4-Formyl­phenyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyran­oside

Heidelberg, T.; Hussen, R.S.D.; Rodzi, N.Z.M.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811008099

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o825

doi:10.1107/S1600536811008099

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4-Formylphenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside

Thorsten Heidelberg,^a ‡ Rusnah Syahila Duali Hussen,^a Nasrul Zamani Mohd Rodzi,^a Seik Weng Ng ^a and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 16 February 2011; accepted 3 March 2011; online 9 March 2011)

The pyranoside ring in the title compound, C₂₁H₂₄O₁₁, has a chair conformation with the substituted benzene ring occupying an equatorial position. The crystal packing is dominated by C—H⋯O interactions that lead to the formation of supramolecular layers in the ab plane.

Related literature

For synthesis, see: Bao et al. (2004 ); Hongu et al. (1999 ); Patil & Ravindranathan Kartha (2008 ). For the natural anti-oxidant glucosylated resveratrol, see: La Torre et al. (2004 ). For the biological activity of related structures, see: Wen et al. (2008 ); Yan et al. (2009 ). For the structure of the isomeric allopyranoside and galactose derivatives, see: Ye et al. (2009 ); Hussen et al. (2011 ). For conformational analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₂₁H₂₄O₁₁
M_r = 452.40
Triclinic, P 1
a = 5.7868 (2) Å
b = 8.9166 (3) Å
c = 11.4716 (3) Å
α = 102.473 (3)°
β = 93.481 (2)°
γ = 102.780 (3)°
V = 559.96 (3) Å³
Z = 1
Cu Kα radiation
μ = 0.94 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.20 mm

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010 ) T_min = 0.919, T_max = 1.000
7392 measured reflections
4097 independent reflections
4087 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.115
S = 1.07
4097 reflections
293 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 1855 Friedel pairs
Flack parameter: -0.02(12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O5ⁱ	1.00	2.51	3.356 (2)	143
C3—H3⋯O5ⁱ	1.00	2.35	3.207 (2)	143
C6—H6A⋯O9ⁱⁱ	0.99	2.40	3.324 (2)	155
C8—H8C⋯O11ⁱⁱⁱ	0.98	2.54	3.475 (3)	160
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z; (iii) x-1, y, z.

Data collection: CrysAlis PRO (Agilent Technologies, 2010); 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: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008099/ez2235sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008099/ez2235Isup2.hkl

checkCIF report

Comment top

The title compound, 4-formyl-phenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside, a known species (Bao et al., 2004, Hongu et al., 1999; Patil et al.; 2008), which has been used for the preparation of potential pharmaceutically active compounds (Wen et al., 2008; Yan et al., 2009) was prepared as a precursor for the synthesis of glucosylated resveratrol, an interesting natural antioxidant (La Torre et al., 2004). The present analysis complements the recent report of the isomeric galactose derivative, see: Hussen et al. (2011).

The structure determination, Fig. 1, confirms the relative stereochemistry as well as the absolute structure, i.e. R, R, S, R and S for C1–C5, respectively. The pyranoside ring has a chair conformation as seen in the puckering parameters (Cremer & Pople, 1975): puckering amplitude (Q) = 0.6016 (18) Å, θ = 172.53 (16) °, and ϕ = 178.0 (14) °. Around the ring, all substituents are equatorial.

The crystal packing is dominated by C–H···O interactions, Table 1, involving carbonyl atoms as acceptors and methine-, methylene methyl-H as the donors. The carbonyl-O5 atom is bifurcated, spanning two methine-H atoms of a neighbouring molecule to form a supramolecular chain along the a axis. Altogether, the C–H···O interactions lead to the formation of supramolecular layers that stack along the c axis, Fig. 2.

The present report complements the structures reported recently for the isomeric allopyranoside (Ye et al., 2009) and galactose (Duali Hussen et al., 2011) derivatives.

Related literature top

For synthesis, see: Bao et al. (2004); Hongu et al. (1999); Patil et al. (2008). For the natural anti-oxidant glucosylated resveratrol, see: La Torre et al. (2004). For the biological activity of related structures, see: Wen et al. (2008); Yan et al. (2009). For the structure of the isomeric allopyranoside and galactose derivatives, see: Ye et al. (2009); Hussen et al. (2011). For conformational analysis, see: Cremer & Pople (1975).

Experimental top

2,3,4,6-Tetra-O-acetyl-α-D-gluctopyranosyl bromide (4.0 g) and 4-hydroxybenzaldehyde (3.0 g) were dissolved in chloroform (30 ml) and the mixture treated with a solution of aqueous solution (15 ml) of sodium carbonate (2.7 g) and tetrabutylammonium bromide (0.7 g). The mixture was heated to reflux under vigorous stirring overnight, after which ethyl acetate was added and the organic layer was washed three times with sodium hydroxide solution (1 N) to remove remaining phenols. After drying the solution over magnesium sulfate and evaporation of the solvent, the target product (2.0 g, 45%) was obtained by crystallization from ethanol. Better crystals were obtained from 2-propanol.

¹H NMR (400 MHz, CDCl₃): δ 9.92 (s; CHO), 7.85 & 7.09 (AB syst; aromatic 4H), 5.34–5.26 & 5.24–5.14 (2 m, 2 x 2H; H1–H4), 4.27 (dd; H6a), 4.16 (dd; H6b), 3.92 (ddd; H5), 2.05–2.03 (3 s, 12H; Ac); ³J_4,5 = 10.0 Hz, ³J_5,6a = 5.0 Hz, ³J_{5,6 b} = 2.5 Hz and ²J₆ = 12.0 Hz.

Computing details top

Data collection: CrysAlis PRO (Agilent Technologies, 2010); cell refinement: CrysAlis PRO (Agilent Technologies, 2010); data reduction: CrysAlis PRO (Agilent Technologies, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure, showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.
	Fig. 2. A view in projection down the a axis of the unit-cell contents highlighting the stacking of layers. The C—H···O interactions are shown as orange dashed lines.

4-Formylphenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside top

Crystal data top

C₂₁H₂₄O₁₁	Z = 1
M_r = 452.40	F(000) = 238
Triclinic, P1	D_x = 1.342 Mg m⁻³
Hall symbol: P 1	Cu Kα radiation, λ = 1.54184 Å
a = 5.7868 (2) Å	Cell parameters from 7285 reflections
b = 8.9166 (3) Å	θ = 4.0–74.1°
c = 11.4716 (3) Å	µ = 0.94 mm⁻¹
α = 102.473 (3)°	T = 100 K
β = 93.481 (2)°	Block, colourless
γ = 102.780 (3)°	0.30 × 0.30 × 0.20 mm
V = 559.96 (3) Å³

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	4097 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	4087 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.021
Detector resolution: 10.4041 pixels mm^-1	θ_max = 74.3°, θ_min = 4.0°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010)	k = −9→10
T_min = 0.919, T_max = 1.000	l = −13→14
7392 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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + (0.0908P)² + 0.072P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
4097 reflections	Δρ_max = 0.27 e Å⁻³
293 parameters	Δρ_min = −0.17 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 1855 Friedel pairs
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₁H₂₄O₁₁	γ = 102.780 (3)°
M_r = 452.40	V = 559.96 (3) Å³
Triclinic, P1	Z = 1
a = 5.7868 (2) Å	Cu Kα radiation
b = 8.9166 (3) Å	µ = 0.94 mm⁻¹
c = 11.4716 (3) Å	T = 100 K
α = 102.473 (3)°	0.30 × 0.30 × 0.20 mm
β = 93.481 (2)°

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	4097 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010)	4087 reflections with I > 2σ(I)
T_min = 0.919, T_max = 1.000	R_int = 0.021
7392 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	3 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.07	Δρ_max = 0.27 e Å⁻³
4097 reflections	Δρ_min = −0.17 e Å⁻³
293 parameters	Absolute structure: Flack (1983), 1855 Friedel pairs

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	0.9987 (2)	0.49931 (15)	0.49910 (11)	0.0174 (3)
O2	1.0120 (2)	0.81529 (16)	0.57609 (11)	0.0218 (3)
O3	0.7432 (3)	0.95346 (19)	0.63881 (14)	0.0305 (3)
O4	0.7892 (2)	0.55996 (15)	0.20730 (10)	0.0167 (3)
O5	0.4356 (2)	0.59974 (16)	0.26001 (12)	0.0208 (3)
O6	0.7723 (2)	0.23423 (15)	0.15960 (11)	0.0192 (3)
O7	1.0136 (3)	0.2794 (2)	0.01679 (14)	0.0385 (4)
O8	1.1640 (2)	0.17486 (15)	0.30105 (11)	0.0196 (3)
O9	0.8768 (3)	−0.04604 (17)	0.28892 (15)	0.0297 (3)
O10	1.1933 (2)	0.31718 (15)	0.54454 (11)	0.0204 (3)
O11	2.0808 (3)	0.73176 (19)	0.92751 (14)	0.0330 (4)
C1	0.9617 (3)	0.5930 (2)	0.41525 (15)	0.0166 (3)
H1	1.1190	0.6460	0.3937	0.020*
C2	0.8116 (3)	0.4800 (2)	0.30264 (15)	0.0155 (3)
H2	0.6503	0.4316	0.3225	0.019*
C3	0.9368 (3)	0.3515 (2)	0.25138 (15)	0.0163 (3)
H3	1.0817	0.3980	0.2159	0.020*
C4	1.0071 (3)	0.2710 (2)	0.34749 (16)	0.0171 (3)
H4	0.8624	0.2051	0.3712	0.021*
C5	1.1452 (3)	0.3968 (2)	0.45629 (15)	0.0168 (3)
H5	1.2968	0.4572	0.4343	0.020*
C6	0.8401 (3)	0.7168 (2)	0.47781 (16)	0.0187 (3)
H6A	0.7979	0.7799	0.4222	0.022*
H6B	0.6930	0.6665	0.5080	0.022*
C7	0.9388 (3)	0.9279 (2)	0.65168 (16)	0.0220 (4)
C8	1.1278 (4)	1.0105 (3)	0.75474 (18)	0.0291 (4)
H8A	1.1138	1.1193	0.7845	0.044*
H8B	1.2855	1.0119	0.7277	0.044*
H8C	1.1077	0.9543	0.8194	0.044*
C9	0.5824 (3)	0.6053 (2)	0.19069 (15)	0.0163 (3)
C10	0.5674 (3)	0.6549 (3)	0.07482 (17)	0.0234 (4)
H10A	0.4287	0.7001	0.0685	0.035*
H10B	0.5507	0.5627	0.0077	0.035*
H10C	0.7128	0.7344	0.0721	0.035*
C11	0.8311 (4)	0.2113 (2)	0.04513 (17)	0.0250 (4)
C12	0.6319 (5)	0.0922 (3)	−0.0371 (2)	0.0428 (6)
H12A	0.6747	0.0749	−0.1195	0.064*
H12B	0.4866	0.1315	−0.0340	0.064*
H12C	0.6041	−0.0078	−0.0117	0.064*
C13	1.0775 (3)	0.0158 (2)	0.27726 (16)	0.0214 (4)
C14	1.2625 (4)	−0.0679 (3)	0.2328 (3)	0.0385 (5)
H14A	1.1877	−0.1802	0.1990	0.058*
H14B	1.3833	−0.0573	0.2997	0.058*
H14C	1.3381	−0.0212	0.1706	0.058*
C15	1.3937 (3)	0.3914 (2)	0.62530 (15)	0.0185 (4)
C16	1.5446 (4)	0.2974 (3)	0.64956 (18)	0.0230 (4)
H16	1.5095	0.1883	0.6104	0.028*
C17	1.7455 (4)	0.3644 (3)	0.73110 (18)	0.0249 (4)
H17	1.8490	0.3008	0.7482	0.030*
C18	1.7984 (3)	0.5252 (2)	0.78886 (16)	0.0229 (4)
C19	1.6452 (3)	0.6178 (2)	0.76354 (15)	0.0216 (4)
H19	1.6803	0.7268	0.8028	0.026*
C20	1.4427 (3)	0.5528 (2)	0.68196 (16)	0.0209 (4)
H20	1.3390	0.6162	0.6647	0.025*
C21	2.0148 (4)	0.5937 (3)	0.87497 (18)	0.0279 (4)
H21	2.1099	0.5244	0.8905	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0207 (6)	0.0178 (6)	0.0153 (5)	0.0077 (5)	0.0026 (4)	0.0040 (5)
O2	0.0222 (6)	0.0195 (7)	0.0197 (6)	0.0055 (5)	−0.0015 (5)	−0.0030 (5)
O3	0.0332 (8)	0.0268 (8)	0.0305 (7)	0.0149 (6)	0.0023 (6)	−0.0032 (6)
O4	0.0163 (6)	0.0200 (6)	0.0160 (5)	0.0071 (4)	0.0020 (4)	0.0061 (4)
O5	0.0175 (6)	0.0221 (7)	0.0231 (6)	0.0063 (5)	0.0035 (5)	0.0043 (5)
O6	0.0202 (6)	0.0176 (6)	0.0160 (6)	0.0022 (5)	−0.0017 (5)	−0.0006 (5)
O7	0.0419 (9)	0.0422 (9)	0.0211 (7)	−0.0038 (7)	0.0091 (6)	−0.0018 (6)
O8	0.0178 (6)	0.0166 (6)	0.0245 (6)	0.0057 (5)	0.0023 (5)	0.0034 (5)
O9	0.0278 (7)	0.0171 (7)	0.0435 (8)	0.0040 (5)	0.0079 (6)	0.0062 (6)
O10	0.0231 (6)	0.0186 (7)	0.0203 (6)	0.0041 (5)	−0.0020 (5)	0.0083 (5)
O11	0.0293 (7)	0.0380 (9)	0.0279 (7)	0.0037 (6)	−0.0054 (6)	0.0066 (6)
C1	0.0191 (8)	0.0156 (9)	0.0157 (8)	0.0049 (6)	0.0017 (6)	0.0041 (6)
C2	0.0167 (7)	0.0166 (9)	0.0148 (7)	0.0051 (6)	0.0034 (6)	0.0054 (6)
C3	0.0162 (8)	0.0156 (8)	0.0150 (7)	0.0027 (6)	−0.0006 (6)	0.0013 (6)
C4	0.0170 (8)	0.0148 (8)	0.0189 (8)	0.0043 (6)	0.0022 (6)	0.0022 (6)
C5	0.0183 (8)	0.0166 (9)	0.0164 (7)	0.0052 (6)	0.0010 (6)	0.0048 (6)
C6	0.0189 (8)	0.0167 (8)	0.0182 (8)	0.0039 (6)	0.0004 (6)	0.0000 (6)
C7	0.0286 (10)	0.0169 (9)	0.0206 (9)	0.0073 (7)	0.0045 (7)	0.0024 (7)
C8	0.0365 (11)	0.0227 (10)	0.0228 (9)	0.0043 (8)	−0.0018 (8)	−0.0014 (7)
C9	0.0154 (8)	0.0147 (8)	0.0176 (8)	0.0043 (6)	−0.0011 (6)	0.0012 (6)
C10	0.0244 (9)	0.0298 (10)	0.0189 (8)	0.0116 (7)	0.0008 (6)	0.0075 (7)
C11	0.0334 (10)	0.0234 (10)	0.0172 (8)	0.0073 (8)	0.0028 (7)	0.0017 (7)
C12	0.0504 (14)	0.0434 (14)	0.0206 (10)	−0.0062 (11)	−0.0034 (9)	−0.0024 (9)
C13	0.0243 (9)	0.0171 (9)	0.0224 (8)	0.0046 (7)	−0.0001 (7)	0.0048 (7)
C14	0.0350 (11)	0.0218 (11)	0.0614 (16)	0.0118 (9)	0.0152 (10)	0.0073 (10)
C15	0.0191 (8)	0.0225 (10)	0.0161 (8)	0.0054 (7)	0.0032 (6)	0.0084 (6)
C16	0.0263 (9)	0.0229 (9)	0.0238 (8)	0.0090 (7)	0.0049 (7)	0.0102 (7)
C17	0.0243 (9)	0.0309 (11)	0.0258 (9)	0.0124 (8)	0.0043 (7)	0.0139 (8)
C18	0.0228 (9)	0.0310 (11)	0.0175 (8)	0.0068 (7)	0.0035 (7)	0.0101 (7)
C19	0.0254 (9)	0.0233 (10)	0.0160 (8)	0.0065 (7)	0.0019 (7)	0.0041 (7)
C20	0.0240 (9)	0.0229 (10)	0.0180 (8)	0.0085 (7)	0.0014 (7)	0.0070 (7)
C21	0.0223 (9)	0.0400 (13)	0.0235 (9)	0.0075 (8)	0.0010 (7)	0.0120 (9)

Geometric parameters (Å, º) top

O1—C5	1.413 (2)	C7—C8	1.499 (3)
O1—C1	1.439 (2)	C8—H8A	0.9800
O2—C7	1.340 (2)	C8—H8B	0.9800
O2—C6	1.443 (2)	C8—H8C	0.9800
O3—C7	1.210 (3)	C9—C10	1.492 (2)
O4—C9	1.361 (2)	C10—H10A	0.9800
O4—C2	1.443 (2)	C10—H10B	0.9800
O5—C9	1.199 (2)	C10—H10C	0.9800
O6—C11	1.360 (2)	C11—C12	1.497 (3)
O6—C3	1.4389 (19)	C12—H12A	0.9800
O7—C11	1.197 (3)	C12—H12B	0.9800
O8—C13	1.356 (2)	C12—H12C	0.9800
O8—C4	1.431 (2)	C13—C14	1.489 (3)
O9—C13	1.199 (3)	C14—H14A	0.9800
O10—C15	1.381 (2)	C14—H14B	0.9800
O10—C5	1.404 (2)	C14—H14C	0.9800
O11—C21	1.212 (3)	C15—C16	1.391 (3)
C1—C6	1.513 (2)	C15—C20	1.403 (3)
C1—C2	1.534 (2)	C16—C17	1.380 (3)
C1—H1	1.0000	C16—H16	0.9500
C2—C3	1.521 (2)	C17—C18	1.400 (3)
C2—H2	1.0000	C17—H17	0.9500
C3—C4	1.520 (2)	C18—C19	1.396 (3)
C3—H3	1.0000	C18—C21	1.472 (3)
C4—C5	1.527 (2)	C19—C20	1.384 (3)
C4—H4	1.0000	C19—H19	0.9500
C5—H5	1.0000	C20—H20	0.9500
C6—H6A	0.9900	C21—H21	0.9500
C6—H6B	0.9900

C5—O1—C1	111.07 (12)	H8B—C8—H8C	109.5
C7—O2—C6	116.65 (14)	O5—C9—O4	122.82 (15)
C9—O4—C2	117.18 (13)	O5—C9—C10	127.05 (16)
C11—O6—C3	117.74 (14)	O4—C9—C10	110.10 (14)
C13—O8—C4	117.05 (14)	C9—C10—H10A	109.5
C15—O10—C5	115.77 (13)	C9—C10—H10B	109.5
O1—C1—C6	106.88 (13)	H10A—C10—H10B	109.5
O1—C1—C2	107.27 (13)	C9—C10—H10C	109.5
C6—C1—C2	113.52 (14)	H10A—C10—H10C	109.5
O1—C1—H1	109.7	H10B—C10—H10C	109.5
C6—C1—H1	109.7	O7—C11—O6	124.08 (17)
C2—C1—H1	109.7	O7—C11—C12	126.49 (19)
O4—C2—C3	104.57 (13)	O6—C11—C12	109.41 (17)
O4—C2—C1	111.42 (13)	C11—C12—H12A	109.5
C3—C2—C1	110.19 (13)	C11—C12—H12B	109.5
O4—C2—H2	110.2	H12A—C12—H12B	109.5
C3—C2—H2	110.2	C11—C12—H12C	109.5
C1—C2—H2	110.2	H12A—C12—H12C	109.5
O6—C3—C2	107.91 (13)	H12B—C12—H12C	109.5
O6—C3—C4	108.09 (14)	O9—C13—O8	123.37 (18)
C2—C3—C4	111.16 (13)	O9—C13—C14	125.80 (19)
O6—C3—H3	109.9	O8—C13—C14	110.81 (17)
C2—C3—H3	109.9	C13—C14—H14A	109.5
C4—C3—H3	109.9	C13—C14—H14B	109.5
O8—C4—C3	108.55 (14)	H14A—C14—H14B	109.5
O8—C4—C5	107.52 (13)	C13—C14—H14C	109.5
C3—C4—C5	109.22 (14)	H14A—C14—H14C	109.5
O8—C4—H4	110.5	H14B—C14—H14C	109.5
C3—C4—H4	110.5	O10—C15—C16	116.66 (17)
C5—C4—H4	110.5	O10—C15—C20	122.13 (16)
O10—C5—O1	109.38 (13)	C16—C15—C20	121.21 (17)
O10—C5—C4	106.87 (14)	C17—C16—C15	119.31 (19)
O1—C5—C4	108.50 (13)	C17—C16—H16	120.3
O10—C5—H5	110.7	C15—C16—H16	120.3
O1—C5—H5	110.7	C16—C17—C18	120.59 (17)
C4—C5—H5	110.7	C16—C17—H17	119.7
O2—C6—C1	105.19 (14)	C18—C17—H17	119.7
O2—C6—H6A	110.7	C19—C18—C17	119.37 (17)
C1—C6—H6A	110.7	C19—C18—C21	121.21 (18)
O2—C6—H6B	110.7	C17—C18—C21	119.42 (18)
C1—C6—H6B	110.7	C20—C19—C18	120.91 (18)
H6A—C6—H6B	108.8	C20—C19—H19	119.5
O3—C7—O2	123.64 (17)	C18—C19—H19	119.5
O3—C7—C8	125.73 (18)	C19—C20—C15	118.61 (17)
O2—C7—C8	110.58 (16)	C19—C20—H20	120.7
C7—C8—H8A	109.5	C15—C20—H20	120.7
C7—C8—H8B	109.5	O11—C21—C18	124.9 (2)
H8A—C8—H8B	109.5	O11—C21—H21	117.5
C7—C8—H8C	109.5	C18—C21—H21	117.5
H8A—C8—H8C	109.5

C5—O1—C1—C6	−170.55 (13)	C3—C4—C5—O1	58.77 (17)
C5—O1—C1—C2	67.38 (15)	C7—O2—C6—C1	−174.96 (14)
C9—O4—C2—C3	140.73 (14)	O1—C1—C6—O2	64.96 (16)
C9—O4—C2—C1	−100.26 (16)	C2—C1—C6—O2	−176.99 (13)
O1—C1—C2—O4	−173.01 (13)	C6—O2—C7—O3	−2.8 (3)
C6—C1—C2—O4	69.16 (17)	C6—O2—C7—C8	174.88 (15)
O1—C1—C2—C3	−57.40 (16)	C2—O4—C9—O5	9.6 (2)
C6—C1—C2—C3	−175.23 (13)	C2—O4—C9—C10	−168.33 (15)
C11—O6—C3—C2	117.13 (16)	C3—O6—C11—O7	2.1 (3)
C11—O6—C3—C4	−122.56 (16)	C3—O6—C11—C12	−176.77 (19)
O4—C2—C3—O6	−69.99 (15)	C4—O8—C13—O9	2.9 (3)
C1—C2—C3—O6	170.17 (13)	C4—O8—C13—C14	−178.48 (17)
O4—C2—C3—C4	171.65 (13)	C5—O10—C15—C16	−134.15 (17)
C1—C2—C3—C4	51.81 (18)	C5—O10—C15—C20	46.8 (2)
C13—O8—C4—C3	−110.11 (16)	O10—C15—C16—C17	−178.90 (15)
C13—O8—C4—C5	131.85 (15)	C20—C15—C16—C17	0.2 (3)
O6—C3—C4—O8	73.14 (16)	C15—C16—C17—C18	−0.2 (3)
C2—C3—C4—O8	−168.61 (13)	C16—C17—C18—C19	0.2 (3)
O6—C3—C4—C5	−169.91 (13)	C16—C17—C18—C21	−179.67 (17)
C2—C3—C4—C5	−51.66 (18)	C17—C18—C19—C20	−0.2 (3)
C15—O10—C5—O1	−89.74 (17)	C21—C18—C19—C20	179.63 (17)
C15—O10—C5—C4	152.99 (14)	C18—C19—C20—C15	0.2 (3)
C1—O1—C5—O10	175.14 (12)	O10—C15—C20—C19	178.82 (15)
C1—O1—C5—C4	−68.62 (16)	C16—C15—C20—C19	−0.2 (3)
O8—C4—C5—O10	−65.78 (16)	C19—C18—C21—O11	−1.9 (3)
C3—C4—C5—O10	176.62 (13)	C17—C18—C21—O11	177.97 (19)
O8—C4—C5—O1	176.37 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O5ⁱ	1.00	2.51	3.356 (2)	143
C3—H3···O5ⁱ	1.00	2.35	3.207 (2)	143
C6—H6A···O9ⁱⁱ	0.99	2.40	3.324 (2)	155
C8—H8C···O11ⁱⁱⁱ	0.98	2.54	3.475 (3)	160

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

Experimental details

Crystal data
Chemical formula	C₂₁H₂₄O₁₁
M_r	452.40
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	5.7868 (2), 8.9166 (3), 11.4716 (3)
α, β, γ (°)	102.473 (3), 93.481 (2), 102.780 (3)
V (Å³)	559.96 (3)
Z	1
Radiation type	Cu Kα
µ (mm⁻¹)	0.94
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent Technologies, 2010)
T_min, T_max	0.919, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7392, 4097, 4087
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.115, 1.07
No. of reflections	4097
No. of parameters	293
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.17
Absolute structure	Flack (1983), 1855 Friedel pairs

Computer programs: CrysAlis PRO (Agilent Technologies, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O5ⁱ	1.00	2.51	3.356 (2)	143
C3—H3···O5ⁱ	1.00	2.35	3.207 (2)	143
C6—H6A···O9ⁱⁱ	0.99	2.40	3.324 (2)	155
C8—H8C···O11ⁱⁱⁱ	0.98	2.54	3.475 (3)	160

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

Footnotes

‡Additional correspondence author, e-mail: heidelberg@um.edu.my.

Acknowledgements

This study was supported by the University of Malaya under research grant No. FS306/2007 C. The authors are also grateful to the University of Malaya for support of the crystallographic facility.

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