Methyl 2,3-di-O-acetyl-4-O-levulinoyl-1-O-(2,2,2-trichloro-2-imino­ethyl)-l-ido­pyran­osiduronate

Cai, C.; Wei, G.; Du, Y.

doi:10.1107/S1600536810010895

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o949

doi:10.1107/S1600536810010895

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Methyl 2,3-di-O-acetyl-4-O-levulinoyl-1-O-(2,2,2-trichloro-2-iminoethyl)-L-idopyranosiduronate

Chao Cai,^a Guohua Wei ^a ^* and Yuguo Du ^a

^aResearch Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People's Republic of China
^*Correspondence e-mail: wgh@rcees.ac.cn

(Received 4 March 2010; accepted 23 March 2010; online 27 March 2010)

In the title compound, C₁₈H₂₂Cl₃NO₁₁, a novel derivative of L-idopyranosiduronic acid, the six-membered ring adopts a chair conformation.

Related literature

For background to L-iduronic acids, see: Capila & Linhardt (2002 ); Jobron & Jacquinet (1998 ); Lee et al. (2004 ). For the synthesis of iduronic acid derivatives, see: Yu et al. (2004 ); Sanjoy et al. (2001 ); Lubineau et al. (2000 ); Lohman et al. (2003 ).

Experimental

Crystal data

C₁₈H₂₂Cl₃NO₁₁
M_r = 534.72
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.0498 (10) Å
b = 9.7560 (11) Å
c = 26.570 (3) Å
V = 2345.8 (4) Å³
Z = 4
Cu Kα radiation
μ = 4.07 mm⁻¹
T = 173 K
0.41 × 0.30 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: numerical (ABSCOR; Higashi, 1995 ) T_min = 0.286, T_max = 0.395
16340 measured reflections
4259 independent reflections
3893 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.100
S = 1.09
4259 reflections
302 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.48 e Å⁻³
Absolute structure: Flack (1983 ), 1804 Friedel pairs
Flack parameter: 0.023 (18)

Data collection: RAPID-AUTO (Rigaku, 2001 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010895/bt5207sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010895/bt5207Isup2.hkl

checkCIF report

Comment top

L-iduronic acids are key components of numerous biologically potent oligosaccharides and glycopeptides (Capila & Linhardt, 2002). For example, heparin, heparan sulfate (Jobron & Jacquinet, 1998), dermatan sulfate (Lee et al., 2004). This series of glycosaminoglycans plays an important role in a diverse set of biological processes which all contain L-idopyranosiduronic acids. To study the structure-activity relationship of such polymers, there is a need for chemically pure oligosaccharide sequences which can be prepared by organic syntheses.

Since iduronic acid itself is not commercially available, syntheses of iduronic acid derivatives (Yu et al., 2004) from a variety of starting materials, including idose, glucose, glycals,and glucuronic acid have been developed (Lubineau et al., 2000 & Lohman et al., 2003). Herein, we have explored a novel and efficient route toward the synthesis of L-idopyranosiduronate trichloroacetimidate which will be used as a key building block to synthesize dermatan sulfate.

Related literature top

For background to L-iduronic acids, see: Capila & Linhardt (2002); Jobron & Jacquinet (1998); Lee et al. (2004). For the synthesis of iduronic acid derivatives, see: Yu et al. (2004); Sanjoy et al. (2001); Lubineau et al. (2000); Lohman et al. (2003).

Experimental top

The title compound was prepared in 76.8% yield by treatment with trichloroaceonitrile and DBU at 0 °C. The reaction was stirred for 30 min then allowed to warm to room temperature. Solvent was evaporated and the residue purified by Flash silica gel column chromatography (silica quenched with 1% NEt₃) afford the title compound as syrupy.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, displacement ellipsoids are at the 50% level.
	Fig. 2. A packing diagram of the title compound.

Methyl 2,3-di-O-acetyl-4-O-levulinoyl-1-O-(2,2,2-trichloro- 2-iminoethyl)-L-idopyranosiduronate top

Crystal data top

C₁₈H₂₂Cl₃NO₁₁	D_x = 1.514 Mg m⁻³
M_r = 534.72	Cu Kα radiation, λ = 1.54186 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 1098 reflections
a = 9.0498 (10) Å	θ = 2.2–27.5°
b = 9.7560 (11) Å	µ = 4.07 mm⁻¹
c = 26.570 (3) Å	T = 173 K
V = 2345.8 (4) Å³	Block, colorless
Z = 4	0.41 × 0.30 × 0.28 mm
F(000) = 1104

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	4259 independent reflections
Radiation source: rotating anode	3893 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ω scans at fixed χ = 45°	θ_max = 68.2°, θ_min = 3.3°
Absorption correction: numerical (ABSCOR; Higashi, 1995)	h = −10→10
T_min = 0.286, T_max = 0.395	k = −11→11
16340 measured reflections	l = −32→31

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0268P)² + 1.8534P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
4259 reflections	Δρ_max = 0.45 e Å⁻³
302 parameters	Δρ_min = −0.48 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1804 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.023 (18)

Crystal data top

C₁₈H₂₂Cl₃NO₁₁	V = 2345.8 (4) Å³
M_r = 534.72	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 9.0498 (10) Å	µ = 4.07 mm⁻¹
b = 9.7560 (11) Å	T = 173 K
c = 26.570 (3) Å	0.41 × 0.30 × 0.28 mm

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	4259 independent reflections
Absorption correction: numerical (ABSCOR; Higashi, 1995)	3893 reflections with I > 2σ(I)
T_min = 0.286, T_max = 0.395	R_int = 0.047
16340 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	H-atom parameters constrained
wR(F²) = 0.100	Δρ_max = 0.45 e Å⁻³
S = 1.09	Δρ_min = −0.48 e Å⁻³
4259 reflections	Absolute structure: Flack (1983), 1804 Friedel pairs
302 parameters	Absolute structure parameter: 0.023 (18)
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cl1	0.43622 (11)	0.42769 (10)	−0.00915 (3)	0.0470 (2)
Cl2	0.44529 (14)	0.72085 (10)	−0.00601 (4)	0.0578 (3)
Cl3	0.62102 (10)	0.56765 (16)	0.06361 (4)	0.0664 (3)
O1	0.2587 (2)	0.4459 (2)	0.17647 (7)	0.0275 (5)
O2	0.3250 (2)	0.4443 (2)	0.09152 (8)	0.0329 (5)
O3	0.0181 (2)	0.2548 (2)	0.14357 (8)	0.0332 (5)
O4	−0.0977 (3)	0.3313 (3)	0.07477 (9)	0.0527 (7)
O5	0.3933 (2)	0.1578 (2)	0.10987 (8)	0.0320 (5)
O6	0.2917 (3)	−0.0176 (3)	0.06774 (10)	0.0488 (7)
O7	0.1922 (2)	0.1967 (2)	0.22751 (8)	0.0285 (5)
O8	0.2316 (3)	−0.0295 (2)	0.23558 (11)	0.0493 (7)
O9	0.1750 (4)	0.1508 (4)	0.35252 (12)	0.0780 (11)
O10	0.3492 (3)	0.4899 (3)	0.27135 (9)	0.0462 (7)
O11	0.4850 (3)	0.2966 (3)	0.26989 (8)	0.0402 (6)
N1	0.2424 (3)	0.6658 (3)	0.08223 (11)	0.0411 (7)
H1A	0.2761	0.7351	0.0630	0.049*
C1	0.2099 (3)	0.4196 (4)	0.12743 (10)	0.0284 (7)
H1C	0.1257	0.4827	0.1198	0.034*
C2	0.1588 (3)	0.2725 (3)	0.11851 (12)	0.0280 (7)
H2A	0.1470	0.2558	0.0816	0.034*
C3	0.2619 (3)	0.1663 (3)	0.14075 (11)	0.0269 (7)
H3A	0.2117	0.0751	0.1419	0.032*
C4	0.3162 (4)	0.2048 (3)	0.19295 (11)	0.0260 (7)
H4A	0.3971	0.1416	0.2038	0.031*
C5	0.3679 (4)	0.3526 (3)	0.19531 (11)	0.0271 (7)
H5A	0.4609	0.3628	0.1754	0.033*
C6	0.3286 (4)	0.5705 (4)	0.06991 (11)	0.0315 (7)
C7	0.4526 (4)	0.5722 (4)	0.03110 (11)	0.0352 (7)
C8	−0.1037 (4)	0.2905 (4)	0.11727 (13)	0.0366 (8)
C9	−0.2403 (4)	0.2721 (4)	0.14798 (15)	0.0458 (10)
H9A	−0.3271	0.2931	0.1273	0.069*
H9B	−0.2373	0.3341	0.1770	0.069*
H9C	−0.2461	0.1771	0.1598	0.069*
C10	0.3914 (4)	0.0610 (4)	0.07321 (11)	0.0343 (7)
C11	0.5308 (4)	0.0652 (4)	0.04323 (13)	0.0471 (9)
H11A	0.5075	0.0543	0.0074	0.071*
H11B	0.5962	−0.0092	0.0540	0.071*
H11C	0.5802	0.1535	0.0485	0.071*
C12	0.1578 (4)	0.0694 (4)	0.24437 (11)	0.0323 (7)
C13	0.0114 (4)	0.0687 (4)	0.27120 (12)	0.0350 (7)
H13A	0.0108	−0.0084	0.2954	0.042*
H13B	−0.0674	0.0511	0.2462	0.042*
C14	−0.0258 (4)	0.1992 (4)	0.29934 (12)	0.0349 (8)
H14A	−0.0291	0.2762	0.2751	0.042*
H14B	−0.1254	0.1898	0.3143	0.042*
C15	0.0820 (4)	0.2329 (4)	0.34006 (13)	0.0434 (9)
C16	0.0726 (6)	0.3724 (4)	0.36322 (14)	0.0572 (12)
H16A	0.1519	0.3832	0.3881	0.086*
H16B	−0.0233	0.3832	0.3799	0.086*
H16C	0.0832	0.4422	0.3369	0.086*
C17	0.3974 (4)	0.3918 (3)	0.24983 (12)	0.0308 (7)
C18	0.5206 (4)	0.3098 (4)	0.32281 (13)	0.0481 (10)
H18A	0.5860	0.2346	0.3329	0.072*
H18B	0.4295	0.3062	0.3427	0.072*
H18C	0.5705	0.3975	0.3286	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0627 (6)	0.0425 (5)	0.0358 (4)	−0.0035 (5)	0.0135 (4)	−0.0068 (4)
Cl2	0.0917 (8)	0.0412 (5)	0.0405 (5)	−0.0004 (5)	0.0219 (5)	0.0099 (4)
Cl3	0.0339 (5)	0.1146 (10)	0.0507 (5)	−0.0158 (6)	−0.0041 (4)	0.0145 (7)
O1	0.0301 (11)	0.0272 (12)	0.0252 (10)	0.0002 (10)	0.0028 (9)	−0.0002 (9)
O2	0.0336 (12)	0.0322 (13)	0.0330 (11)	0.0029 (11)	0.0122 (10)	0.0045 (10)
O3	0.0228 (12)	0.0440 (14)	0.0328 (11)	−0.0007 (11)	0.0049 (10)	−0.0025 (10)
O4	0.0407 (15)	0.079 (2)	0.0381 (15)	0.0149 (15)	−0.0022 (12)	−0.0001 (14)
O5	0.0287 (12)	0.0353 (13)	0.0321 (11)	−0.0007 (10)	0.0113 (10)	−0.0070 (10)
O6	0.0489 (16)	0.0484 (16)	0.0492 (15)	−0.0084 (14)	0.0079 (13)	−0.0188 (13)
O7	0.0303 (12)	0.0276 (12)	0.0276 (11)	−0.0022 (10)	0.0105 (10)	0.0035 (9)
O8	0.0546 (17)	0.0269 (14)	0.0664 (18)	0.0040 (13)	0.0261 (15)	0.0048 (12)
O9	0.079 (2)	0.089 (3)	0.067 (2)	0.029 (2)	−0.0329 (19)	−0.0091 (19)
O10	0.0583 (17)	0.0445 (16)	0.0359 (13)	0.0033 (14)	−0.0002 (13)	−0.0117 (12)
O11	0.0410 (14)	0.0437 (14)	0.0358 (12)	0.0008 (12)	−0.0087 (11)	0.0005 (11)
N1	0.052 (2)	0.0306 (16)	0.0402 (16)	0.0008 (16)	0.0072 (15)	0.0049 (13)
C1	0.0252 (15)	0.0342 (17)	0.0259 (14)	−0.0011 (15)	0.0053 (12)	0.0028 (15)
C2	0.0214 (15)	0.0346 (18)	0.0281 (16)	−0.0045 (15)	0.0052 (13)	−0.0032 (14)
C3	0.0249 (16)	0.0300 (17)	0.0258 (15)	−0.0021 (14)	0.0094 (13)	−0.0001 (13)
C4	0.0266 (16)	0.0278 (17)	0.0236 (15)	−0.0022 (14)	0.0063 (13)	−0.0010 (13)
C5	0.0237 (16)	0.0273 (16)	0.0304 (16)	−0.0014 (14)	0.0025 (14)	0.0014 (13)
C6	0.0374 (17)	0.0334 (18)	0.0237 (15)	0.0014 (17)	−0.0004 (13)	0.0029 (15)
C7	0.0366 (18)	0.0417 (19)	0.0273 (15)	−0.0030 (18)	−0.0002 (14)	0.0004 (15)
C8	0.0291 (18)	0.043 (2)	0.0373 (19)	−0.0020 (17)	0.0018 (15)	−0.0103 (16)
C9	0.0248 (19)	0.055 (2)	0.058 (2)	−0.0024 (18)	0.0058 (17)	−0.006 (2)
C10	0.0381 (18)	0.0355 (18)	0.0295 (16)	0.0043 (18)	0.0005 (14)	−0.0050 (15)
C11	0.050 (2)	0.050 (2)	0.0415 (19)	0.002 (2)	0.0182 (17)	−0.0085 (19)
C12	0.0360 (18)	0.0289 (17)	0.0319 (16)	−0.0055 (17)	0.0062 (14)	0.0035 (15)
C13	0.0318 (17)	0.0350 (18)	0.0383 (17)	−0.0042 (17)	0.0068 (14)	0.0049 (16)
C14	0.0305 (18)	0.0380 (19)	0.0363 (17)	0.0014 (16)	0.0072 (15)	0.0054 (15)
C15	0.048 (2)	0.055 (2)	0.0276 (17)	0.002 (2)	0.0040 (17)	0.0029 (17)
C16	0.075 (3)	0.058 (3)	0.039 (2)	−0.008 (2)	0.007 (2)	−0.0088 (18)
C17	0.0275 (16)	0.0347 (19)	0.0301 (16)	−0.0089 (15)	0.0022 (14)	−0.0008 (14)
C18	0.047 (2)	0.065 (3)	0.0320 (18)	−0.011 (2)	−0.0091 (17)	0.0113 (18)

Geometric parameters (Å, º) top

Cl1—C7	1.776 (4)	C4—C5	1.517 (4)
Cl2—C7	1.754 (4)	C4—H4A	1.0000
Cl3—C7	1.753 (3)	C5—C17	1.522 (4)
O1—C1	1.399 (3)	C5—H5A	1.0000
O1—C5	1.433 (4)	C6—C7	1.524 (4)
O2—C6	1.359 (4)	C8—C9	1.492 (5)
O2—C1	1.433 (3)	C9—H9A	0.9800
O3—C8	1.351 (4)	C9—H9B	0.9800
O3—C2	1.447 (3)	C9—H9C	0.9800
O4—C8	1.199 (4)	C10—C11	1.492 (4)
O5—C10	1.357 (4)	C11—H11A	0.9800
O5—C3	1.447 (3)	C11—H11B	0.9800
O6—C10	1.194 (4)	C11—H11C	0.9800
O7—C12	1.356 (4)	C12—C13	1.504 (4)
O7—C4	1.452 (3)	C13—C14	1.515 (5)
O8—C12	1.197 (4)	C13—H13A	0.9900
O9—C15	1.208 (5)	C13—H13B	0.9900
O10—C17	1.197 (4)	C14—C15	1.493 (5)
O11—C17	1.333 (4)	C14—H14A	0.9900
O11—C18	1.448 (4)	C14—H14B	0.9900
N1—C6	1.256 (4)	C15—C16	1.496 (5)
N1—H1A	0.9001	C16—H16A	0.9800
C1—C2	1.527 (4)	C16—H16B	0.9800
C1—H1C	1.0000	C16—H16C	0.9800
C2—C3	1.514 (4)	C18—H18A	0.9800
C2—H2A	1.0000	C18—H18B	0.9800
C3—C4	1.518 (4)	C18—H18C	0.9800
C3—H3A	1.0000

C1—O1—C5	115.3 (2)	C8—C9—H9A	109.5
C6—O2—C1	116.8 (2)	C8—C9—H9B	109.5
C8—O3—C2	116.7 (2)	H9A—C9—H9B	109.5
C10—O5—C3	115.9 (2)	C8—C9—H9C	109.5
C12—O7—C4	115.9 (2)	H9A—C9—H9C	109.5
C17—O11—C18	117.3 (3)	H9B—C9—H9C	109.5
C6—N1—H1A	101.4	O6—C10—O5	123.0 (3)
O1—C1—O2	111.1 (2)	O6—C10—C11	126.3 (3)
O1—C1—C2	114.3 (3)	O5—C10—C11	110.7 (3)
O2—C1—C2	105.9 (2)	C10—C11—H11A	109.5
O1—C1—H1C	108.4	C10—C11—H11B	109.5
O2—C1—H1C	108.4	H11A—C11—H11B	109.5
C2—C1—H1C	108.4	C10—C11—H11C	109.5
O3—C2—C3	106.3 (2)	H11A—C11—H11C	109.5
O3—C2—C1	107.9 (2)	H11B—C11—H11C	109.5
C3—C2—C1	113.3 (3)	O8—C12—O7	123.1 (3)
O3—C2—H2A	109.7	O8—C12—C13	125.5 (3)
C3—C2—H2A	109.7	O7—C12—C13	111.3 (3)
C1—C2—H2A	109.7	C12—C13—C14	115.2 (3)
O5—C3—C2	108.9 (2)	C12—C13—H13A	108.5
O5—C3—C4	105.4 (2)	C14—C13—H13A	108.5
C2—C3—C4	112.8 (3)	C12—C13—H13B	108.5
O5—C3—H3A	109.9	C14—C13—H13B	108.5
C2—C3—H3A	109.9	H13A—C13—H13B	107.5
C4—C3—H3A	109.9	C15—C14—C13	113.4 (3)
O7—C4—C5	105.3 (2)	C15—C14—H14A	108.9
O7—C4—C3	108.3 (2)	C13—C14—H14A	108.9
C5—C4—C3	111.9 (3)	C15—C14—H14B	108.9
O7—C4—H4A	110.4	C13—C14—H14B	108.9
C5—C4—H4A	110.4	H14A—C14—H14B	107.7
C3—C4—H4A	110.4	O9—C15—C14	120.5 (4)
O1—C5—C4	112.1 (3)	O9—C15—C16	122.0 (4)
O1—C5—C17	107.1 (3)	C14—C15—C16	117.5 (4)
C4—C5—C17	109.4 (3)	C15—C16—H16A	109.5
O1—C5—H5A	109.4	C15—C16—H16B	109.5
C4—C5—H5A	109.4	H16A—C16—H16B	109.5
C17—C5—H5A	109.4	C15—C16—H16C	109.5
N1—C6—O2	123.1 (3)	H16A—C16—H16C	109.5
N1—C6—C7	128.7 (3)	H16B—C16—H16C	109.5
O2—C6—C7	108.2 (3)	O10—C17—O11	125.6 (3)
C6—C7—Cl3	107.9 (2)	O10—C17—C5	126.3 (3)
C6—C7—Cl2	111.2 (3)	O11—C17—C5	108.1 (3)
Cl3—C7—Cl2	109.31 (19)	O11—C18—H18A	109.5
C6—C7—Cl1	109.7 (2)	O11—C18—H18B	109.5
Cl3—C7—Cl1	110.4 (2)	H18A—C18—H18B	109.5
Cl2—C7—Cl1	108.34 (16)	O11—C18—H18C	109.5
O4—C8—O3	122.4 (3)	H18A—C18—H18C	109.5
O4—C8—C9	126.3 (4)	H18B—C18—H18C	109.5
O3—C8—C9	111.2 (3)

C5—O1—C1—O2	−68.1 (3)	C3—C4—C5—C17	171.0 (3)
C5—O1—C1—C2	51.8 (3)	C1—O2—C6—N1	4.3 (5)
C6—O2—C1—O1	−94.0 (3)	C1—O2—C6—C7	−176.8 (2)
C6—O2—C1—C2	141.3 (3)	N1—C6—C7—Cl3	108.7 (4)
C8—O3—C2—C3	−151.7 (3)	O2—C6—C7—Cl3	−70.2 (3)
C8—O3—C2—C1	86.4 (3)	N1—C6—C7—Cl2	−11.1 (5)
O1—C1—C2—O3	72.9 (3)	O2—C6—C7—Cl2	170.0 (2)
O2—C1—C2—O3	−164.5 (2)	N1—C6—C7—Cl1	−131.0 (3)
O1—C1—C2—C3	−44.6 (3)	O2—C6—C7—Cl1	50.2 (3)
O2—C1—C2—C3	78.1 (3)	C2—O3—C8—O4	2.0 (5)
C10—O5—C3—C2	−93.1 (3)	C2—O3—C8—C9	−177.9 (3)
C10—O5—C3—C4	145.6 (3)	C3—O5—C10—O6	−3.6 (5)
O3—C2—C3—O5	167.4 (2)	C3—O5—C10—C11	178.4 (3)
C1—C2—C3—O5	−74.3 (3)	C4—O7—C12—O8	6.8 (5)
O3—C2—C3—C4	−75.9 (3)	C4—O7—C12—C13	−168.6 (3)
C1—C2—C3—C4	42.4 (3)	O8—C12—C13—C14	152.1 (4)
C12—O7—C4—C5	−159.4 (3)	O7—C12—C13—C14	−32.6 (4)
C12—O7—C4—C3	80.8 (3)	C12—C13—C14—C15	−61.0 (4)
O5—C3—C4—O7	−172.2 (2)	C13—C14—C15—O9	−9.9 (5)
C2—C3—C4—O7	69.0 (3)	C13—C14—C15—C16	168.3 (3)
O5—C3—C4—C5	72.1 (3)	C18—O11—C17—O10	2.6 (5)
C2—C3—C4—C5	−46.6 (3)	C18—O11—C17—C5	−176.6 (3)
C1—O1—C5—C4	−55.9 (3)	O1—C5—C17—O10	−6.6 (4)
C1—O1—C5—C17	−175.8 (2)	C4—C5—C17—O10	−128.3 (4)
O7—C4—C5—O1	−65.1 (3)	O1—C5—C17—O11	172.7 (2)
C3—C4—C5—O1	52.4 (3)	C4—C5—C17—O11	50.9 (3)
O7—C4—C5—C17	53.6 (3)

Experimental details

Crystal data
Chemical formula	C₁₈H₂₂Cl₃NO₁₁
M_r	534.72
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	9.0498 (10), 9.7560 (11), 26.570 (3)
V (Å³)	2345.8 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	4.07
Crystal size (mm)	0.41 × 0.30 × 0.28

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Numerical (ABSCOR; Higashi, 1995)
T_min, T_max	0.286, 0.395
No. of measured, independent and observed [I > 2σ(I)] reflections	16340, 4259, 3893
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.100, 1.09
No. of reflections	4259
No. of parameters	302
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.48
Absolute structure	Flack (1983), 1804 Friedel pairs
Absolute structure parameter	0.023 (18)

Computer programs: RAPID-AUTO (Rigaku, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008).

Acknowledgements

The authors thank the NSFC for financial support.

References

Capila, I. & Linhardt, R. J. (2002). Angew. Chem. Int. Ed. 41, 390–412. CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Jobron, L. R. & Jacquinet, J. C. (1998). Carbohydr. Res. 305, 181–191. Google Scholar
Lee, J. C., Lu, X. A., Kulkarni, S. S., Wen, Y. S. & Hung, S. C. (2004). J. Am. Chem. Soc. 126, 476–477. Web of Science CSD CrossRef PubMed CAS Google Scholar
Lohman, G. J. S., Hunt, D. K., Hogermeier, J. A. & Seeberger, P. H. (2003). J. Org. Chem. 68, 7559–7561. Web of Science CrossRef PubMed CAS Google Scholar
Lubineau, A., Gavard, O., Alais, J. & Bonnaffe, D. (2000). Tetrahedron Lett. 41, 307–311. Web of Science CrossRef CAS Google Scholar
Rigaku (2001). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sanjoy, K. D., Jean-Maurice, M., Jacques, E., Pierre-Alexandre, D., Philippe, D., Philippe, S., Jean-Pascal, H., Jean-Marc, H., Maurice, P. & Pierre, S. (2001). Chem. Eur. J. 7, 4821–4834. PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, H. N., Furukawa, J. I., Ikeda, T. & Wong, C. H. (2004). Org. Lett. 6, 723–726. Web of Science CrossRef PubMed CAS Google Scholar

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