1,2:1′,2′-Di-O-iso­propyl­idenedi­furan­ose-C12 higher carbon sugar

Zhang, Q.; Zhou, G.; He, P.; Chen, X.; Liu, H.

doi:10.1107/S1600536813021776

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1399

doi:10.1107/S1600536813021776

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1,2:1′,2′-Di-O-isopropylidenedifuranose-C12 higher carbon sugar

Qiurong Zhang,^a Guangqiang Zhou,^a Peng He,^a Xuebin Chen ^a and Hongmin Liu ^a ^*

^aNew Drug Reseach & Development Center, Zhengzhou Univresity, Zhengzhou 450001, People's Republic of China
^*Correspondence e-mail: zqr409@163.com

(Received 24 June 2013; accepted 5 August 2013; online 10 August 2013)

In the title compound, C₁₈H₂₈O₈, the five-membered ring with one O atom attached to the ethyl substituent has a twisted conformation about the C—O bond. The adjacent cis-fused ring with two O atoms also has a twisted conformation about one of the C—O bonds. The dihedral angle between these rings (all atoms) is 59.05 (12)°. The five-membered ring linked to the ethynyl susbtituent is twisted about a C—C bond; the cis-fused adjacent ring is twisted about a C—O bond [dihedral angle between the rings (all atoms) = 71.78 (12)°]. Two intramolecular O—H⋯O hydrogen bonds occur. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, generating [001] chains.

Related literature

For further synthetic details, see: Meyer & Jochims (1969 ). For background to higher-carbon sugars, see: Iwasa et al. (1978 ); Harada et al. (1981 ); Liu et al. (2006 ).

Experimental

Crystal data

C₁₈H₂₈O₈
M_r = 372.40
Orthorhombic, P 2₁ 2₁ 2
a = 21.5802 (6) Å
b = 15.3758 (4) Å
c = 5.73626 (14) Å
V = 1903.37 (8) Å³
Z = 4
Cu Kα radiation
μ = 0.86 mm⁻¹
T = 291 K
0.28 × 0.25 × 0.25 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T_min = 0.796, T_max = 0.815
7406 measured reflections
3407 independent reflections
3079 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.099
S = 1.05
3407 reflections
262 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3′—H3′⋯O4′ⁱ	0.79 (3)	2.36 (3)	3.038 (2)	144 (2)
O3′—H3′⋯O2′	0.79 (3)	2.22 (3)	2.685 (2)	119 (2)
O3—H3⋯O2	0.82 (4)	2.11 (3)	2.647 (2)	122 (3)
Symmetry code: (i) x, y, z+1.

Data collection: CrysAlis PRO (Agilent, 2011 ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813021776/hb7100sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021776/hb7100Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813021776/hb7100Isup3.cml

checkCIF report

Comment top

The term higher carbon sugars is customarily employed with monosaccharides containing seven or more consecutive carbon atoms in the chain. Higher carbon sugars have been attracting the increasing attention of organic chemists in the past decades due to the fact that they can be used as non-metabolized analogues of di- and oligosaccharides and are components of some antibiotics (Iwasa et al., 1978; Harada et al., 1981) and also that they are carbohydrate precursors for higher carbon amino sugars (Liu et al., 2006).

C₁₈H₂₈O₈,the title compound (I), is a free C12 higher carbon sugar,whose structure consists of a fused system made up of two methylenedioxy ring and two tetrahydrofuran rings. Both of them, one methylenedioxy ring connects parallelly to tetrahydrofuran, give two fragments with V-shaped models. In the crystal, O—H···O hydrogen bonds (Table 1), link the molecules into [001] chains.

The crystal packing is shown in Figure 2.

Related literature top

For further synthetic details, see: Meyer & Jochims (1969). For background to higher-carbon sugars, see: Iwasa et al. (1978); Harada et al. (1981); Liu et al. (2006).

Experimental top

The title compound (I) was synthesized from 5,6;5',6'-di-alkene-C12 higher carbon sugar as described previously (Meyer & Jochims, 1969), whose starting material was D-Glucose. A solution of 5,6;5',6'-di-alkene-C12 higher carbon sugar(400 mg, 1 mmol) in aq. CH₃OH(10 ml) was stirred at room temperature overnight

A suspension of 5,6;5',6'-di-alkene-C12 higher carbon sugar(400 mg, 1 mmol) and NaBH₄ (0.080 g, 2.08 mmol) in anhydrous MeOH (15 ml) was stirred at room temperature for 1 h. the solvent was evaporated and water (10 ml) was added to the residue, and the mixture was extracted with EtOAc. The combined organic layers were washed with water and dried with anhydrous Na₂SO₄. After filtration and evaporation of the solvent, the residue

was dissolved in methanol (20 ml) and 5% Pd/C [500 mg, suspended in methanol (5 ml)] was added. The mixture was degassed, and stirred under an atmosphere of hydrogen. After 4 h, the mixture was filtered and evaporated, Purification of the residue by column chromatography gave the title compound as white solid. Colourless prisms were grown by slow evaporation from CH₃OH solution at room temperature for two weeks. mp: 398 K; R_f = 0.40 (petroleum ether/EtOAc, 2:1); ¹H NMR (400 MHz, CDCl₃)σ: 5.98 (1H, d, J = 3.6 Hz), 5.78 (1H, s), 4.84 (1H, q, J = 6.9 Hz), 4.54 (1H, d, J = 3.6 Hz), 4.22 (1H, t), 3.74(1H, m), 2.89 (1H, s), 2.22 (1H, d, J = 3.2 Hz), 1.78 2H, m), 1.70 (3H, d), 1.68 (3H, s), 1.58 (3H, s), 1.48 (3H, s), 1.46 (3H, s), 1.03 (3H, d, J = 7.5 Hz); ¹³C NMR (100 MHz, CDCl₃) σ: 154.51, 117.02, 114.03, 106.48, 104.54, 98.57, 94.88, 83.93, 80.18, 79.70, 70.21, 28.03, 27.97, 27.82, 27.62, 21.85, 10.33, 10.23.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.
	Fig. 2. Packing diagram.

6-{5-Ethyl-6-hydroxy-2,2-dimethyltetrahydro-2H-furo[2,3-d][1,3]dioxol-6a-yl}-5-ethylidene-2,2-dimethyl-tetrahydro-2H-furo[2,3-d][1,3]dioxol-6-ol top

Crystal data top

C₁₈H₂₈O₈	D_x = 1.300 Mg m⁻³
M_r = 372.40	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2	Cell parameters from 3059 reflections
a = 21.5802 (6) Å	θ = 2.9–66.9°
b = 15.3758 (4) Å	µ = 0.86 mm⁻¹
c = 5.73626 (14) Å	T = 291 K
V = 1903.37 (8) Å³	Prism, colourless
Z = 4	0.28 × 0.25 × 0.25 mm
F(000) = 800

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	3407 independent reflections
Radiation source: fine-focus sealed tube	3079 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 0 pixels mm^-1	θ_max = 67.1°, θ_min = 3.5°
ω scans	h = −24→25
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −18→17
T_min = 0.796, T_max = 0.815	l = −4→6
7406 measured reflections

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0493P)² + 0.1435P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3407 reflections	Δρ_max = 0.18 e Å⁻³
262 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0064 (4)

Crystal data top

C₁₈H₂₈O₈	V = 1903.37 (8) Å³
M_r = 372.40	Z = 4
Orthorhombic, P2₁2₁2	Cu Kα radiation
a = 21.5802 (6) Å	µ = 0.86 mm⁻¹
b = 15.3758 (4) Å	T = 291 K
c = 5.73626 (14) Å	0.28 × 0.25 × 0.25 mm

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	3407 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3079 reflections with I > 2σ(I)
T_min = 0.796, T_max = 0.815	R_int = 0.026
7406 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.18 e Å⁻³
3407 reflections	Δρ_min = −0.14 e Å⁻³
262 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	0.67974 (7)	0.17289 (11)	0.8701 (3)	0.0581 (4)
O1'	0.43970 (8)	0.11163 (12)	0.6552 (3)	0.0671 (5)
O2	0.63054 (6)	0.23737 (9)	0.5648 (2)	0.0418 (3)
O2'	0.48323 (7)	0.15439 (10)	0.9957 (3)	0.0589 (4)
O3	0.66664 (9)	0.40182 (11)	0.5529 (3)	0.0587 (4)
O3'	0.53146 (7)	0.31495 (9)	1.0267 (2)	0.0484 (3)
O4	0.69581 (7)	0.31202 (12)	1.0229 (3)	0.0659 (5)
O4'	0.48425 (7)	0.23484 (9)	0.4771 (2)	0.0520 (3)
C1	0.65181 (9)	0.24742 (14)	0.9636 (4)	0.0496 (5)
H1	0.6260	0.2325	1.0984	0.060*
C1'	0.49427 (10)	0.15364 (13)	0.5914 (4)	0.0506 (5)
H1'	0.5199	0.1155	0.4944	0.061*
C2	0.61210 (9)	0.28500 (12)	0.7651 (3)	0.0402 (4)
C2'	0.52685 (9)	0.17335 (13)	0.8211 (3)	0.0436 (4)
H2'	0.5644	0.1382	0.8392	0.052*
C3	0.63097 (9)	0.38264 (13)	0.7514 (3)	0.0440 (4)
H3A	0.5938	0.4192	0.7538	0.053*
C3'	0.54226 (9)	0.27154 (13)	0.8134 (3)	0.0398 (4)
C4	0.66772 (10)	0.39550 (15)	0.9764 (4)	0.0522 (5)
H4	0.6386	0.4087	1.1025	0.063*
C4'	0.49988 (9)	0.30348 (13)	0.6225 (3)	0.0430 (4)
C5	0.71713 (12)	0.4649 (2)	0.9732 (5)	0.0689 (7)
C5'	0.47675 (10)	0.38174 (15)	0.5919 (4)	0.0528 (5)
C6	0.69055 (13)	0.55472 (19)	0.9364 (6)	0.0798 (8)
H6A	0.6581	0.5649	1.0476	0.120*
H6B	0.6741	0.5591	0.7814	0.120*
H6C	0.7226	0.5973	0.9570	0.120*
C6'	0.43255 (12)	0.40709 (18)	0.4031 (5)	0.0679 (7)
H6'A	0.4021	0.4463	0.4648	0.102*
H6'B	0.4124	0.3560	0.3437	0.102*
H6'C	0.4548	0.4352	0.2794	0.102*
C7	0.68335 (10)	0.18190 (16)	0.6219 (4)	0.0544 (5)
C7'	0.42493 (10)	0.13080 (15)	0.8936 (4)	0.0561 (6)
C8	0.74382 (10)	0.2237 (2)	0.5493 (5)	0.0704 (7)
H8A	0.7776	0.1860	0.5890	0.106*
H8B	0.7486	0.2782	0.6288	0.106*
H8C	0.7436	0.2335	0.3840	0.106*
C8'	0.40403 (12)	0.04898 (16)	1.0145 (6)	0.0737 (8)
H8'A	0.4364	0.0063	1.0071	0.111*
H8'B	0.3676	0.0268	0.9390	0.111*
H8'C	0.3948	0.0617	1.1746	0.111*
C9	0.67296 (12)	0.09468 (15)	0.5109 (5)	0.0677 (7)
H9A	0.6340	0.0715	0.5621	0.101*
H9B	0.7057	0.0558	0.5552	0.101*
H9C	0.6725	0.1010	0.3444	0.101*
C9'	0.37906 (14)	0.2033 (2)	0.9154 (7)	0.0895 (10)
H9'A	0.3409	0.1868	0.8420	0.134*
H9'B	0.3952	0.2545	0.8408	0.134*
H9'C	0.3717	0.2153	1.0772	0.134*
H5'	0.4875 (10)	0.4262 (15)	0.710 (4)	0.053 (6)*
H3'	0.5069 (12)	0.2890 (17)	1.101 (5)	0.058 (7)*
H3	0.6667 (15)	0.360 (2)	0.465 (7)	0.098 (11)*
H5A	0.7420 (12)	0.4587 (17)	1.114 (5)	0.062 (7)*
H5B	0.7476 (13)	0.4461 (19)	0.861 (6)	0.073 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0578 (8)	0.0739 (10)	0.0424 (8)	0.0150 (7)	−0.0015 (7)	0.0186 (7)
O1'	0.0701 (10)	0.0719 (10)	0.0592 (10)	−0.0228 (8)	−0.0003 (8)	−0.0176 (9)
O2	0.0427 (6)	0.0527 (7)	0.0299 (6)	0.0081 (5)	−0.0010 (5)	0.0049 (6)
O2'	0.0650 (9)	0.0692 (9)	0.0425 (8)	−0.0251 (7)	0.0092 (7)	−0.0090 (7)
O3	0.0817 (11)	0.0624 (9)	0.0319 (8)	−0.0183 (8)	0.0031 (8)	0.0065 (7)
O3'	0.0597 (8)	0.0523 (7)	0.0330 (7)	−0.0070 (7)	0.0067 (7)	−0.0056 (6)
O4	0.0618 (9)	0.0881 (11)	0.0478 (9)	−0.0116 (8)	−0.0254 (8)	0.0167 (9)
O4'	0.0642 (8)	0.0547 (8)	0.0370 (7)	0.0048 (6)	−0.0076 (7)	−0.0093 (6)
C1	0.0485 (10)	0.0668 (12)	0.0334 (10)	−0.0007 (9)	−0.0060 (8)	0.0112 (9)
C1'	0.0598 (11)	0.0494 (10)	0.0426 (11)	−0.0011 (9)	0.0042 (10)	−0.0135 (8)
C2	0.0438 (9)	0.0489 (10)	0.0279 (8)	−0.0001 (8)	−0.0022 (8)	0.0044 (7)
C2'	0.0465 (10)	0.0446 (10)	0.0396 (10)	−0.0009 (8)	0.0041 (8)	−0.0010 (8)
C3	0.0470 (10)	0.0539 (10)	0.0311 (9)	−0.0067 (8)	−0.0039 (8)	0.0044 (9)
C3'	0.0451 (10)	0.0434 (9)	0.0310 (9)	−0.0013 (8)	0.0014 (7)	−0.0023 (8)
C4	0.0516 (11)	0.0718 (13)	0.0334 (10)	−0.0135 (10)	−0.0070 (9)	0.0048 (10)
C4'	0.0397 (9)	0.0521 (11)	0.0371 (9)	−0.0013 (8)	0.0010 (8)	−0.0058 (8)
C5	0.0569 (13)	0.1004 (19)	0.0494 (14)	−0.0283 (13)	−0.0095 (12)	−0.0036 (14)
C5'	0.0528 (11)	0.0533 (11)	0.0525 (12)	0.0079 (9)	−0.0060 (10)	−0.0030 (10)
C6	0.0788 (16)	0.0816 (18)	0.079 (2)	−0.0332 (14)	0.0106 (16)	−0.0152 (15)
C6'	0.0632 (13)	0.0748 (16)	0.0657 (16)	0.0218 (12)	−0.0114 (12)	0.0000 (13)
C7	0.0501 (11)	0.0722 (14)	0.0408 (11)	0.0182 (10)	0.0019 (9)	0.0149 (10)
C7'	0.0547 (11)	0.0557 (12)	0.0579 (13)	−0.0105 (10)	0.0084 (11)	−0.0128 (11)
C8	0.0471 (11)	0.1052 (19)	0.0590 (15)	0.0145 (12)	0.0032 (11)	0.0242 (15)
C8'	0.0734 (15)	0.0600 (13)	0.088 (2)	−0.0209 (11)	0.0128 (15)	−0.0109 (14)
C9	0.0784 (15)	0.0659 (14)	0.0587 (15)	0.0272 (12)	0.0125 (13)	0.0090 (12)
C9'	0.0757 (17)	0.0783 (18)	0.114 (3)	0.0070 (14)	0.0291 (19)	0.0034 (18)

Geometric parameters (Å, º) top

O1—C1	1.401 (3)	C4'—C5'	1.315 (3)
O1—C7	1.433 (3)	C5—C6	1.510 (4)
O1'—C1'	1.392 (3)	C5—H5A	0.98 (3)
O1'—C7'	1.434 (3)	C5—H5B	0.96 (3)
O2—C2	1.420 (2)	C5'—C6'	1.495 (3)
O2—C7	1.461 (2)	C5'—H5'	0.99 (2)
O2'—C2'	1.405 (2)	C6—H6A	0.9600
O2'—C7'	1.435 (3)	C6—H6B	0.9600
O3—C3	1.406 (2)	C6—H6C	0.9600
O3—H3	0.82 (4)	C6'—H6'A	0.9600
O3'—C3'	1.413 (2)	C6'—H6'B	0.9600
O3'—H3'	0.79 (3)	C6'—H6'C	0.9600
O4—C1	1.416 (3)	C7—C9	1.501 (4)
O4—C4	1.444 (3)	C7—C8	1.513 (3)
O4'—C4'	1.387 (2)	C7'—C9'	1.496 (4)
O4'—C1'	1.427 (3)	C7'—C8'	1.506 (4)
C1—C2	1.538 (3)	C8—H8A	0.9600
C1—H1	0.9800	C8—H8B	0.9600
C1'—C2'	1.524 (3)	C8—H8C	0.9600
C1'—H1'	0.9800	C8'—H8'A	0.9600
C2—C3'	1.546 (3)	C8'—H8'B	0.9600
C2—C3	1.557 (3)	C8'—H8'C	0.9600
C2'—C3'	1.547 (3)	C9—H9A	0.9600
C2'—H2'	0.9800	C9—H9B	0.9600
C3—C4	1.528 (3)	C9—H9C	0.9600
C3—H3A	0.9800	C9'—H9'A	0.9600
C3'—C4'	1.509 (3)	C9'—H9'B	0.9600
C4—C5	1.508 (3)	C9'—H9'C	0.9600
C4—H4	0.9800

C1—O1—C7	108.93 (17)	C6—C5—H5A	114.4 (16)
C1'—O1'—C7'	110.09 (16)	C4—C5—H5B	106.1 (18)
C2—O2—C7	109.79 (14)	C6—C5—H5B	116.1 (19)
C2'—O2'—C7'	110.41 (16)	H5A—C5—H5B	99 (2)
C3—O3—H3	109 (2)	C4'—C5'—C6'	125.3 (2)
C3'—O3'—H3'	109.9 (19)	C4'—C5'—H5'	116.9 (14)
C1—O4—C4	107.33 (15)	C6'—C5'—H5'	117.7 (14)
C4'—O4'—C1'	110.65 (15)	C5—C6—H6A	109.5
O1—C1—O4	112.17 (17)	C5—C6—H6B	109.5
O1—C1—C2	105.30 (17)	H6A—C6—H6B	109.5
O4—C1—C2	106.74 (16)	C5—C6—H6C	109.5
O1—C1—H1	110.8	H6A—C6—H6C	109.5
O4—C1—H1	110.8	H6B—C6—H6C	109.5
C2—C1—H1	110.8	C5'—C6'—H6'A	109.5
O1'—C1'—O4'	113.50 (18)	C5'—C6'—H6'B	109.5
O1'—C1'—C2'	104.77 (17)	H6'A—C6'—H6'B	109.5
O4'—C1'—C2'	107.05 (16)	C5'—C6'—H6'C	109.5
O1'—C1'—H1'	110.4	H6'A—C6'—H6'C	109.5
O4'—C1'—H1'	110.4	H6'B—C6'—H6'C	109.5
C2'—C1'—H1'	110.4	O1—C7—O2	103.70 (17)
O2—C2—C1	104.42 (15)	O1—C7—C9	109.1 (2)
O2—C2—C3'	110.43 (15)	O2—C7—C9	108.06 (19)
C1—C2—C3'	111.12 (15)	O1—C7—C8	111.2 (2)
O2—C2—C3	112.52 (15)	O2—C7—C8	111.28 (18)
C1—C2—C3	104.71 (15)	C9—C7—C8	113.0 (2)
C3'—C2—C3	113.14 (16)	O1'—C7'—O2'	104.26 (17)
O2'—C2'—C1'	105.43 (16)	O1'—C7'—C9'	112.3 (3)
O2'—C2'—C3'	111.52 (16)	O2'—C7'—C9'	110.9 (2)
C1'—C2'—C3'	105.59 (16)	O1'—C7'—C8'	109.5 (2)
O2'—C2'—H2'	111.3	O2'—C7'—C8'	106.6 (2)
C1'—C2'—H2'	111.3	C9'—C7'—C8'	112.7 (2)
C3'—C2'—H2'	111.3	C7—C8—H8A	109.5
O3—C3—C4	111.89 (16)	C7—C8—H8B	109.5
O3—C3—C2	112.73 (17)	H8A—C8—H8B	109.5
C4—C3—C2	102.58 (16)	C7—C8—H8C	109.5
O3—C3—H3A	109.8	H8A—C8—H8C	109.5
C4—C3—H3A	109.8	H8B—C8—H8C	109.5
C2—C3—H3A	109.8	C7'—C8'—H8'A	109.5
O3'—C3'—C4'	112.00 (15)	C7'—C8'—H8'B	109.5
O3'—C3'—C2	104.63 (15)	H8'A—C8'—H8'B	109.5
C4'—C3'—C2	114.66 (15)	C7'—C8'—H8'C	109.5
O3'—C3'—C2'	113.63 (16)	H8'A—C8'—H8'C	109.5
C4'—C3'—C2'	102.01 (15)	H8'B—C8'—H8'C	109.5
C2—C3'—C2'	110.20 (15)	C7—C9—H9A	109.5
O4—C4—C5	109.52 (19)	C7—C9—H9B	109.5
O4—C4—C3	104.99 (17)	H9A—C9—H9B	109.5
C5—C4—C3	116.62 (19)	C7—C9—H9C	109.5
O4—C4—H4	108.5	H9A—C9—H9C	109.5
C5—C4—H4	108.5	H9B—C9—H9C	109.5
C3—C4—H4	108.5	C7'—C9'—H9'A	109.5
C5'—C4'—O4'	121.58 (19)	C7'—C9'—H9'B	109.5
C5'—C4'—C3'	128.69 (19)	H9'A—C9'—H9'B	109.5
O4'—C4'—C3'	109.65 (16)	C7'—C9'—H9'C	109.5
C4—C5—C6	112.3 (2)	H9'A—C9'—H9'C	109.5
C4—C5—H5A	108.0 (16)	H9'B—C9'—H9'C	109.5

C7—O1—C1—O4	−90.8 (2)	C3—C2—C3'—C2'	179.19 (16)
C7—O1—C1—C2	24.9 (2)	O2'—C2'—C3'—O3'	24.3 (2)
C4—O4—C1—O1	145.01 (18)	C1'—C2'—C3'—O3'	138.29 (16)
C4—O4—C1—C2	30.2 (2)	O2'—C2'—C3'—C4'	−96.47 (18)
C7'—O1'—C1'—O4'	−95.8 (2)	C1'—C2'—C3'—C4'	17.55 (19)
C7'—O1'—C1'—C2'	20.6 (2)	O2'—C2'—C3'—C2	141.33 (16)
C4'—O4'—C1'—O1'	107.62 (19)	C1'—C2'—C3'—C2	−104.65 (18)
C4'—O4'—C1'—C2'	−7.5 (2)	C1—O4—C4—C5	−164.72 (19)
C7—O2—C2—C1	−6.9 (2)	C1—O4—C4—C3	−38.8 (2)
C7—O2—C2—C3'	−126.46 (17)	O3—C3—C4—O4	−90.6 (2)
C7—O2—C2—C3	106.07 (18)	C2—C3—C4—O4	30.5 (2)
O1—C1—C2—O2	−10.73 (19)	O3—C3—C4—C5	30.8 (3)
O4—C1—C2—O2	108.66 (18)	C2—C3—C4—C5	151.9 (2)
O1—C1—C2—C3'	108.34 (18)	C1'—O4'—C4'—C5'	−157.3 (2)
O4—C1—C2—C3'	−132.27 (17)	C1'—O4'—C4'—C3'	19.9 (2)
O1—C1—C2—C3	−129.19 (17)	O3'—C3'—C4'—C5'	32.0 (3)
O4—C1—C2—C3	−9.8 (2)	C2—C3'—C4'—C5'	−87.0 (3)
C7'—O2'—C2'—C1'	−4.3 (2)	C2'—C3'—C4'—C5'	153.9 (2)
C7'—O2'—C2'—C3'	109.84 (19)	O3'—C3'—C4'—O4'	−144.87 (16)
O1'—C1'—C2'—O2'	−9.9 (2)	C2—C3'—C4'—O4'	96.09 (19)
O4'—C1'—C2'—O2'	110.96 (17)	C2'—C3'—C4'—O4'	−23.00 (19)
O1'—C1'—C2'—C3'	−128.03 (17)	O4—C4—C5—C6	−177.3 (2)
O4'—C1'—C2'—C3'	−7.2 (2)	C3—C4—C5—C6	63.7 (3)
O2—C2—C3—O3	−4.8 (2)	O4'—C4'—C5'—C6'	−0.5 (4)
C1—C2—C3—O3	107.97 (18)	C3'—C4'—C5'—C6'	−177.0 (2)
C3'—C2—C3—O3	−130.87 (17)	C1—O1—C7—O2	−28.9 (2)
O2—C2—C3—C4	−125.35 (16)	C1—O1—C7—C9	−143.91 (18)
C1—C2—C3—C4	−12.5 (2)	C1—O1—C7—C8	90.7 (2)
C3'—C2—C3—C4	108.61 (18)	C2—O2—C7—O1	21.6 (2)
O2—C2—C3'—O3'	174.56 (14)	C2—O2—C7—C9	137.29 (18)
C1—C2—C3'—O3'	59.2 (2)	C2—O2—C7—C8	−98.0 (2)
C3—C2—C3'—O3'	−58.30 (19)	C1'—O1'—C7'—O2'	−23.2 (3)
O2—C2—C3'—C4'	−62.3 (2)	C1'—O1'—C7'—C9'	97.0 (2)
C1—C2—C3'—C4'	−177.75 (17)	C1'—O1'—C7'—C8'	−137.0 (2)
C3—C2—C3'—C4'	64.8 (2)	C2'—O2'—C7'—O1'	16.3 (2)
O2—C2—C3'—C2'	52.04 (19)	C2'—O2'—C7'—C9'	−104.8 (2)
C1—C2—C3'—C2'	−63.4 (2)	C2'—O2'—C7'—C8'	132.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3′—H3′···O4′ⁱ	0.79 (3)	2.36 (3)	3.038 (2)	144 (2)
O3′—H3′···O2′	0.79 (3)	2.22 (3)	2.685 (2)	119 (2)
O3—H3···O2	0.82 (4)	2.11 (3)	2.647 (2)	122 (3)

Symmetry code: (i) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3'—H3'···O4'ⁱ	0.79 (3)	2.36 (3)	3.038 (2)	144 (2)
O3'—H3'···O2'	0.79 (3)	2.22 (3)	2.685 (2)	119 (2)
O3—H3···O2	0.82 (4)	2.11 (3)	2.647 (2)	122 (3)

Symmetry code: (i) x, y, z+1.

Acknowledgements

We gratefully acknowledge the financial support of the National Natural Science Foundation of China (grant No. 81172937).

References

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