003) for aplyroseol-14 (1b). The stereochemistry at atoms C5 (S), C9 (R) and C10 (S) is invariant during the synthesis, but three new asymmetric centres were introduced at C8 (S), C13 (R) and C14 (R). The molecule contains a trans–anti–trans 6/6/6 tricyclic hydrocarbon system to which a six-membered lactone ring is attached at atoms C8 and C13. All six-membered rings adopt chair conformations with axially disposed methyl or lactone substituents. However, the lactone ring (C8/C14/C13/C16/O17/C17) is distorted towards a half-chair conformation; while atom C8 lies 0.734 (3) Å below the least-squares mean plane through atoms C14, C13, O17 and C17, atom C16 lies only 0.329 (3) Å above it. The acetoxymethyl group at atom C14 lies in an equatorial position. Bond lengths and angles are typical for such sterically non-strained molecules.

Molecules are linked by almost linear pairwise C—H⋯O interactions (Table 1 and Fig. 2). One of these interactions occurs between carbonyl atom O21 of the acetoxy group and atom H15 of the methylene group adjacent to the acetoxy group in a neighbouring molecule; the other involves methine atom H14 and lactone atom O17 in the same neighbouring molecule. The interactions link the molecules into chains running along the b axis. The C—H⋯O interactions contrast with the situation in analogous compounds containing hydroxy groups (Schmitz et al., 1985 ; Karuso et al., 1986 ; Miyamoto et al., 1996), where the presence of the hydroxy groups leads to O—H⋯O=C hydrogen bonds being the primary intermolecular contacts.

Figure 1
A view of (1b), showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level.

Figure 2
A view of the chains of molecules linked along the b axis by pairwise near-linear C—H⋯O interactions. C atoms are shown as large open circles, O atoms as dotted circles and H atoms as small open circles. [Symmetry codes: (i) x, y + 1, z; (ii) x, y − 1, z.]

Experimental

Compound (1b) was synthesized from the chiral synthon (+)-podocarp-8(14)-en-13-one, readily available from commercial (−)-abietic acid (Abad et al., 1985 ; see scheme below). The absolute stereochemistry at atoms C5, C9 and C10 was therefore fixed. During the synthesis, the key intermediate methyl 8β,14β-dioxopodocarpan-13β-oate was prepared, in which three new stereocentres, viz. C8, C13 and C14, were introduced. This intermediate was transformed into (−)-16-oxospongian-17-al, confirming the absolute stereochemistry of all asymmetric centres. Finally, the latter was converted into (1b) by standard reduction followed by acetylation. This two-step process involved a translactonization reaction that occurred during the reduction step. Crystals were grown from a solution of (1b) in dichloromethane/hexane (1:4).

Crystal data

C₂₂H₃₄O₄
M_r = 362.49
Monoclinic, C 2
a = 13.377 (2) Å
b = 6.0824 (8) Å
c = 23.834 (3) Å
β = 94.235 (2)°
V = 1933.9 (5) Å³
Z = 4
D_x = 1.245 Mg m⁻³
Mo Kα radiation
Cell parameters from 3476 reflections
θ = 2.6–27.5°
μ = 0.08 mm⁻¹
T = 150 (2) K
Tablet, colourless
1.07 × 0.50 × 0.13 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
ω scans
5352 measured reflections
2382 independent reflections
2200 reflections with I > 2σ(I)
R_int = 0.133
θ_max = 27.5°
h = −17 → 15
k = −7 → 7
l = −30 → 22

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.133
S = 0.92
2382 reflections
239 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.106P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O17ⁱ	1.00	2.49	3.486 (3)	171
C15—H15⋯O21ⁱⁱ	0.99	2.52	3.509 (3)	173
Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z.

The absolute configuration of (1b) was assigned as for (+)-podocarp-8(14)-en-13-one (Abad et al., 1985), based on the absolute configuration of (−)-abietic acid as determined by optical rotatory dispersion measurements (e.g. Bose & Struck, 1959 ). All H atoms were included at geometrically calculated positions and constrained to ride on their parent C atoms at distances of 0.98, 0.99 or 1.00 Å for methyl, methylene or methine groups, respectively, and with U_iso(H) values of 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for others. As there are no significant anomalous dispersion effects, Friedel opposites were merged prior to the final cycles of refinement.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT and SHELXTL (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: PLATON (Spek, 2003 ) and SHELXTL; software used to prepare material for publication: enCIFer (Allen et al., 2004 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, 1b. DOI: 10.1107/S0108270106006366/ln3004sup1.cif

Structure factors: contains datablock 1b. DOI: 10.1107/S0108270106006366/ln30041bsup2.hkl

Comment top

The carbon skeleton (I) (Scheme 1), named `spongian' in accordance with IUPAC recommendations (Kazlauskas et al., 1979), was chosen as the fundamental parent structure for this family of natural compounds with the numbering depicted. Thus, spongians typically exhibit the hydrocarbon ring system (I), consisting of a steroid-like ABCD ring system containing an oxygenated group, such as a tetrahydrofuran ring, and with varying oxidation patterns on rings A–D.

The title compound, (1b), was isolated from the sponge Aplysilla rosea Barrois by Taylor & Toth (1997) and the structure (1a), in which ring D is usually a five-membered lactone typical of other members of the spongian family (Cimino et al., 1974; Karuso & Taylor, 1986; Miyamoto et al., 1996), was assigned from one-dimensional and two-dimensional ¹H NMR data, high-resolution mass spectrometry and IR spectroscopy. Following our studies directed towards the synthesis of C-17-functionalized spongians (Arnó et al., 2001), we selected (1a) as a potential target compound and we readily synthesized a compound (Arnó, González & Zaragozá, 2003) whose spectroscopic data were in apparently good agreement with those reported for natural aplyroseol-14. However, a careful study of the spectroscopic data, in particular the IR and NMR spectra, indicated that the molecule contained the six-membered lactone (1b) instead of the expected five-membered one seen, for example, in 5R*,7S*,8S*,9S*,10R*,13S*,14S*)-16-oxospongian-7,17-diyl diacetate (Karuso & Taylor, 1986) or 7α-hydroxyspongian-16-one (Miyamoto et al., 1996). We supported our assignment by synthesizing the proposed structure (1a) for aplyroseol-14 and making comparisons with the published data. As expected, the synthetic compound (1a) gave spectroscopic data that, although generally similar to those reported for natural (1b), were nevertheless clearly different. Owing to the uniqueness of the carbon skeleton of (1b), together with apparent disagreement in some reported data (IR bands), a single-crystal X-ray study was carried out on synthetic (1b) in order to confirm the structural assignment. The ¹H NMR spectra of synthetic (1b) and natural (1b) were found be be in excellent agreement.

A perspective view of the molecule is shown in Fig. 1. Both chemical connectivity and relative stereochemistry are in full agreement with those proposed by Arnó, González & Zaragozá (2003) for aplyroseol-14, (1b). The stereochemistry at C5 (S), C9 (R) and C10 (S) is invariant during the synthesis, but three new asymmetric centres were introduced at C8 (S), C13 (R) and C14 (R). The molecule contains a trans–anti–trans 6/6/6 tricyclic hydrocarbon group to which a six-membered lactone ring is attached at C8 and C13. All six-membered rings adopt chair conformations with axially disposed methyl or lactone substituents. However, the lactone ring (atoms C8/C14/C13/C16/O17/C17) is distorted towards a half-chair conformation; while atom C8 lies 0.734 (3) Å below the least-squares mean plane through atoms C14, C13, O17 and C17, atom C16 lies only 0.329 (3) Å above it. The acetoxymethyl group at atom C14 lies in an equatorial position. Bond lengths and angles are typical for such sterically non-strained molecules.

Molecules are linked by almost linear pairwise C—H···O interactions (Table 1 and Fig. 2). One of these interactions occurs between carbonyl atom O21 of the acetoxy group and atom H15 of the methylene group adjacent to the acetoxy group in a neighbouring molecule; the other involves methine atom H14 and lactone atom O17 in the same neighbouring molecule. The interactions link the molecules into chains running along the b axis. The C—H···O interactions contrast with the situation in analogous compounds containing hydroxy groups (Schmitz et al., 1985; Karuso et al., 1986; Miyamoto et al., 1996), where the presence of the hydroxy groups leads to O—H···O═C hydrogen bonds being the primary intermolecular contacts.

Experimental top

Compound (1b) was synthesized from the chiral synthon (+)-podocarp-8(14)-en-13-one, readily available from commercial (-)-abietic acid (Abad et al., 1985; see Scheme 2). The absolute stereochemistry at atoms C5, C9 and C10 was therefore fixed. During the synthesis, the key intermediate methyl 8β,14β-dioxopodocarpan-13β-oate was prepared, in which three new stereocenters, C8, C13 and C14, were introduced. This intermediate was transformed into (-)-spongian-16-oxo-17-al confirming the absolute stereochemistry of all asymmetric centers. Finally, the latter was converted into aplyroseol-14, (1b), by standard reduction followed by acetylation. This two-step process involved a translactonization reaction that occurred during the reduction step. Crystals were grown from a solution of (1b) in dichloromethane/hexane (1/4).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT and SHELXTL (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: enCIFer (Allen et al., 2004) and PLATON.

Figures top

	Fig. 1. A view of (1b), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A view of the chains of molecules linked along the b axis by pairwise, near-linear C—H···O interactions. C atoms are shown as large open circles, O atoms as dotted circles and H atoms as small open circles. [Symmetry codes: (i) x, y + 1, z; (ii) x, y − 1, z.]

(-)-(5S,8S,9R,10S,13R,14R)-15-Acetoxy-15,16-dideoxy-16,17-epoxyspongian-16-one top

Crystal data top

C₂₂H₃₄O₄	F(000) = 792
M_r = 362.49	D_x = 1.245 Mg m⁻³
Monoclinic, C2	Melting point = 419–421 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 13.377 (2) Å	Cell parameters from 3476 reflections
b = 6.0824 (8) Å	θ = 2.6–27.5°
c = 23.834 (3) Å	µ = 0.08 mm⁻¹
β = 94.235 (2)°	T = 150 K
V = 1933.9 (5) Å³	Tablet, colourless
Z = 4	1.07 × 0.50 × 0.13 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2200 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.133
Graphite monochromator	θ_max = 27.5°, θ_min = 2.6°
ω scans	h = −17→15
5352 measured reflections	k = −7→7
2382 independent reflections	l = −30→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.106P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max = 0.001
2382 reflections	Δρ_max = 0.40 e Å⁻³
239 parameters	Δρ_min = −0.27 e Å⁻³
1 restraint

Crystal data top

C₂₂H₃₄O₄	V = 1933.9 (5) Å³
M_r = 362.49	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 13.377 (2) Å	µ = 0.08 mm⁻¹
b = 6.0824 (8) Å	T = 150 K
c = 23.834 (3) Å	1.07 × 0.50 × 0.13 mm
β = 94.235 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2200 reflections with I > 2σ(I)
5352 measured reflections	R_int = 0.133
2382 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.133	H-atom parameters constrained
S = 0.92	Δρ_max = 0.40 e Å⁻³
2382 reflections	Δρ_min = −0.27 e Å⁻³
239 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.

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

	x	y	z	U_iso*/U_eq
C1	0.17249 (16)	0.5239 (4)	0.64125 (8)	0.0223 (4)
H1A	0.1075	0.4550	0.6481	0.027*
H1B	0.1710	0.6774	0.6550	0.027*
C2	0.18436 (16)	0.5260 (5)	0.57783 (8)	0.0261 (5)
H2A	0.1790	0.3739	0.5631	0.031*
H2B	0.1295	0.6137	0.5587	0.031*
C3	0.28490 (18)	0.6232 (5)	0.56464 (9)	0.0287 (5)
H3A	0.2857	0.7812	0.5747	0.034*
H3B	0.2913	0.6124	0.5236	0.034*
C4	0.37618 (16)	0.5113 (4)	0.59559 (8)	0.0233 (5)
C5	0.35872 (16)	0.4998 (4)	0.65979 (8)	0.0198 (4)
H5	0.3554	0.6569	0.6719	0.024*
C6	0.44649 (16)	0.4030 (4)	0.69668 (8)	0.0219 (4)
H6A	0.4495	0.2422	0.6905	0.026*
H6B	0.5101	0.4678	0.6857	0.026*
C7	0.43527 (15)	0.4490 (4)	0.75898 (8)	0.0213 (4)
H7A	0.4386	0.6098	0.7653	0.026*
H7B	0.4923	0.3813	0.7815	0.026*
C8	0.33666 (16)	0.3610 (3)	0.78006 (8)	0.0186 (4)
C9	0.24753 (15)	0.4441 (3)	0.73928 (8)	0.0182 (4)
H9	0.2502	0.6079	0.7427	0.022*
C10	0.25741 (16)	0.3985 (3)	0.67533 (8)	0.0177 (4)
C11	0.14387 (16)	0.3811 (4)	0.75895 (9)	0.0226 (4)
H11A	0.0912	0.4600	0.7355	0.027*
H11B	0.1331	0.2215	0.7531	0.027*
C12	0.13324 (16)	0.4360 (4)	0.82095 (8)	0.0233 (4)
H12A	0.0707	0.3698	0.8330	0.028*
H12B	0.1286	0.5974	0.8255	0.028*
C13	0.22299 (18)	0.3487 (4)	0.85824 (9)	0.0219 (4)
H13	0.2150	0.3927	0.8981	0.026*
C14	0.31962 (16)	0.4501 (3)	0.83942 (8)	0.0191 (4)
H14	0.3080	0.6120	0.8356	0.023*
O15	0.38191 (13)	0.5208 (3)	0.93589 (6)	0.0271 (4)
C15	0.40754 (18)	0.4176 (4)	0.88379 (8)	0.0232 (5)
H15	0.4202	0.2588	0.8900	0.028*
H15B	0.4690	0.4853	0.8708	0.028*
O16	0.16935 (14)	−0.0141 (3)	0.88247 (8)	0.0368 (4)
C16	0.21947 (18)	0.0995 (4)	0.85418 (9)	0.0253 (5)
O17	0.26571 (13)	0.0020 (3)	0.81182 (7)	0.0271 (4)
C17	0.34732 (17)	0.1109 (4)	0.78647 (9)	0.0226 (4)
H17A	0.3538	0.0464	0.7488	0.027*
H17B	0.4103	0.0794	0.8096	0.027*
C18	0.46733 (19)	0.6582 (5)	0.58765 (10)	0.0331 (6)
H18A	0.4714	0.6888	0.5475	0.050*
H18B	0.5285	0.5829	0.6024	0.050*
H18C	0.4603	0.7968	0.6080	0.050*
C19	0.3960 (2)	0.2883 (5)	0.56855 (9)	0.0306 (5)
H19A	0.4155	0.3111	0.5301	0.046*
H19B	0.3350	0.1986	0.5675	0.046*
H19C	0.4502	0.2126	0.5907	0.046*
C20	0.24679 (17)	0.1503 (4)	0.66120 (9)	0.0233 (4)
H20A	0.2072	0.0784	0.6889	0.035*
H20B	0.3134	0.0829	0.6622	0.035*
H20C	0.2130	0.1327	0.6236	0.035*
O21	0.43121 (13)	0.8479 (3)	0.90373 (7)	0.0309 (4)
C21	0.39490 (18)	0.7387 (4)	0.93946 (8)	0.0260 (5)
C22	0.3563 (2)	0.8273 (5)	0.99275 (10)	0.0385 (6)
H22A	0.3875	0.9701	1.0017	0.058*
H22B	0.3729	0.7244	1.0237	0.058*
H22C	0.2834	0.8450	0.9876	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0168 (9)	0.0248 (10)	0.0245 (9)	0.0007 (8)	−0.0048 (7)	−0.0005 (8)
C2	0.0203 (10)	0.0348 (12)	0.0219 (9)	−0.0002 (10)	−0.0068 (7)	0.0014 (9)
C3	0.0316 (12)	0.0304 (12)	0.0233 (10)	−0.0042 (10)	−0.0026 (8)	0.0033 (9)
C4	0.0184 (10)	0.0316 (12)	0.0193 (9)	−0.0048 (9)	−0.0021 (7)	−0.0023 (9)
C5	0.0190 (10)	0.0206 (10)	0.0193 (8)	−0.0024 (8)	−0.0026 (7)	−0.0014 (8)
C6	0.0155 (10)	0.0279 (11)	0.0219 (9)	−0.0015 (8)	−0.0014 (7)	−0.0018 (8)
C7	0.0146 (9)	0.0274 (11)	0.0211 (9)	−0.0031 (9)	−0.0045 (7)	−0.0003 (8)
C8	0.0186 (10)	0.0177 (10)	0.0189 (9)	−0.0012 (8)	−0.0020 (7)	−0.0005 (7)
C9	0.0182 (9)	0.0165 (9)	0.0193 (8)	0.0013 (8)	−0.0035 (7)	−0.0004 (7)
C10	0.0129 (9)	0.0201 (10)	0.0194 (8)	−0.0005 (7)	−0.0031 (7)	−0.0026 (7)
C11	0.0183 (10)	0.0263 (11)	0.0225 (9)	0.0007 (8)	−0.0019 (7)	0.0004 (8)
C12	0.0209 (10)	0.0244 (11)	0.0245 (10)	0.0026 (9)	0.0015 (8)	0.0003 (9)
C13	0.0245 (11)	0.0197 (10)	0.0214 (9)	−0.0014 (9)	0.0006 (8)	0.0013 (8)
C14	0.0204 (10)	0.0170 (9)	0.0194 (8)	−0.0004 (8)	−0.0026 (7)	0.0005 (7)
O15	0.0348 (9)	0.0272 (8)	0.0189 (7)	−0.0042 (8)	−0.0018 (6)	0.0008 (6)
C15	0.0265 (11)	0.0220 (10)	0.0203 (9)	0.0009 (8)	−0.0046 (8)	0.0004 (8)
O16	0.0387 (10)	0.0287 (9)	0.0434 (10)	−0.0067 (8)	0.0052 (8)	0.0100 (8)
C16	0.0266 (12)	0.0219 (10)	0.0266 (10)	−0.0003 (9)	−0.0034 (8)	0.0045 (9)
O17	0.0317 (9)	0.0171 (7)	0.0323 (8)	−0.0017 (7)	0.0002 (6)	0.0022 (6)
C17	0.0214 (10)	0.0203 (10)	0.0256 (9)	0.0025 (8)	−0.0019 (8)	0.0013 (8)
C18	0.0280 (12)	0.0452 (15)	0.0261 (10)	−0.0139 (11)	0.0005 (9)	0.0028 (10)
C19	0.0303 (12)	0.0368 (12)	0.0248 (10)	0.0004 (10)	0.0020 (9)	−0.0077 (10)
C20	0.0218 (10)	0.0207 (10)	0.0272 (10)	−0.0031 (8)	−0.0001 (8)	−0.0050 (8)
O21	0.0365 (10)	0.0263 (8)	0.0299 (8)	−0.0033 (8)	0.0012 (7)	−0.0004 (7)
C21	0.0301 (12)	0.0281 (12)	0.0190 (9)	−0.0004 (10)	−0.0045 (8)	−0.0029 (9)
C22	0.0455 (15)	0.0419 (15)	0.0283 (11)	−0.0005 (13)	0.0041 (10)	−0.0100 (11)

Geometric parameters (Å, º) top

C1—C2	1.532 (3)	C12—C13	1.535 (3)
C1—C10	1.548 (3)	C12—H12A	0.9900
C1—H1A	0.9900	C12—H12B	0.9900
C1—H1B	0.9900	C13—C16	1.519 (3)
C2—C3	1.523 (3)	C13—C14	1.529 (3)
C2—H2A	0.9900	C13—H13	1.0000
C2—H2B	0.9900	C14—C15	1.535 (3)
C3—C4	1.538 (3)	C14—H14	1.0000
C3—H3A	0.9900	O15—C21	1.339 (3)
C3—H3B	0.9900	O15—C15	1.455 (3)
C4—C19	1.533 (4)	C15—H15	0.9900
C4—C18	1.535 (3)	C15—H15B	0.9900
C4—C5	1.566 (3)	O16—C16	1.204 (3)
C5—C6	1.531 (3)	C16—O17	1.359 (3)
C5—C10	1.558 (3)	O17—C17	1.447 (3)
C5—H5	1.0000	C17—H17A	0.9900
C6—C7	1.529 (3)	C17—H17B	0.9900
C6—H6A	0.9900	C18—H18A	0.9800
C6—H6B	0.9900	C18—H18B	0.9800
C7—C8	1.542 (3)	C18—H18C	0.9800
C7—H7A	0.9900	C19—H19A	0.9800
C7—H7B	0.9900	C19—H19B	0.9800
C8—C17	1.534 (3)	C19—H19C	0.9800
C8—C14	1.548 (3)	C20—H20A	0.9800
C8—C9	1.566 (3)	C20—H20B	0.9800
C9—C11	1.545 (3)	C20—H20C	0.9800
C9—C10	1.564 (3)	O21—C21	1.210 (3)
C9—H9	1.0000	C21—C22	1.505 (3)
C10—C20	1.551 (3)	C22—H22A	0.9800
C11—C12	1.532 (3)	C22—H22B	0.9800
C11—H11A	0.9900	C22—H22C	0.9800
C11—H11B	0.9900

C2—C1—C10	113.37 (18)	C9—C11—H11B	109.0
C2—C1—H1A	108.9	H11A—C11—H11B	107.8
C10—C1—H1A	108.9	C11—C12—C13	111.03 (17)
C2—C1—H1B	108.9	C11—C12—H12A	109.4
C10—C1—H1B	108.9	C13—C12—H12A	109.4
H1A—C1—H1B	107.7	C11—C12—H12B	109.4
C3—C2—C1	111.37 (17)	C13—C12—H12B	109.4
C3—C2—H2A	109.4	H12A—C12—H12B	108.0
C1—C2—H2A	109.4	C16—C13—C14	114.0 (2)
C3—C2—H2B	109.4	C16—C13—C12	106.8 (2)
C1—C2—H2B	109.4	C14—C13—C12	109.43 (17)
H2A—C2—H2B	108.0	C16—C13—H13	108.8
C2—C3—C4	114.3 (2)	C14—C13—H13	108.8
C2—C3—H3A	108.7	C12—C13—H13	108.8
C4—C3—H3A	108.7	C13—C14—C15	111.54 (17)
C2—C3—H3B	108.7	C13—C14—C8	108.16 (16)
C4—C3—H3B	108.7	C15—C14—C8	115.32 (18)
H3A—C3—H3B	107.6	C13—C14—H14	107.1
C19—C4—C18	107.43 (19)	C15—C14—H14	107.1
C19—C4—C3	110.23 (18)	C8—C14—H14	107.1
C18—C4—C3	107.0 (2)	C21—O15—C15	116.34 (18)
C19—C4—C5	114.4 (2)	O15—C15—C14	108.41 (18)
C18—C4—C5	108.89 (17)	O15—C15—H15	110.0
C3—C4—C5	108.55 (17)	C14—C15—H15	110.0
C6—C5—C10	110.79 (17)	O15—C15—H15B	110.0
C6—C5—C4	114.51 (17)	C14—C15—H15B	110.0
C10—C5—C4	116.42 (16)	H15—C15—H15B	108.4
C6—C5—H5	104.5	O16—C16—O17	117.9 (2)
C10—C5—H5	104.5	O16—C16—C13	123.6 (2)
C4—C5—H5	104.5	O17—C16—C13	118.0 (2)
C7—C6—C5	111.16 (17)	C16—O17—C17	120.63 (17)
C7—C6—H6A	109.4	O17—C17—C8	115.34 (19)
C5—C6—H6A	109.4	O17—C17—H17A	108.4
C7—C6—H6B	109.4	C8—C17—H17A	108.4
C5—C6—H6B	109.4	O17—C17—H17B	108.4
H6A—C6—H6B	108.0	C8—C17—H17B	108.4
C6—C7—C8	113.61 (16)	H17A—C17—H17B	107.5
C6—C7—H7A	108.8	C4—C18—H18A	109.5
C8—C7—H7A	108.8	C4—C18—H18B	109.5
C6—C7—H7B	108.8	H18A—C18—H18B	109.5
C8—C7—H7B	108.8	C4—C18—H18C	109.5
H7A—C7—H7B	107.7	H18A—C18—H18C	109.5
C17—C8—C7	107.54 (19)	H18B—C18—H18C	109.5
C17—C8—C14	105.97 (17)	C4—C19—H19A	109.5
C7—C8—C14	111.32 (16)	C4—C19—H19B	109.5
C17—C8—C9	116.30 (19)	H19A—C19—H19B	109.5
C7—C8—C9	108.42 (16)	C4—C19—H19C	109.5
C14—C8—C9	107.31 (16)	H19A—C19—H19C	109.5
C11—C9—C10	113.20 (16)	H19B—C19—H19C	109.5
C11—C9—C8	113.02 (16)	C10—C20—H20A	109.5
C10—C9—C8	115.61 (16)	C10—C20—H20B	109.5
C11—C9—H9	104.5	H20A—C20—H20B	109.5
C10—C9—H9	104.5	C10—C20—H20C	109.5
C8—C9—H9	104.5	H20A—C20—H20C	109.5
C1—C10—C20	108.29 (18)	H20B—C20—H20C	109.5
C1—C10—C5	107.33 (17)	O21—C21—O15	123.8 (2)
C20—C10—C5	113.61 (18)	O21—C21—C22	125.3 (2)
C1—C10—C9	108.20 (16)	O15—C21—C22	110.9 (2)
C20—C10—C9	111.80 (17)	C21—C22—H22A	109.5
C5—C10—C9	107.40 (16)	C21—C22—H22B	109.5
C12—C11—C9	112.84 (18)	H22A—C22—H22B	109.5
C12—C11—H11A	109.0	C21—C22—H22C	109.5
C9—C11—H11A	109.0	H22A—C22—H22C	109.5
C12—C11—H11B	109.0	H22B—C22—H22C	109.5

C10—C1—C2—C3	−56.6 (3)	C11—C9—C10—C20	−62.7 (2)
C1—C2—C3—C4	54.7 (3)	C8—C9—C10—C20	70.0 (2)
C2—C3—C4—C19	75.4 (2)	C11—C9—C10—C5	172.06 (17)
C2—C3—C4—C18	−168.08 (19)	C8—C9—C10—C5	−55.3 (2)
C2—C3—C4—C5	−50.7 (3)	C10—C9—C11—C12	−177.40 (17)
C19—C4—C5—C6	59.6 (2)	C8—C9—C11—C12	48.7 (2)
C18—C4—C5—C6	−60.6 (3)	C9—C11—C12—C13	−49.5 (2)
C3—C4—C5—C6	−176.84 (19)	C11—C12—C13—C16	−65.0 (2)
C19—C4—C5—C10	−71.9 (2)	C11—C12—C13—C14	58.9 (2)
C18—C4—C5—C10	167.9 (2)	C16—C13—C14—C15	−75.3 (2)
C3—C4—C5—C10	51.7 (3)	C12—C13—C14—C15	165.17 (18)
C10—C5—C6—C7	−60.0 (2)	C16—C13—C14—C8	52.5 (2)
C4—C5—C6—C7	165.89 (18)	C12—C13—C14—C8	−67.0 (2)
C5—C6—C7—C8	57.3 (2)	C17—C8—C14—C13	−61.2 (2)
C6—C7—C8—C17	75.4 (2)	C7—C8—C14—C13	−177.80 (17)
C6—C7—C8—C14	−168.96 (17)	C9—C8—C14—C13	63.7 (2)
C6—C7—C8—C9	−51.1 (2)	C17—C8—C14—C15	64.5 (2)
C17—C8—C9—C11	63.3 (2)	C7—C8—C14—C15	−52.2 (2)
C7—C8—C9—C11	−175.42 (16)	C9—C8—C14—C15	−170.65 (18)
C14—C8—C9—C11	−55.1 (2)	C21—O15—C15—C14	−80.9 (2)
C17—C8—C9—C10	−69.4 (2)	C13—C14—C15—O15	−59.3 (2)
C7—C8—C9—C10	51.9 (2)	C8—C14—C15—O15	176.77 (16)
C14—C8—C9—C10	172.21 (17)	C14—C13—C16—O16	154.9 (2)
C2—C1—C10—C20	−68.7 (2)	C12—C13—C16—O16	−84.2 (3)
C2—C1—C10—C5	54.3 (2)	C14—C13—C16—O17	−33.4 (3)
C2—C1—C10—C9	169.90 (18)	C12—C13—C16—O17	87.6 (2)
C6—C5—C10—C1	173.53 (16)	O16—C16—O17—C17	−163.0 (2)
C4—C5—C10—C1	−53.3 (2)	C13—C16—O17—C17	24.8 (3)
C6—C5—C10—C20	−66.8 (2)	C16—O17—C17—C8	−37.0 (3)
C4—C5—C10—C20	66.4 (2)	C7—C8—C17—O17	173.55 (16)
C6—C5—C10—C9	57.4 (2)	C14—C8—C17—O17	54.4 (2)
C4—C5—C10—C9	−169.45 (18)	C9—C8—C17—O17	−64.7 (2)
C11—C9—C10—C1	56.5 (2)	C15—O15—C21—O21	−4.3 (4)
C8—C9—C10—C1	−170.88 (17)	C15—O15—C21—C22	174.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O17ⁱ	1.00	2.49	3.486 (3)	171
C15—H15···O21ⁱⁱ	0.99	2.52	3.509 (3)	173

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

Experimental details

Crystal data
Chemical formula	C₂₂H₃₄O₄
M_r	362.49
Crystal system, space group	Monoclinic, C2
Temperature (K)	150
a, b, c (Å)	13.377 (2), 6.0824 (8), 23.834 (3)
β (°)	94.235 (2)
V (Å³)	1933.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	1.07 × 0.50 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5352, 2382, 2200
R_int	0.133
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.133, 0.92
No. of reflections	2382
No. of parameters	239
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.27

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT and SHELXTL (Bruker, 2001), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), enCIFer (Allen et al., 2004) and PLATON.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O17ⁱ	1.00	2.49	3.486 (3)	171
C15—H15···O21ⁱⁱ	0.99	2.52	3.509 (3)	173

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

Acknowledgements

The authors thank the EPSRC (UK) for the funding of a diffractometer. We also gratefully acknowledge financial support by the Spanish Ministry of Education and Science under a `Ramón y Cajal' research grant.

References

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ISSN: 2053-2296

Volume 62| Part 4| April 2006| Pages o208-o210

doi:10.1107/S0108270106006366

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

(–)-(5S,8S,9R,10S,13R,14R)-15,16-Dide­­oxy-16,17-ep­oxy-16-oxospongian-15-yl acetate

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(–)-(5S,8S,9R,10S,13R,14R)-15,16-Dideoxy-16,17-epoxy-16-oxospongian-15-yl acetate