1,2-Bis[(3,6,9-trimethyl-3,12-ep­oxy-3,4,5,5a,6,7,8,8a,9,10,12,12a-dodeca­hydro­pyrano[4,3-j][1,2]benzodioxepin-4-yl)­oxy]ethane

Jia, L.; Yue, Z.; Lv, D.; Gao, P.

doi:10.1107/S1600536812005089

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o661

doi:10.1107/S1600536812005089

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1,2-Bis[(3,6,9-trimethyl-3,12-epoxy-3,4,5,5a,6,7,8,8a,9,10,12,12a-dodecahydropyrano[4,3-j][1,2]benzodioxepin-4-yl)oxy]ethane

Liwei Jia,^a ^* Zhengyu Yue,^b Dongying Lv ^c and Po Gao ^b

^aSchool of Pharmacy, Heilongjiang University of Chinese Medicine, Harbin 150040, People's Republic of China, ^bSchool of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^cHeilongjiang Environmental Monitoring Central Station, Harbin 150056, People's Republic of China
^*Correspondence e-mail: wsjlw@yahoo.cn

(Received 27 December 2011; accepted 5 February 2012; online 10 February 2012)

The title compound, C₃₂H₅₀O₁₀, prepared from a mixture of α- and β-dihydroartemisinin, has two β-arteether moieties linked via an –OCH₂CH₂O– bridge, so that the molecule is symmetric about the bridge. Each asymmetric unit contains a β-arteether moiety and an –OCH₂ group, which is only one-half of the molecule. The endo-peroxide bridges of the parent compounds have been retained in each half of the diol-bridged dimer. The rings exhibit chair and twist-boat conformations.

Related literature

For related literature and structures, see: Brossi et al. (1988 ); Dominguez Gerpe et al. (1988 ); Flack & Bernardinelli (2000 ); Flippen-Anderson et al. (1989 ); Haynes et al. (2002 ); Luo et al. (1984 ); Paik et al. (2006 ); Qinghaosu Research Group (1980 ); Venugopalan et al. (1995 ); Woerdenbag et al. (1993 ); Yue et al. (2006 ). For the synthesis, see: Posner et al. (1997 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₃₂H₅₀O₁₀
M_r = 594.72
Monoclinic, C 2
a = 18.033 (4) Å
b = 9.3127 (19) Å
c = 11.061 (2) Å
β = 123.58 (3)°
V = 1547.5 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.42 × 0.38 × 0.31 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.962, T_max = 0.972
6717 measured reflections
1614 independent reflections
1195 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.129
S = 1.10
1614 reflections
194 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812005089/jj2118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005089/jj2118Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812005089/jj2118Isup3.cml

checkCIF report

Comment top

Dihydroartemisinin is reported to be more therapeutically active than the parent compound. Some trioxane dimers have been found to possess high antimalarial activities (Venugopalan et al., 1995) and moderate antitumor activities. (Woerdenbag et al., 1993). The dihydroartemisinin triethylene glycol dimers, have strong in vitro growth-inhibitory activity. The dimer with β-stereochemistry at both of the lactol acetal positions is very active and highly antiproliferative (Posner et al., 1997). We conclude, therefore, that the stereochemistry of the diol linkage is an important determinant for cytotoxicity. We chose the simplified analogue, the title compound, whose structure and activity have not been reported, to find out the relationship between the activity and stereo-structure. Hence, knowledge of the structure of the title compound is of interest and is reported here.

The X-ray structures of artemisinin and artemisinin derivatives have been reported, including dihydroartemisinin, artemether, artesunic acid (Luo et al., 1984), both cis-deoxyarteether (Brossi et al., 1988) and trans-deoxyarteether (Dominguez Gerpe et al., 1988), α-artesunate, β-artesunate (Haynes et al., 2002), the symmetric form of the ether dimer of deoxydihydroartemisinin (Flippen-Anderson et al.,1989), the asymmetric form of the ether dimer of dihydroartemisinin (Yue et al., 2006), and the phthalate dimer (Paik et al. 2006). Although the endoperoxide group is an important determinant for cytotoxicity, no crystal structure of a diol dimer of dihydroartemisinin with a peroxy unit has been reported previously. We report here the crystal structure of a diol dimer of dihydroartemisinin, the title compound, which is a diol dimer of dihydroartemisinin with a unique 1,2,4-trioxane peroxy bridge.

The title molecule is symmetrical. Each moiety of the dimer is totally the same, hence we describe only the asymmetric unit here.

The seven-membered ring A(C1/C2/C3/C4/C12/O2/O1) includes key peroxy linkages [O1—O2 = 1.463 (3) Å]. The length of peroxy linkages is very close to that of the ether dimer of dihydroartemisinin (1.467 (4) Å and 1.461 (3) Å respectively) (Yue et al.,2006). The six-membered ring B(C4/C5/C6/C7/C8/C12) has a distorted chair conformation, with Cremer & Pople (1975) puckering parameters Q, θ and ϕ of 0.5422 (42) Å, 8.33 (43)° and 150 (3)°. For an ideal chair, θ has a value of 0 or 180°. The six-membered ring C(O4/C10/C9/C8/C12/C11) also has a distorted chair conformation, with puckering parameters Q, θ and ϕ of 0.5157 (39) Å, 179.09 (44)°, 93 (20)°. Similar conformations were found in the corresponding six-membered rings of dihydroartemisinin(Luo et al., 1984). The six-membered ring involving the endoperoxide bridges D(C1/O1/O2/C12/C11/O3), is best described by a twist-boat conformation, for which the puckering parameters Q, θ and ϕ are 0.7463 (38) Å, 85.77 (27)°, 335.6 (3)°. For an ideal twist-boat conformation, θ and ϕ are 90 and (60n + 30)° respectively. In contrast, the six-membered ring formed by the endoperoxide bridge in dihydroartemisinin has a distorted boat conformation.

Related literature top

For related literature and structures, see: Brossi et al. (1988); Dominguez Gerpe et al. (1988); Flack & Bernardinelli (2000); Flippen-Anderson et al. (1989); Haynes et al. (2002); Luo et al. (1984); Paik et al. (2006); Qinghaosu Research Group (1980); Venugopalan et al. (1995); Woerdenbag et al. (1993); Yue et al. (2006). For the synthesis, see: Posner et al. (1997). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

The title compound has been prepared according to a literature procedure (Posner et al., 1997). To a solution of dihydroartemisinin (297 mg, 1.05 mmol) in toluene (30 mL) at 293~298 K, glycol (0.029 mL, 0.53 mmol) was added followed by BF₃Et₂O (0.032 mL, 0.26 mmol). The reaction was stirred at the same temperature for 3 h. The mixture was then diluted with methylene chloride and was washed twice with water. The organic portions were collected, dried over (MgSO₄) and concentrated. The crude product was purified by column chromatography (flash, 7–20% ethyl acetate/petro ether) to produce the title compound (50.7 mg, 0.085 mmol, yield 17%). Crystals were obtained from ether, diffused with hexane at room temperature.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of the asymmetric unit showing with the atom-labeling and with displacement ellipsoids drawn at the 30% probability level.

1,2-Bis[(3,6,9-trimethyl-3,12-epoxy-3,4,5,5a,6,7,8,8a,9,10,12,12a- dodecahydropyrano[4,3-j][1,2]benzodioxepin-4-yl)oxy]ethane top

Crystal data top

C₃₂H₅₀O₁₀	F(000) = 644
M_r = 594.72	D_x = 1.276 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 5507 reflections
a = 18.033 (4) Å	θ = 3.7–26.0°
b = 9.3127 (19) Å	µ = 0.09 mm⁻¹
c = 11.061 (2) Å	T = 295 K
β = 123.58 (3)°	Prism, colorless
V = 1547.5 (8) Å³	0.42 × 0.38 × 0.31 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1614 independent reflections
Radiation source: fine-focus sealed tube	1195 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 10.000 pixels mm^-1	θ_max = 26.0°, θ_min = 3.7°
ω scans	h = −22→22
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→9
T_min = 0.962, T_max = 0.972	l = −13→13
6717 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0715P)² + 0.1671P] where P = (F_o² + 2F_c²)/3
1614 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.20 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₃₂H₅₀O₁₀	V = 1547.5 (8) Å³
M_r = 594.72	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 18.033 (4) Å	µ = 0.09 mm⁻¹
b = 9.3127 (19) Å	T = 295 K
c = 11.061 (2) Å	0.42 × 0.38 × 0.31 mm
β = 123.58 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1614 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1195 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.972	R_int = 0.043
6717 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	1 restraint
wR(F²) = 0.129	H-atom parameters constrained
S = 1.10	Δρ_max = 0.20 e Å⁻³
1614 reflections	Δρ_min = −0.20 e Å⁻³
194 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	0.85534 (15)	0.7920 (3)	0.4203 (3)	0.0696 (7)
O2	0.81128 (13)	0.6711 (3)	0.4401 (2)	0.0638 (7)
O3	0.76331 (14)	0.7918 (3)	0.1695 (2)	0.0578 (6)
O4	0.68018 (14)	0.8818 (2)	0.2453 (3)	0.0600 (6)
O5	0.52997 (15)	0.8430 (3)	0.1553 (3)	0.0655 (7)
C1	0.8536 (2)	0.7701 (5)	0.2924 (4)	0.0638 (9)
C2	0.8844 (2)	0.6212 (5)	0.2839 (5)	0.0741 (11)
H2A	0.9172	0.6284	0.2382	0.089*
H2B	0.9251	0.5858	0.3818	0.089*
C3	0.8104 (2)	0.5128 (4)	0.2012 (5)	0.0694 (10)
H3A	0.8369	0.4211	0.2041	0.083*
H3B	0.7740	0.5427	0.1005	0.083*
C4	0.7496 (2)	0.4904 (4)	0.2559 (4)	0.0590 (8)
H4A	0.7836	0.4307	0.3431	0.071*
C5	0.6668 (2)	0.4016 (4)	0.1475 (4)	0.0652 (9)
H5	0.6336	0.4546	0.0557	0.078*
C6	0.6066 (2)	0.3825 (4)	0.2020 (4)	0.0700 (10)
H6A	0.5535	0.3308	0.1298	0.084*
H6B	0.6371	0.3255	0.2901	0.084*
C7	0.5804 (2)	0.5246 (4)	0.2323 (4)	0.0642 (9)
H7A	0.5408	0.5085	0.2645	0.077*
H7B	0.5485	0.5805	0.1435	0.077*
C8	0.6620 (2)	0.6093 (4)	0.3487 (4)	0.0576 (8)
H8	0.6917	0.5495	0.4362	0.069*
C9	0.6407 (2)	0.7511 (4)	0.3906 (4)	0.0634 (9)
H9	0.6964	0.7825	0.4786	0.076*
C10	0.6163 (2)	0.8677 (4)	0.2800 (4)	0.0643 (9)
H10	0.6147	0.9586	0.3231	0.077*
C11	0.6992 (2)	0.7533 (3)	0.1973 (4)	0.0505 (7)
H11	0.6452	0.7232	0.1059	0.061*
C12	0.72923 (18)	0.6310 (4)	0.3060 (3)	0.0497 (7)
C13	0.9078 (3)	0.8911 (6)	0.2898 (5)	0.0916 (15)
H13A	0.8908	0.9796	0.3125	0.137*
H13B	0.8974	0.8977	0.1950	0.137*
H13C	0.9698	0.8732	0.3603	0.137*
C14	0.6926 (4)	0.2560 (5)	0.1183 (6)	0.0950 (14)
H14A	0.7275	0.2040	0.2078	0.143*
H14B	0.7269	0.2700	0.0768	0.143*
H14C	0.6398	0.2025	0.0520	0.143*
C15	0.5731 (3)	0.7405 (6)	0.4325 (5)	0.0923 (15)
H15A	0.5162	0.7137	0.3490	0.138*
H15B	0.5684	0.8318	0.4680	0.138*
H15C	0.5924	0.6693	0.5070	0.138*
C16	0.4917 (3)	0.9620 (4)	0.0595 (5)	0.0737 (10)
H16A	0.5156	1.0498	0.1152	0.088*
H16B	0.4280	0.9619	0.0162	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0611 (13)	0.0951 (18)	0.0531 (14)	−0.0343 (13)	0.0319 (11)	−0.0154 (14)
O2	0.0523 (11)	0.0890 (17)	0.0424 (12)	−0.0224 (12)	0.0214 (9)	−0.0031 (12)
O3	0.0544 (11)	0.0700 (15)	0.0532 (13)	−0.0115 (10)	0.0324 (10)	0.0023 (11)
O4	0.0605 (13)	0.0547 (13)	0.0710 (16)	−0.0134 (11)	0.0401 (12)	−0.0100 (12)
O5	0.0583 (12)	0.0607 (14)	0.0762 (17)	−0.0088 (11)	0.0364 (12)	−0.0090 (13)
C1	0.0488 (17)	0.091 (2)	0.0528 (19)	−0.0159 (17)	0.0287 (15)	−0.0025 (19)
C2	0.0547 (19)	0.098 (3)	0.073 (3)	0.002 (2)	0.0372 (18)	0.007 (2)
C3	0.067 (2)	0.078 (3)	0.067 (2)	0.0031 (18)	0.0399 (19)	0.002 (2)
C4	0.0566 (17)	0.061 (2)	0.050 (2)	−0.0021 (15)	0.0237 (15)	0.0081 (16)
C5	0.073 (2)	0.056 (2)	0.055 (2)	−0.0097 (17)	0.0284 (18)	0.0009 (17)
C6	0.073 (2)	0.060 (2)	0.062 (2)	−0.0256 (18)	0.0282 (18)	−0.0002 (19)
C7	0.0589 (18)	0.068 (2)	0.065 (2)	−0.0213 (16)	0.0337 (17)	−0.0048 (18)
C8	0.0548 (17)	0.071 (2)	0.0455 (18)	−0.0178 (15)	0.0267 (15)	−0.0040 (17)
C9	0.0580 (18)	0.086 (2)	0.054 (2)	−0.0178 (17)	0.0354 (16)	−0.0146 (19)
C10	0.0571 (17)	0.068 (2)	0.074 (2)	−0.0143 (17)	0.0399 (17)	−0.020 (2)
C11	0.0509 (17)	0.0509 (17)	0.0500 (18)	−0.0146 (13)	0.0281 (15)	−0.0052 (14)
C12	0.0446 (14)	0.0619 (19)	0.0361 (15)	−0.0144 (13)	0.0183 (12)	−0.0016 (14)
C13	0.073 (2)	0.129 (4)	0.079 (3)	−0.044 (3)	0.046 (2)	−0.013 (3)
C14	0.116 (3)	0.066 (3)	0.100 (4)	−0.009 (2)	0.057 (3)	−0.013 (3)
C15	0.087 (3)	0.129 (4)	0.086 (3)	−0.030 (3)	0.063 (3)	−0.024 (3)
C16	0.071 (2)	0.0533 (19)	0.093 (3)	0.0042 (17)	0.043 (2)	−0.005 (2)

Geometric parameters (Å, º) top

O1—C1	1.412 (4)	C6—H6B	0.9700
O1—O2	1.463 (3)	C7—C8	1.532 (4)
O2—C12	1.450 (3)	C7—H7A	0.9700
O3—C11	1.397 (3)	C7—H7B	0.9700
O3—C1	1.446 (4)	C8—C9	1.518 (5)
O4—C10	1.407 (4)	C8—C12	1.538 (4)
O4—C11	1.426 (4)	C8—H8	0.9800
O5—C10	1.416 (4)	C9—C10	1.508 (5)
O5—C16	1.421 (5)	C9—C15	1.528 (5)
C1—C13	1.502 (5)	C9—H9	0.9800
C1—C2	1.516 (6)	C10—H10	0.9800
C2—C3	1.512 (6)	C11—C12	1.522 (4)
C2—H2A	0.9700	C11—H11	0.9800
C2—H2B	0.9700	C13—H13A	0.9600
C3—C4	1.532 (5)	C13—H13B	0.9600
C3—H3A	0.9700	C13—H13C	0.9600
C3—H3B	0.9700	C14—H14A	0.9600
C4—C5	1.539 (5)	C14—H14B	0.9600
C4—C12	1.544 (5)	C14—H14C	0.9600
C4—H4A	0.9800	C15—H15A	0.9600
C5—C6	1.515 (5)	C15—H15B	0.9600
C5—C14	1.525 (6)	C15—H15C	0.9600
C5—H5	0.9800	C16—C16ⁱ	1.504 (9)
C6—C7	1.504 (5)	C16—H16A	0.9700
C6—H6A	0.9700	C16—H16B	0.9700

C1—O1—O2	109.0 (2)	C7—C8—H8	106.5
C12—O2—O1	112.1 (2)	C12—C8—H8	106.5
C11—O3—C1	113.3 (2)	C10—C9—C8	112.8 (3)
C10—O4—C11	115.2 (2)	C10—C9—C15	111.6 (3)
C10—O5—C16	114.8 (3)	C8—C9—C15	114.6 (3)
O1—C1—O3	108.1 (3)	C10—C9—H9	105.6
O1—C1—C13	104.9 (3)	C8—C9—H9	105.6
O3—C1—C13	106.5 (3)	C15—C9—H9	105.6
O1—C1—C2	112.8 (3)	O4—C10—O5	112.0 (3)
O3—C1—C2	109.3 (3)	O4—C10—C9	111.9 (3)
C13—C1—C2	114.8 (3)	O5—C10—C9	110.1 (3)
C3—C2—C1	114.7 (3)	O4—C10—H10	107.6
C3—C2—H2A	108.6	O5—C10—H10	107.6
C1—C2—H2A	108.6	C9—C10—H10	107.6
C3—C2—H2B	108.6	O3—C11—O4	105.4 (2)
C1—C2—H2B	108.6	O3—C11—C12	113.0 (2)
H2A—C2—H2B	107.6	O4—C11—C12	112.8 (2)
C2—C3—C4	115.9 (3)	O3—C11—H11	108.5
C2—C3—H3A	108.3	O4—C11—H11	108.5
C4—C3—H3A	108.3	C12—C11—H11	108.5
C2—C3—H3B	108.3	O2—C12—C11	109.4 (2)
C4—C3—H3B	108.3	O2—C12—C8	104.6 (2)
H3A—C3—H3B	107.4	C11—C12—C8	110.1 (2)
C3—C4—C5	111.3 (3)	O2—C12—C4	106.0 (2)
C3—C4—C12	113.0 (3)	C11—C12—C4	113.7 (2)
C5—C4—C12	114.5 (3)	C8—C12—C4	112.5 (2)
C3—C4—H4A	105.7	C1—C13—H13A	109.5
C5—C4—H4A	105.7	C1—C13—H13B	109.5
C12—C4—H4A	105.7	H13A—C13—H13B	109.5
C6—C5—C14	110.4 (3)	C1—C13—H13C	109.5
C6—C5—C4	110.7 (3)	H13A—C13—H13C	109.5
C14—C5—C4	111.3 (3)	H13B—C13—H13C	109.5
C6—C5—H5	108.1	C5—C14—H14A	109.5
C14—C5—H5	108.1	C5—C14—H14B	109.5
C4—C5—H5	108.1	H14A—C14—H14B	109.5
C7—C6—C5	111.5 (3)	C5—C14—H14C	109.5
C7—C6—H6A	109.3	H14A—C14—H14C	109.5
C5—C6—H6A	109.3	H14B—C14—H14C	109.5
C7—C6—H6B	109.3	C9—C15—H15A	109.5
C5—C6—H6B	109.3	C9—C15—H15B	109.5
H6A—C6—H6B	108.0	H15A—C15—H15B	109.5
C6—C7—C8	111.5 (3)	C9—C15—H15C	109.5
C6—C7—H7A	109.3	H15A—C15—H15C	109.5
C8—C7—H7A	109.3	H15B—C15—H15C	109.5
C6—C7—H7B	109.3	O5—C16—C16ⁱ	113.8 (3)
C8—C7—H7B	109.3	O5—C16—H16A	108.8
H7A—C7—H7B	108.0	C16ⁱ—C16—H16A	108.8
C9—C8—C7	114.6 (3)	O5—C16—H16B	108.8
C9—C8—C12	110.8 (3)	C16ⁱ—C16—H16B	108.8
C7—C8—C12	111.3 (3)	H16A—C16—H16B	107.7
C9—C8—H8	106.5

C1—O1—O2—C12	−44.0 (3)	C8—C9—C10—O4	−51.6 (4)
O2—O1—C1—O3	72.2 (3)	C15—C9—C10—O4	177.6 (3)
O2—O1—C1—C13	−174.5 (3)	C8—C9—C10—O5	73.6 (3)
O2—O1—C1—C2	−48.8 (3)	C15—C9—C10—O5	−57.2 (4)
C11—O3—C1—O1	−31.6 (4)	C1—O3—C11—O4	92.6 (3)
C11—O3—C1—C13	−143.8 (3)	C1—O3—C11—C12	−31.0 (4)
C11—O3—C1—C2	91.6 (3)	C10—O4—C11—O3	−180.0 (3)
O1—C1—C2—C3	94.4 (4)	C10—O4—C11—C12	−56.3 (3)
O3—C1—C2—C3	−25.9 (4)	O1—O2—C12—C11	−17.4 (3)
C13—C1—C2—C3	−145.5 (4)	O1—O2—C12—C8	−135.4 (2)
C1—C2—C3—C4	−56.7 (5)	O1—O2—C12—C4	105.6 (3)
C2—C3—C4—C5	168.8 (3)	O3—C11—C12—O2	57.2 (3)
C2—C3—C4—C12	38.4 (4)	O4—C11—C12—O2	−62.2 (3)
C3—C4—C5—C6	−179.1 (3)	O3—C11—C12—C8	171.6 (3)
C12—C4—C5—C6	−49.4 (4)	O4—C11—C12—C8	52.2 (3)
C3—C4—C5—C14	57.7 (4)	O3—C11—C12—C4	−61.0 (3)
C12—C4—C5—C14	−172.7 (3)	O4—C11—C12—C4	179.6 (2)
C14—C5—C6—C7	179.8 (3)	C9—C8—C12—O2	68.0 (3)
C4—C5—C6—C7	56.0 (4)	C7—C8—C12—O2	−163.2 (3)
C5—C6—C7—C8	−60.4 (4)	C9—C8—C12—C11	−49.4 (3)
C6—C7—C8—C9	−177.2 (3)	C7—C8—C12—C11	79.4 (3)
C6—C7—C8—C12	56.1 (4)	C9—C8—C12—C4	−177.4 (3)
C7—C8—C9—C10	−77.1 (3)	C7—C8—C12—C4	−48.6 (4)
C12—C8—C9—C10	49.9 (4)	C3—C4—C12—O2	−71.1 (3)
C7—C8—C9—C15	52.1 (4)	C5—C4—C12—O2	160.1 (3)
C12—C8—C9—C15	179.1 (3)	C3—C4—C12—C11	49.1 (4)
C11—O4—C10—O5	−69.3 (4)	C5—C4—C12—C11	−79.8 (3)
C11—O4—C10—C9	54.9 (4)	C3—C4—C12—C8	175.2 (3)
C16—O5—C10—O4	−69.2 (4)	C5—C4—C12—C8	46.4 (4)
C16—O5—C10—C9	165.7 (3)	C10—O5—C16—C16ⁱ	92.8 (4)

Symmetry code: (i) −x+1, y, −z.

Experimental details

Crystal data
Chemical formula	C₃₂H₅₀O₁₀
M_r	594.72
Crystal system, space group	Monoclinic, C2
Temperature (K)	295
a, b, c (Å)	18.033 (4), 9.3127 (19), 11.061 (2)
β (°)	123.58 (3)
V (Å³)	1547.5 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.42 × 0.38 × 0.31

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.962, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	6717, 1614, 1195
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.129, 1.10
No. of reflections	1614
No. of parameters	194
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

References

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