(E)-(25S)-23-Acetyl-5β-furost-22-ene-3β,26-diol

Hernández Linares, M.-G.; Sandoval Ramírez, J.; Meza Reyes, S.; Montiel Smith, S.; Bernès, S.

doi:10.1107/S1600536808004509

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o613

doi:10.1107/S1600536808004509

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(E)-(25S)-23-Acetyl-5β-furost-22-ene-3β,26-diol

María-Guadalupe Hernández Linares,^a Jesús Sandoval Ramírez,^b Socorro Meza Reyes,^b Sara Montiel Smith ^b and Sylvain Bernès ^c ^*

^aEscuela de Ingeniería Química, Universidad del Istmo, Ciudad Universitaria S/N, 70760 Sto. Domingo Tehuantepec, Oax., Mexico, ^bFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, Ciudad Universitaria, San Manuel, 72000 Puebla, Pue., Mexico, and ^cDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, NL, Mexico
^*Correspondence e-mail: sylvain_bernes@hotmail.com

(Received 4 February 2008; accepted 14 February 2008; online 22 February 2008)

The title steroid, C₂₉H₄₆O₄, is a furostene derivative with a C=C double-bond length of 1.353 (3) Å and an E configuration. The side chain is oriented toward the α face of the A–E steroidal nucleus and presents a disordered terminal CH₂—OH group [occupancies for resolved sites are 0.591 (9) and 0.409 (9)]. The methyl group at C20 attached to ring E is also oriented toward the α face, avoiding steric hindrance with the carbonyl O atom of the acetyl group. The furostene and acetyl functionalities form an α,β-unsaturated ketone system, with an s-cis configuration. All hydroxy and carbonyl groups are involved in weak intermolecular hydrogen bonds. The absolute configuration was assigned from the synthesis.

Related literature

The diacetate of the title compound has been characterized by X-ray crystallography (Sandoval-Ramírez et al., 2003 ), as well as a related furost-22-ene derivate with the C20 site substituted by a methyl group and an acetyl group (Meza-Reyes et al., 2004 ).

Experimental

Crystal data

C₂₉H₄₆O₄
M_r = 458.66
Monoclinic, C 2
a = 23.568 (2) Å
b = 7.8420 (9) Å
c = 14.7840 (14) Å
β = 101.046 (5)°
V = 2681.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 (1) K
0.65 × 0.35 × 0.32 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
4351 measured reflections
2559 independent reflections
2121 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 97 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.097
S = 1.02
2559 reflections
323 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Selected torsion angles (°)

C20—C22—C23—C23′	−3.5 (4)
C20—C22—C23—C24	175.4 (3)
O22′—C22—C23—C23′	179.3 (2)
O22′—C22—C23—C24	−1.8 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3′—H3′⋯O23"ⁱ	0.98	1.89	2.841 (3)	163
O26A—H26E⋯O3′ⁱⁱ	0.82	2.20	2.951 (6)	153
O26B—H26F⋯O3′ⁱⁱ	0.82	2.24	2.919 (16)	140
Symmetry codes: (i) x, y, z-1; (ii) x, y+1, z+1.

Data collection: XSCANS (Siemens, 1996 ); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Release 5.10; Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXTL-Plus.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004509/rz2197sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004509/rz2197Isup2.hkl

checkCIF report

Comment top

We are interested in the preparation of new steroidal derivatives, through the cleavage of the F ring in sarsasapogenin (Sandoval-Ramírez et al., 2003; Meza-Reyes et al., 2004). Such reactions are valuable entries to furostenes; the title compound is a new representative of this family.

The molecular conformation of the title compound compares well with that previously observed for the corresponding diacetate (Sandoval-Ramírez et al., 2003). The functionality C22?C23 has a bond length of 1.353 (3) Å [1.355 (3) Å for the diacetate] and is E configured. The side chain C24/C25/C26/O26 is oriented toward the α face of the A–E steroidal nucleus (Fig. 1). The terminal group CH₂—OH is disordered over two positions (denoted a and b), and has a poorly defined geometry (see Experimental). The acetyl group substituting the furostenic atom C23 forms a s-cis α,β-unsaturated ketone system with the E configuration at the C22?C23 double bond. The methyl group C21 is placed on the α steroidal face, in agreement with a general rule followed by furostenes: the bulkier group at C20 avoids steric hindrance with groups substituting C23 (Meza-Reyes et al., 2004). The solid-state conformation of the title compound is retained in solution, as confirmed by NMR data.

The crystal structure contains rather weak intermolecular hydrogen bonds, involving all hydroxyl (O3', O26a/O26b) and carbonyl (O23") groups. The main contact, O3'—H3'···O23", links molecules into chains running in the [001] direction.

Related literature top

The diacetate of the title compound has been characterized by X-ray (Sandoval-Ramírez et al., 2003), as well as a related furost-22-ene derivate with the C20 site substituted by a methyl group and an acetyl group (Meza-Reyes et al., 2004).

Experimental top

(E)-(25S)-23-Acetyl-3β,26-diacetoxy-5β,16β-furost-22-ene (500 mg, 0.9 mmol) was added under stirring to a 10% ethanolic solution of KOH (25 ml), following the reaction course by TLC. After completion, the mixture was treated with saturated NaCl and washed with water. The organic phase was extracted using CH₂Cl₂ (3×30 ml) and then dried over Na₂SO₄. After removing solvent, the crude was chromatographed (ethyl acetate/hexane, 2:3). Single crystals were obtained from an ethyl acetate solution, at 298 K. (I) has been characterized by spectroscopy: ¹H-NMR, δ (400 MHz, CDCl₃, 298 K) 4.10 (1H, s, H-3), 4.96 (1H, ddd, J = 4.2, 7.6 and 11.6 Hz, H-16), 1.86 (1H, d, J = 7.3 Hz, H-17), 0.60 (3H, s, H-18), 0.95 (3H, s, H-19), 3.70 (1H, c, J_20–21 = 7.0 Hz, H-20), 2.24 (3H, s, H-23²), 1.27 (3H, d, J_21–20 = 7.0 Hz, H-21), 2.44 and 2.22 (2H, ABX system, H-24), 3.38 and 3.45 (2H, ABX system, H-26), 0.94 (3H, d, J_27–25 = 7.0 Hz, H-27). ¹³C-NMR, δ (100 MHz, CDCl₃, 298 K) 29.87 (C-1), 27.78 (C-2), 66.95 (C-3), 30.38 (C-4), 36.40 (C-5), 26.38 (C-6), 26.44 (C-7), 35.77 (C-8), 39.90 (C-9), 35.22 (C-10), 20.39 (C-11), 38.46 (C-12), 41.75 (C-13), 55.52 (C-14), 34.98 (C-15), 86.29 (C-16), 62.59 (C-17), 13.35 (C-18), 23.81 (C-19), 37.84 (C-20), 20.17 (C-21), 178.60 (C-22), 108.32 (C-23), 33.43 (C-24), 30.27 (C-25), 66.56 (C-26), 17.08 (C-27), 199.08 (C-23¹), 29.24 (C-23²). IR (KBr, ν_max, cm^-1): 3498 (OH), 1653 (α,β-unsaturated C?O). [α]²⁰_D = +119.17 (c = 0.01 g.ml^-1, CHCl₃).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXTL-Plus (Release 5.10; Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Release 5.10; Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Release 5.10; Sheldrick, 2008); software used to prepare material for publication: SHELXTL-Plus (Release 5.10; Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with 50% displacement ellipsoids for non-H atoms. Disordered atoms C26b and O26b (lateral chain) have been omitted for clarity.

(E)-(25S)-23-Acetyl-5β-furost-22-ene-3β,26-diol top

Crystal data top

C₂₉H₄₆O₄	F(000) = 1008
M_r = 458.66	D_x = 1.136 Mg m⁻³
Monoclinic, C2	Melting point = 354–356 K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 23.568 (2) Å	Cell parameters from 74 reflections
b = 7.8420 (9) Å	θ = 4.9–12.2°
c = 14.7840 (14) Å	µ = 0.07 mm⁻¹
β = 101.046 (5)°	T = 296 K
V = 2681.7 (5) Å³	Irregular, colourless
Z = 4	0.65 × 0.35 × 0.32 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.026
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.0°
Graphite monochromator	h = −1→28
2θ/ω scans	k = −9→5
4351 measured reflections	l = −17→17
2559 independent reflections	3 standard reflections every 97 reflections
2121 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.039	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0494P)² + 0.4384P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2559 reflections	Δρ_max = 0.13 e Å⁻³
323 parameters	Δρ_min = −0.13 e Å⁻³
2 restraints	Extinction correction: SHELXTL-Plus, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.0026 (5)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₉H₄₆O₄	V = 2681.7 (5) Å³
M_r = 458.66	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 23.568 (2) Å	µ = 0.07 mm⁻¹
b = 7.8420 (9) Å	T = 296 K
c = 14.7840 (14) Å	0.65 × 0.35 × 0.32 mm
β = 101.046 (5)°

Data collection top

Bruker P4 diffractometer	R_int = 0.026
4351 measured reflections	3 standard reflections every 97 reflections
2559 independent reflections	intensity decay: 1%
2121 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.039	2 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.02	Δρ_max = 0.13 e Å⁻³
2559 reflections	Δρ_min = −0.13 e Å⁻³
323 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.34699 (12)	0.0303 (4)	0.50200 (18)	0.0581 (7)
H1A	0.3696	−0.0244	0.4619	0.070*
H1B	0.3400	−0.0537	0.5467	0.070*
C2	0.28939 (12)	0.0842 (5)	0.44463 (18)	0.0638 (8)
H2A	0.2649	0.1283	0.4851	0.077*
H2B	0.2703	−0.0147	0.4130	0.077*
C3	0.29628 (11)	0.2195 (5)	0.37409 (17)	0.0601 (8)
H3A	0.2580	0.2618	0.3453	0.072*
O3'	0.32240 (9)	0.1390 (3)	0.30500 (12)	0.0705 (6)
H3'	0.3269	0.2348	0.2647	0.106*
C4	0.33188 (11)	0.3665 (4)	0.42067 (17)	0.0558 (7)
H4A	0.3093	0.4271	0.4587	0.067*
H4B	0.3394	0.4450	0.3736	0.067*
C5	0.38998 (11)	0.3145 (4)	0.48114 (16)	0.0544 (7)
H5A	0.4135	0.2638	0.4402	0.065*
C6	0.42273 (13)	0.4707 (5)	0.52571 (19)	0.0691 (9)
H6A	0.4244	0.5557	0.4786	0.083*
H6B	0.4621	0.4380	0.5524	0.083*
C7	0.39424 (13)	0.5492 (4)	0.60094 (18)	0.0612 (8)
H7A	0.4183	0.6413	0.6307	0.073*
H7B	0.3571	0.5971	0.5728	0.073*
C8	0.38548 (11)	0.4176 (4)	0.67347 (16)	0.0488 (7)
H8A	0.4235	0.3826	0.7075	0.059*
C9	0.35351 (11)	0.2576 (4)	0.62918 (16)	0.0453 (6)
H9A	0.3155	0.2972	0.5973	0.054*
C10	0.38278 (10)	0.1769 (4)	0.55348 (16)	0.0495 (7)
C11	0.34185 (13)	0.1317 (4)	0.70299 (17)	0.0554 (7)
H11A	0.3183	0.0388	0.6730	0.066*
H11B	0.3784	0.0837	0.7340	0.066*
C12	0.31126 (12)	0.2120 (4)	0.77530 (17)	0.0543 (7)
H12A	0.2722	0.2435	0.7462	0.065*
H12B	0.3087	0.1283	0.8227	0.065*
C13	0.34296 (10)	0.3699 (3)	0.82002 (15)	0.0419 (6)
C14	0.35120 (11)	0.4910 (4)	0.74173 (16)	0.0463 (6)
H14A	0.3123	0.5116	0.7061	0.056*
C15	0.36958 (13)	0.6583 (4)	0.79078 (17)	0.0586 (7)
H15A	0.3614	0.7543	0.7489	0.070*
H15B	0.4105	0.6577	0.8178	0.070*
C16	0.33268 (12)	0.6649 (4)	0.86521 (16)	0.0520 (7)
H16A	0.3018	0.7499	0.8500	0.062*
C17	0.30738 (10)	0.4861 (4)	0.87245 (16)	0.0446 (6)
H17A	0.2668	0.4851	0.8410	0.054*
C18	0.40118 (11)	0.3167 (4)	0.88110 (17)	0.0549 (7)
H18A	0.4248	0.2613	0.8438	0.082*
H18B	0.3940	0.2397	0.9281	0.082*
H18C	0.4208	0.4162	0.9093	0.082*
C19	0.44245 (12)	0.1014 (5)	0.5966 (2)	0.0722 (9)
H19A	0.4616	0.0637	0.5484	0.108*
H19B	0.4373	0.0064	0.6352	0.108*
H19C	0.4655	0.1871	0.6328	0.108*
C20	0.31059 (10)	0.4638 (4)	0.97677 (15)	0.0460 (6)
H20A	0.3199	0.3454	0.9951	0.055*
C21	0.25366 (14)	0.5186 (5)	1.0048 (2)	0.0666 (8)
H21A	0.2590	0.5234	1.0708	0.100*
H21B	0.2239	0.4374	0.9816	0.100*
H21C	0.2426	0.6291	0.9795	0.100*
C22	0.35952 (10)	0.5804 (4)	1.01821 (16)	0.0475 (6)
O22'	0.36797 (8)	0.6985 (3)	0.95547 (11)	0.0601 (5)
C23	0.39521 (11)	0.5813 (4)	1.10164 (16)	0.0500 (6)
C23'	0.38752 (13)	0.4580 (4)	1.17199 (17)	0.0554 (7)
C23"	0.43509 (14)	0.4394 (6)	1.2564 (2)	0.0798 (11)
H23A	0.4268	0.3440	1.2924	0.120*
H23B	0.4373	0.5414	1.2928	0.120*
H23C	0.4714	0.4211	1.2374	0.120*
O23"	0.34436 (9)	0.3677 (3)	1.16669 (12)	0.0715 (6)
C24	0.44328 (12)	0.7122 (5)	1.11723 (19)	0.0615 (8)
H24A	0.4731	0.6725	1.1675	0.074*
H24B	0.4602	0.7161	1.0624	0.074*
C25	0.42713 (18)	0.8916 (6)	1.1391 (3)	0.1028 (14)
H25A	0.3916	0.9267	1.1003	0.123*	0.591 (9)
H25B	0.4080	0.9136	1.0768	0.123*	0.409 (9)
C26A	0.4232 (7)	0.9015 (16)	1.2456 (6)	0.089 (3)	0.591 (9)
H26A	0.4203	1.0204	1.2622	0.107*	0.591 (9)
H26B	0.4589	0.8573	1.2817	0.107*	0.591 (9)
O26A	0.3760 (3)	0.8110 (8)	1.2709 (5)	0.118 (3)	0.591 (9)
H26E	0.3527	0.8792	1.2846	0.177*	0.591 (9)
C26B	0.3808 (5)	0.9329 (14)	1.1735 (7)	0.096 (4)	0.409 (9)
H26C	0.3485	0.8560	1.1544	0.115*	0.409 (9)
H26D	0.3688	1.0503	1.1613	0.115*	0.409 (9)
O26B	0.4123 (8)	0.903 (3)	1.2732 (8)	0.123 (5)	0.409 (9)
H26F	0.3974	0.9613	1.3082	0.184*	0.409 (9)
C27	0.47626 (19)	1.0164 (7)	1.1335 (3)	0.1147 (16)
H27A	0.4869	1.0071	1.0742	0.172*
H27B	0.5090	0.9898	1.1807	0.172*
H27C	0.4637	1.1307	1.1421	0.172*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0725 (17)	0.0578 (18)	0.0448 (13)	0.0020 (16)	0.0132 (12)	−0.0001 (13)
C2	0.0620 (15)	0.076 (2)	0.0531 (14)	−0.0184 (16)	0.0093 (12)	−0.0056 (16)
C3	0.0535 (14)	0.078 (2)	0.0470 (13)	−0.0013 (16)	0.0039 (11)	0.0027 (15)
O3'	0.0913 (14)	0.0727 (15)	0.0479 (9)	−0.0049 (13)	0.0146 (9)	0.0015 (11)
C4	0.0602 (15)	0.0618 (19)	0.0464 (13)	0.0021 (16)	0.0126 (12)	0.0106 (14)
C5	0.0495 (14)	0.073 (2)	0.0425 (13)	−0.0035 (14)	0.0132 (11)	0.0026 (14)
C6	0.0679 (17)	0.088 (2)	0.0542 (15)	−0.0252 (19)	0.0196 (13)	0.0086 (18)
C7	0.0704 (17)	0.063 (2)	0.0518 (14)	−0.0228 (16)	0.0146 (13)	0.0034 (14)
C8	0.0441 (12)	0.0570 (18)	0.0441 (12)	−0.0069 (13)	0.0058 (10)	0.0057 (12)
C9	0.0416 (12)	0.0498 (16)	0.0438 (12)	−0.0006 (12)	0.0067 (10)	0.0049 (12)
C10	0.0456 (13)	0.0605 (18)	0.0419 (12)	0.0030 (13)	0.0070 (10)	0.0033 (13)
C11	0.0732 (17)	0.0473 (17)	0.0463 (13)	−0.0074 (15)	0.0131 (12)	0.0016 (13)
C12	0.0686 (16)	0.0490 (16)	0.0480 (13)	−0.0094 (15)	0.0177 (12)	0.0017 (13)
C13	0.0427 (12)	0.0424 (15)	0.0400 (12)	0.0000 (12)	0.0064 (10)	0.0053 (12)
C14	0.0474 (13)	0.0468 (16)	0.0427 (13)	−0.0029 (13)	0.0040 (10)	0.0047 (12)
C15	0.0768 (18)	0.0463 (17)	0.0519 (14)	−0.0076 (15)	0.0105 (13)	0.0070 (14)
C16	0.0603 (15)	0.0444 (16)	0.0478 (13)	0.0051 (13)	0.0018 (11)	0.0027 (13)
C17	0.0389 (12)	0.0488 (16)	0.0429 (12)	0.0007 (12)	−0.0005 (9)	0.0042 (12)
C18	0.0548 (14)	0.0623 (18)	0.0469 (13)	0.0127 (14)	0.0081 (11)	0.0068 (14)
C19	0.0596 (16)	0.098 (3)	0.0585 (15)	0.0196 (19)	0.0089 (13)	−0.0004 (19)
C20	0.0469 (13)	0.0458 (15)	0.0454 (12)	−0.0030 (12)	0.0093 (10)	−0.0009 (12)
C21	0.0573 (14)	0.075 (2)	0.0720 (15)	0.0054 (17)	0.0229 (12)	−0.0050 (17)
C22	0.0550 (14)	0.0441 (14)	0.0453 (12)	0.0000 (13)	0.0142 (11)	−0.0016 (13)
O22'	0.0774 (12)	0.0511 (12)	0.0493 (9)	−0.0155 (11)	0.0058 (8)	0.0015 (9)
C23	0.0502 (13)	0.0565 (17)	0.0439 (12)	−0.0022 (14)	0.0101 (11)	−0.0066 (13)
C23'	0.0585 (16)	0.065 (2)	0.0432 (13)	0.0032 (16)	0.0119 (12)	−0.0062 (14)
C23"	0.0706 (19)	0.109 (3)	0.0560 (16)	0.000 (2)	0.0016 (15)	0.0168 (19)
O23"	0.0800 (13)	0.0824 (16)	0.0506 (10)	−0.0193 (14)	0.0090 (9)	0.0101 (11)
C24	0.0533 (15)	0.083 (2)	0.0492 (13)	−0.0108 (17)	0.0131 (12)	−0.0121 (16)
C25	0.079 (2)	0.067 (2)	0.168 (4)	−0.021 (2)	0.039 (3)	−0.038 (3)
C26A	0.119 (7)	0.087 (5)	0.075 (7)	−0.029 (5)	0.053 (6)	−0.040 (6)
O26A	0.121 (4)	0.106 (4)	0.150 (5)	−0.022 (4)	0.085 (4)	−0.043 (4)
C26B	0.102 (7)	0.080 (7)	0.094 (8)	0.017 (6)	−0.011 (6)	−0.028 (6)
O26B	0.141 (11)	0.182 (12)	0.057 (5)	0.006 (9)	0.047 (6)	−0.008 (6)
C27	0.123 (3)	0.101 (3)	0.127 (3)	−0.054 (3)	0.040 (3)	−0.029 (3)

Geometric parameters (Å, º) top

C1—C2	1.517 (4)	C16—C17	1.536 (4)
C1—C10	1.539 (4)	C16—H16A	0.9800
C1—H1A	0.9700	C17—C20	1.540 (3)
C1—H1B	0.9700	C17—H17A	0.9800
C2—C3	1.518 (4)	C18—H18A	0.9600
C2—H2A	0.9700	C18—H18B	0.9600
C2—H2B	0.9700	C18—H18C	0.9600
C3—O3'	1.436 (3)	C19—H19A	0.9600
C3—C4	1.512 (4)	C19—H19B	0.9600
C3—H3A	0.9800	C19—H19C	0.9600
O3'—H3'	0.9770	C20—C22	1.507 (4)
C4—C5	1.540 (4)	C20—C21	1.539 (4)
C4—H4A	0.9700	C20—H20A	0.9800
C4—H4B	0.9700	C21—H21A	0.9600
C5—C6	1.528 (5)	C21—H21B	0.9600
C5—C10	1.551 (4)	C21—H21C	0.9600
C5—H5A	0.9800	C22—O22'	1.352 (3)
C6—C7	1.534 (4)	C22—C23	1.353 (3)
C6—H6A	0.9700	C23—C23'	1.456 (4)
C6—H6B	0.9700	C23—C24	1.513 (4)
C7—C8	1.531 (4)	C23'—O23"	1.230 (3)
C7—H7A	0.9700	C23'—C23"	1.516 (4)
C7—H7B	0.9700	C23"—H23A	0.9600
C8—C14	1.522 (4)	C23"—H23B	0.9600
C8—C9	1.543 (4)	C23"—H23C	0.9600
C8—H8A	0.9800	C24—C25	1.509 (6)
C9—C11	1.535 (4)	C24—H24A	0.9700
C9—C10	1.557 (3)	C24—H24B	0.9700
C9—H9A	0.9800	C25—C26A	1.597 (7)
C10—C19	1.546 (4)	C25—C26B	1.329 (11)
C11—C12	1.534 (4)	C25—H25A	0.9599
C11—H11A	0.9700	C25—H25B	0.9599
C11—H11B	0.9700	C25—C27	1.531 (6)
C12—C13	1.530 (4)	C26A—O26A	1.428 (15)
C12—H12A	0.9700	C26A—H26A	0.9700
C12—H12B	0.9700	C26A—H26B	0.9700
C13—C14	1.538 (3)	O26A—H26E	0.8200
C13—C17	1.544 (4)	C26B—O26B	1.536 (18)
C13—C18	1.548 (3)	C26B—H26C	0.9700
C14—C15	1.521 (4)	C26B—H26D	0.9700
C14—H14A	0.9800	O26B—H26F	0.8200
C15—C16	1.529 (4)	C27—H27A	0.9600
C15—H15A	0.9700	C27—H27B	0.9600
C15—H15B	0.9700	C27—H27C	0.9600
C16—O22'	1.455 (3)

C2—C1—C10	114.6 (3)	H15A—C15—H15B	109.1
C2—C1—H1A	108.6	O22'—C16—C15	111.2 (2)
C10—C1—H1A	108.6	O22'—C16—C17	105.2 (2)
C2—C1—H1B	108.6	C15—C16—C17	107.5 (2)
C10—C1—H1B	108.6	O22'—C16—H16A	110.9
H1A—C1—H1B	107.6	C15—C16—H16A	110.9
C1—C2—C3	112.1 (2)	C17—C16—H16A	110.9
C1—C2—H2A	109.2	C16—C17—C20	103.2 (2)
C3—C2—H2A	109.2	C16—C17—C13	104.40 (19)
C1—C2—H2B	109.2	C20—C17—C13	120.6 (2)
C3—C2—H2B	109.2	C16—C17—H17A	109.3
H2A—C2—H2B	107.9	C20—C17—H17A	109.3
O3'—C3—C4	112.5 (2)	C13—C17—H17A	109.3
O3'—C3—C2	107.4 (3)	C13—C18—H18A	109.5
C4—C3—C2	110.1 (2)	C13—C18—H18B	109.5
O3'—C3—H3A	108.9	H18A—C18—H18B	109.5
C4—C3—H3A	108.9	C13—C18—H18C	109.5
C2—C3—H3A	108.9	H18A—C18—H18C	109.5
C3—O3'—H3'	102.0	H18B—C18—H18C	109.5
C3—C4—C5	114.6 (3)	C10—C19—H19A	109.5
C3—C4—H4A	108.6	C10—C19—H19B	109.5
C5—C4—H4A	108.6	H19A—C19—H19B	109.5
C3—C4—H4B	108.6	C10—C19—H19C	109.5
C5—C4—H4B	108.6	H19A—C19—H19C	109.5
H4A—C4—H4B	107.6	H19B—C19—H19C	109.5
C6—C5—C4	111.0 (3)	C22—C20—C21	111.1 (2)
C6—C5—C10	111.9 (2)	C22—C20—C17	103.0 (2)
C4—C5—C10	112.4 (2)	C21—C20—C17	111.1 (2)
C6—C5—H5A	107.1	C22—C20—H20A	110.5
C4—C5—H5A	107.1	C21—C20—H20A	110.5
C10—C5—H5A	107.1	C17—C20—H20A	110.5
C5—C6—C7	112.3 (2)	C20—C21—H21A	109.5
C5—C6—H6A	109.1	C20—C21—H21B	109.5
C7—C6—H6A	109.1	H21A—C21—H21B	109.5
C5—C6—H6B	109.1	C20—C21—H21C	109.5
C7—C6—H6B	109.1	H21A—C21—H21C	109.5
H6A—C6—H6B	107.9	H21B—C21—H21C	109.5
C8—C7—C6	111.9 (3)	O22'—C22—C23	118.3 (2)
C8—C7—H7A	109.2	O22'—C22—C20	109.8 (2)
C6—C7—H7A	109.2	C23—C22—C20	131.9 (3)
C8—C7—H7B	109.2	C22—O22'—C16	111.8 (2)
C6—C7—H7B	109.2	C22—C23—C23'	120.5 (3)
H7A—C7—H7B	107.9	C22—C23—C24	117.3 (3)
C14—C8—C7	111.7 (3)	C23'—C23—C24	122.2 (2)
C14—C8—C9	108.12 (19)	O23"—C23'—C23	123.5 (2)
C7—C8—C9	111.8 (2)	O23"—C23'—C23"	118.0 (3)
C14—C8—H8A	108.4	C23—C23'—C23"	118.5 (3)
C7—C8—H8A	108.4	C23'—C23"—H23A	109.5
C9—C8—H8A	108.4	C23'—C23"—H23B	109.5
C11—C9—C8	111.15 (19)	H23A—C23"—H23B	109.5
C11—C9—C10	114.4 (2)	C23'—C23"—H23C	109.5
C8—C9—C10	112.8 (2)	H23A—C23"—H23C	109.5
C11—C9—H9A	105.9	H23B—C23"—H23C	109.5
C8—C9—H9A	105.9	C25—C24—C23	116.9 (2)
C10—C9—H9A	105.9	C25—C24—H24A	108.1
C1—C10—C19	106.6 (3)	C23—C24—H24A	108.1
C1—C10—C5	107.51 (19)	C25—C24—H24B	108.1
C19—C10—C5	109.8 (2)	C23—C24—H24B	108.1
C1—C10—C9	112.5 (2)	H24A—C24—H24B	107.3
C19—C10—C9	110.67 (19)	C26A—C25—H25A	111.5
C5—C10—C9	109.6 (2)	C26B—C25—H25B	93.1
C12—C11—C9	113.8 (2)	C24—C25—C26A	108.7 (6)
C12—C11—H11A	108.8	C27—C25—C26A	102.1 (6)
C9—C11—H11A	108.8	C26B—C25—C24	124.7 (6)
C12—C11—H11B	108.8	C26B—C25—C27	123.3 (6)
C9—C11—H11B	108.8	C24—C25—C27	111.1 (3)
H11A—C11—H11B	107.7	C24—C25—H25A	111.5
C13—C12—C11	112.2 (2)	C27—C25—H25A	111.5
C13—C12—H12A	109.2	C24—C25—H25B	93.1
C11—C12—H12A	109.2	C27—C25—H25B	93.1
C13—C12—H12B	109.2	O26A—C26A—C25	115.4 (8)
C11—C12—H12B	109.2	O26A—C26A—H26A	108.4
H12A—C12—H12B	107.9	O26A—C26A—H26B	108.4
C12—C13—C14	107.25 (19)	C25—C26A—H26A	108.4
C12—C13—C17	115.32 (19)	C25—C26A—H26B	108.4
C14—C13—C17	99.9 (2)	H26A—C26A—H26B	107.5
C12—C13—C18	109.8 (2)	C26A—O26A—H26E	109.5
C14—C13—C18	112.3 (2)	C25—C26B—H26C	113.2
C17—C13—C18	111.84 (19)	C25—C26B—H26D	113.2
C15—C14—C8	120.2 (2)	H26C—C26B—H26D	110.5
C15—C14—C13	103.86 (18)	C26B—O26B—H26F	109.5
C8—C14—C13	115.1 (2)	C25—C26B—O26B	92.8 (8)
C15—C14—H14A	105.5	O26B—C26B—H26C	113.1
C8—C14—H14A	105.5	O26B—C26B—H26D	113.2
C13—C14—H14A	105.5	C25—C27—H27A	109.5
C14—C15—C16	102.9 (2)	C25—C27—H27B	109.5
C14—C15—H15A	111.2	C25—C27—H27C	109.5
C16—C15—H15A	111.2	H27A—C27—H27B	109.5
C14—C15—H15B	111.2	H27A—C27—H27C	109.5
C16—C15—H15B	111.2	H27B—C27—H27C	109.5

C10—C1—C2—C3	56.9 (3)	C18—C13—C14—C8	61.4 (3)
C1—C2—C3—O3'	70.4 (3)	C8—C14—C15—C16	−168.6 (2)
C1—C2—C3—C4	−52.4 (3)	C13—C14—C15—C16	−38.0 (3)
O3'—C3—C4—C5	−67.8 (3)	C14—C15—C16—O22'	129.1 (2)
C2—C3—C4—C5	51.9 (3)	C14—C15—C16—C17	14.4 (3)
C3—C4—C5—C6	−179.7 (2)	O22'—C16—C17—C20	22.5 (2)
C3—C4—C5—C10	−53.5 (3)	C15—C16—C17—C20	141.2 (2)
C4—C5—C6—C7	70.7 (3)	O22'—C16—C17—C13	−104.4 (2)
C10—C5—C6—C7	−55.8 (3)	C15—C16—C17—C13	14.3 (2)
C5—C6—C7—C8	54.0 (3)	C12—C13—C17—C16	−151.2 (2)
C6—C7—C8—C14	−173.6 (2)	C14—C13—C17—C16	−36.6 (2)
C6—C7—C8—C9	−52.3 (3)	C18—C13—C17—C16	82.4 (2)
C14—C8—C9—C11	−53.3 (3)	C12—C13—C17—C20	93.7 (3)
C7—C8—C9—C11	−176.6 (2)	C14—C13—C17—C20	−151.8 (2)
C14—C8—C9—C10	176.6 (2)	C18—C13—C17—C20	−32.7 (3)
C7—C8—C9—C10	53.3 (3)	C16—C17—C20—C22	−25.8 (2)
C2—C1—C10—C19	−172.6 (2)	C13—C17—C20—C22	90.0 (3)
C2—C1—C10—C5	−54.8 (3)	C16—C17—C20—C21	93.3 (3)
C2—C1—C10—C9	65.9 (3)	C13—C17—C20—C21	−150.9 (2)
C6—C5—C10—C1	177.4 (2)	C21—C20—C22—O22'	−98.0 (3)
C4—C5—C10—C1	51.7 (3)	C17—C20—C22—O22'	21.0 (3)
C6—C5—C10—C19	−67.0 (3)	C21—C20—C22—C23	84.6 (4)
C4—C5—C10—C19	167.4 (2)	C17—C20—C22—C23	−156.4 (3)
C6—C5—C10—C9	54.8 (3)	C23—C22—O22'—C16	170.9 (2)
C4—C5—C10—C9	−70.9 (3)	C20—C22—O22'—C16	−7.0 (3)
C11—C9—C10—C1	58.2 (3)	C15—C16—O22'—C22	−126.5 (2)
C8—C9—C10—C1	−173.4 (2)	C17—C16—O22'—C22	−10.3 (3)
C11—C9—C10—C19	−61.0 (3)	C20—C22—C23—C23'	−3.5 (4)
C8—C9—C10—C19	67.4 (3)	C20—C22—C23—C24	175.4 (3)
C11—C9—C10—C5	177.7 (2)	O22'—C22—C23—C23'	179.3 (2)
C8—C9—C10—C5	−53.9 (2)	O22'—C22—C23—C24	−1.8 (4)
C8—C9—C11—C12	52.6 (3)	C22—C23—C23'—O23"	−12.3 (4)
C10—C9—C11—C12	−178.2 (2)	C24—C23—C23'—O23"	168.8 (3)
C9—C11—C12—C13	−53.4 (3)	C22—C23—C23'—C23"	167.7 (3)
C11—C12—C13—C14	53.4 (3)	C24—C23—C23'—C23"	−11.2 (4)
C11—C12—C13—C17	163.7 (2)	C22—C23—C24—C25	79.4 (4)
C11—C12—C13—C18	−68.9 (3)	C23'—C23—C24—C25	−101.7 (4)
C7—C8—C14—C15	−51.6 (3)	C23—C24—C25—C26B	22.1 (8)
C9—C8—C14—C15	−175.1 (2)	C23—C24—C25—C27	−168.3 (3)
C7—C8—C14—C13	−177.1 (2)	C23—C24—C25—C26A	80.1 (7)
C9—C8—C14—C13	59.5 (2)	C26B—C25—C26A—O26A	50.6 (11)
C12—C13—C14—C15	167.2 (2)	C24—C25—C26A—O26A	−69.2 (12)
C17—C13—C14—C15	46.6 (2)	C27—C25—C26A—O26A	173.3 (9)
C18—C13—C14—C15	−72.1 (3)	C24—C25—C26B—O26B	85.8 (11)
C12—C13—C14—C8	−59.3 (3)	C27—C25—C26B—O26B	−82.5 (11)
C17—C13—C14—C8	−179.86 (19)	C26A—C25—C26B—O26B	−2.6 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3′—H3′···O23"ⁱ	0.98	1.89	2.841 (3)	163
O26A—H26E···O3′ⁱⁱ	0.82	2.20	2.951 (6)	153
O26B—H26F···O3′ⁱⁱ	0.82	2.24	2.919 (16)	140

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

Experimental details

Crystal data
Chemical formula	C₂₉H₄₆O₄
M_r	458.66
Crystal system, space group	Monoclinic, C2
Temperature (K)	296
a, b, c (Å)	23.568 (2), 7.8420 (9), 14.7840 (14)
β (°)	101.046 (5)
V (Å³)	2681.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.65 × 0.35 × 0.32

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4351, 2559, 2121
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.097, 1.02
No. of reflections	2559
No. of parameters	323
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.13

Computer programs: XSCANS (Siemens, 1996), SHELXTL-Plus (Release 5.10; Sheldrick, 2008).

Selected torsion angles (º) top

C20—C22—C23—C23'	−3.5 (4)	O22'—C22—C23—C23'	179.3 (2)
C20—C22—C23—C24	175.4 (3)	O22'—C22—C23—C24	−1.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3'—H3'···O23"ⁱ	0.98	1.89	2.841 (3)	162.7
O26A—H26E···O3'ⁱⁱ	0.82	2.20	2.951 (6)	152.8
O26B—H26F···O3'ⁱⁱ	0.82	2.24	2.919 (16)	140.0

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

Acknowledgements

This work was supported by CONACyT (grant 60397).

References

Meza-Reyes, S., Montiel-Smith, S., Sandoval-Ramírez, J., Bernès, S., Hernández-Linares, G., Santillan, R. L. & Rincón, S. (2004). Acta Cryst. E60, o1137–o1139. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sandoval-Ramírez, J., Meza-Reyes, S., Montiel-Smith, S., Bernès, S., Hernández-Linares, G. & Bravo, O. V. (2003). Acta Cryst. E59, o1817–o1819. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). XSCANS. Version 2.21. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar