Glucosyl anthranilate

Liu, H.; Zou, A.; Zhang, H.; Wang, X.; Yang, Y.

doi:10.1107/S1600536809040975

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2725

https://doi.org/10.1107/S1600536809040975

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Glucosyl anthranilate

Haoyan Liu,^a Ailan Zou,^a Hao Zhang,^a Xiaoming Wang ^a ^* and Yonghua Yang ^a ^*

^aState Key Laboratory of Pharmaceutical Biotechnology, School of Life Science, Nanjing University, 22 Hankou Road, Nanjing, 210093, People's Republic of China
^*Correspondence e-mail: wangxm07@nju.edu.cn, yangyh@nju.edu.cn

(Received 9 September 2009; accepted 7 October 2009; online 13 October 2009)

In the crystal structure of the title compound, C₂₁H₂₅NO₁₁, the hexopyranosyl ring adopts a chair conformation and the five substituents are in equatorial positions. An intramolecular hydrogen bond between the amino group and a neighbouring carbonyl group is found. Two carbonyl groups are disordered and were refined using a split model.

Related literature

The title compound was first obtained by Robert & Tabone (1953 ). For the glycosylation reaction of N-hydroxyphthalimide, see: Cao et al. (1995 ); Saulius et al. (2005 ). For the Hofmann rearrangement, see: Aspinall (1941 ); Yu et al. (2001 ).

Experimental

Crystal data

C₂₁H₂₅NO₁₁
M_r = 467.42
Triclinic, P 1
a = 5.8220 (12) Å
b = 9.1210 (18) Å
c = 11.131 (2) Å
α = 98.94 (3)°
β = 94.53 (3)°
γ = 90.22 (3)°
V = 582.0 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2321 measured reflections
2096 independent reflections
1783 reflections with I > 2σ(I)
R_int = 0.020
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.100
S = 1.04
2096 reflections
320 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O11	0.86	2.06	2.704 (5)	131

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040975/nc2157sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040975/nc2157Isup2.hkl

checkCIF report

Comment top

The title compound was obtained as a by-product of the glycosylation reaction of N-hydroxyphthalimide during the synthesis of O-(2,3,4,6-Tetra-O-acetyl-β-D-glucopyranosyl)- N-oxyphthalimide (Cao et al., 1995; Saulius et al., 2005). Hofmann rearrangement is considered to be the reaction mechanism for its formation (Aspinall,1941;Yu et al.,2001).

The hexopyranosyl ring adopts a chair configuration and all substitutents are in equatorial positions (Fig. 1). Between the amino H atoms and the neighboured carbonyl oxygen atom intramolecular N-H···O hydrogen bonding is found (Table 1).

Related literature top

The title compound was first obtained by Robert & Tabone et al. (1953). For the glycosylation reaction of N-hydroxyphthalimide, see: Cao et al. (1995); Saulius et al. (2005). For the Hofmann rearrangement, see: Aspinall (1941); Yu et al. (2001).

Experimental top

A mixture of N-hydroxyphthalimide(1.5 g, 9.2 mmol), tetrabutylammonium hydrogen sulfate (TBAHS 0.34 g, 1 mmol) and Na₂CO₃ (1M, 20 mL) was stirred at room temperature. After one hour a chloroform solution of 2,3,4,6- tetra-O-acetyl-α-D- glucopyranosyl bromide (3.7 g, 9.0 mmol) was added and the mixture was stirred over night. The organic phase was separated, dried over magnesium sulfate, filtered and concentrated under reduced pressure. Afterwards the product was purified by column chromatography on silica gel(ethylacetate: petroleum ether v/v 1:2). Removal of the solvent leads to the title compound. Yield: 0.34 g (8%). Single crystals suitable for X-ray analysis were obtained by recrystallization from EtOAc. m.p. 403–405 K.

Structure description top

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. The bonds to the disordered atoms are shown with dashed lines. H atoms are omitted for clarity.

Glucosyl anthranilate top

Crystal data top

C₂₁H₂₅NO₁₁	Z = 1
M_r = 467.42	F(000) = 246
Triclinic, P1	D_x = 1.334 Mg m⁻³
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8220 (12) Å	Cell parameters from 25 reflections
b = 9.1210 (18) Å	θ = 9–12°
c = 11.131 (2) Å	µ = 0.11 mm⁻¹
α = 98.94 (3)°	T = 293 K
β = 94.53 (3)°	Block, colourless
γ = 90.22 (3)°	0.30 × 0.20 × 0.10 mm
V = 582.0 (2) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.020
Radiation source: fine-focus sealed tube	θ_max = 25.3°, θ_min = 1.9°
Graphite monochromator	h = 0→6
ω/2θ scans	k = −10→10
2321 measured reflections	l = −13→13
2096 independent reflections	3 standard reflections every 200 reflections
1783 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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0551P)² + 0.0615P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2096 reflections	Δρ_min = −0.13 e Å⁻³
320 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
5 restraints	Extinction coefficient: 0.052 (8)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₁H₂₅NO₁₁	γ = 90.22 (3)°
M_r = 467.42	V = 582.0 (2) Å³
Triclinic, P1	Z = 1
a = 5.8220 (12) Å	Mo Kα radiation
b = 9.1210 (18) Å	µ = 0.11 mm⁻¹
c = 11.131 (2) Å	T = 293 K
α = 98.94 (3)°	0.30 × 0.20 × 0.10 mm
β = 94.53 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.020
2321 measured reflections	3 standard reflections every 200 reflections
2096 independent reflections	intensity decay: 1%
1783 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.040	320 parameters
wR(F²) = 0.100	5 restraints
S = 1.04	H-atom parameters constrained
2096 reflections	Δρ_min = −0.13 e Å⁻³

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	Occ. (<1)
O1	0.4723 (4)	0.2186 (3)	0.0201 (2)	0.0473 (6)
O2	0.4296 (4)	0.0007 (3)	−0.1971 (2)	0.0552 (6)
O3	0.6518 (6)	−0.1311 (4)	−0.3260 (4)	0.1014 (13)
O4	0.6863 (4)	0.4159 (3)	−0.2092 (2)	0.0478 (6)
O5	1.0705 (5)	0.4424 (4)	−0.1993 (3)	0.0797 (9)
O6	0.8323 (4)	0.6042 (3)	0.0311 (2)	0.0539 (6)
O7	0.6443 (18)	0.8007 (11)	−0.0182 (10)	0.089 (3)	0.50
O7'	0.697 (2)	0.7638 (13)	−0.0826 (9)	0.102 (4)	0.50
O8	0.4552 (5)	0.5912 (3)	0.1864 (2)	0.0642 (7)
O9	0.715 (3)	0.587 (3)	0.337 (2)	0.172 (11)	0.50
O9'	0.650 (4)	0.562 (2)	0.3641 (18)	0.138 (8)	0.50
O10	0.3348 (4)	0.2984 (3)	0.2025 (2)	0.0538 (6)
O11	−0.0099 (4)	0.2080 (3)	0.1202 (2)	0.0613 (7)
N1	−0.2584 (6)	0.0580 (5)	0.2582 (4)	0.0830 (11)
H1A	−0.3743	0.0071	0.2734	0.100*
H1B	−0.2509	0.0817	0.1868	0.100*
C1	0.3810 (6)	0.3425 (4)	0.0908 (3)	0.0468 (8)
H1C	0.2406	0.3758	0.0493	0.056*
C2	0.5594 (6)	0.4647 (4)	0.1187 (3)	0.0498 (8)
H2A	0.6935	0.4331	0.1665	0.060*
C3	0.6312 (5)	0.5090 (4)	0.0013 (3)	0.0447 (8)
H3A	0.5061	0.5628	−0.0360	0.054*
C4	0.6931 (5)	0.3744 (4)	−0.0887 (3)	0.0442 (8)
H4A	0.8474	0.3406	−0.0653	0.053*
C5	0.5175 (6)	0.2470 (4)	−0.0987 (3)	0.0423 (7)
H5A	0.3740	0.2725	−0.1423	0.051*
C6	0.6126 (6)	0.1085 (4)	−0.1660 (3)	0.0498 (8)
H6A	0.6767	0.1297	−0.2395	0.060*
H6B	0.7344	0.0707	−0.1152	0.060*
C7	0.4769 (8)	−0.1189 (5)	−0.2748 (4)	0.0656 (11)
C8	0.2885 (9)	−0.2322 (5)	−0.2932 (5)	0.0827 (14)
H8A	0.2755	−0.2799	−0.3767	0.124*
H8B	0.1459	−0.1852	−0.2739	0.124*
H8C	0.3223	−0.3049	−0.2407	0.124*
C9	0.8873 (6)	0.4456 (4)	−0.2551 (3)	0.0527 (9)
C10	0.8433 (8)	0.4856 (5)	−0.3784 (4)	0.0667 (11)
H10A	0.7942	0.5867	−0.3718	0.100*
H10B	0.7251	0.4214	−0.4236	0.100*
H10C	0.9822	0.4748	−0.4199	0.100*
C11	0.8326 (8)	0.7376 (4)	−0.0001 (4)	0.0644 (10)
C12	1.0535 (8)	0.8176 (5)	0.0358 (5)	0.0797 (13)
H12A	1.0286	0.9226	0.0444	0.120*	0.50
H12B	1.1587	0.7897	−0.0256	0.120*	0.50
H12C	1.1172	0.7928	0.1122	0.120*	0.50
H12D	1.1744	0.7475	0.0429	0.120*	0.50
H12E	1.0443	0.8804	0.1129	0.120*	0.50
H12F	1.0858	0.8773	−0.0249	0.120*	0.50
C13	0.5261 (15)	0.6275 (7)	0.3044 (5)	0.104 (2)
C14	0.3672 (15)	0.7450 (8)	0.3642 (6)	0.140 (3)
H14A	0.4208	0.7742	0.4483	0.210*
H14B	0.2135	0.7048	0.3589	0.210*
H14C	0.3675	0.8299	0.3229	0.210*
C15	0.1294 (6)	0.2281 (4)	0.2076 (3)	0.0463 (8)
C16	0.1078 (6)	0.1823 (4)	0.3258 (3)	0.0509 (8)
C17	0.2779 (7)	0.2219 (5)	0.4221 (3)	0.0662 (11)
H17A	0.4059	0.2771	0.4093	0.079*
C18	0.2601 (8)	0.1814 (6)	0.5343 (4)	0.0797 (13)
H18A	0.3756	0.2077	0.5967	0.096*
C19	0.0679 (8)	0.1007 (6)	0.5540 (4)	0.0797 (13)
H19A	0.0542	0.0727	0.6300	0.096*
C20	−0.0983 (8)	0.0629 (5)	0.4637 (4)	0.0734 (12)
H20A	−0.2259	0.0093	0.4792	0.088*
C21	−0.0876 (6)	0.1010 (5)	0.3469 (4)	0.0598 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0441 (13)	0.0510 (13)	0.0484 (14)	−0.0033 (10)	0.0031 (10)	0.0132 (11)
O2	0.0537 (14)	0.0508 (14)	0.0595 (15)	−0.0097 (11)	0.0062 (11)	0.0030 (12)
O3	0.103 (3)	0.079 (2)	0.117 (3)	−0.0201 (19)	0.056 (2)	−0.026 (2)
O4	0.0410 (12)	0.0614 (14)	0.0442 (13)	−0.0013 (10)	0.0038 (10)	0.0185 (10)
O5	0.0482 (16)	0.115 (3)	0.085 (2)	0.0004 (16)	0.0113 (14)	0.0408 (19)
O6	0.0488 (13)	0.0473 (13)	0.0660 (15)	−0.0081 (10)	−0.0006 (11)	0.0135 (11)
O7	0.097 (6)	0.059 (5)	0.111 (8)	−0.001 (4)	−0.026 (6)	0.027 (6)
O7'	0.137 (9)	0.074 (7)	0.097 (7)	−0.030 (6)	−0.043 (7)	0.048 (6)
O8	0.0817 (19)	0.0653 (17)	0.0434 (14)	−0.0074 (14)	0.0076 (13)	0.0007 (12)
O9	0.195 (14)	0.25 (2)	0.054 (10)	−0.041 (14)	−0.044 (11)	−0.003 (10)
O9'	0.24 (2)	0.120 (9)	0.045 (7)	0.027 (12)	−0.037 (9)	0.012 (6)
O10	0.0464 (13)	0.0762 (17)	0.0416 (13)	−0.0096 (12)	0.0003 (10)	0.0195 (12)
O11	0.0465 (13)	0.0835 (18)	0.0562 (15)	−0.0085 (12)	−0.0038 (12)	0.0225 (13)
N1	0.056 (2)	0.113 (3)	0.084 (3)	−0.024 (2)	0.0081 (19)	0.029 (2)
C1	0.0431 (18)	0.057 (2)	0.0412 (18)	−0.0010 (16)	0.0010 (14)	0.0115 (16)
C2	0.053 (2)	0.055 (2)	0.0421 (17)	−0.0015 (16)	−0.0016 (15)	0.0115 (16)
C3	0.0415 (18)	0.0468 (19)	0.0463 (19)	−0.0008 (15)	−0.0011 (14)	0.0115 (15)
C4	0.0395 (17)	0.051 (2)	0.0440 (18)	−0.0010 (15)	−0.0026 (14)	0.0153 (15)
C5	0.0365 (16)	0.0510 (19)	0.0408 (17)	−0.0019 (14)	0.0005 (13)	0.0127 (14)
C6	0.0476 (19)	0.052 (2)	0.0501 (19)	−0.0045 (16)	0.0055 (15)	0.0068 (16)
C7	0.083 (3)	0.055 (2)	0.057 (2)	−0.010 (2)	0.007 (2)	0.0042 (19)
C8	0.099 (4)	0.064 (3)	0.080 (3)	−0.028 (3)	0.008 (3)	−0.005 (2)
C9	0.050 (2)	0.052 (2)	0.059 (2)	−0.0008 (16)	0.0101 (18)	0.0132 (17)
C10	0.074 (3)	0.074 (3)	0.056 (2)	−0.011 (2)	0.014 (2)	0.019 (2)
C11	0.076 (3)	0.050 (2)	0.069 (3)	−0.007 (2)	0.001 (2)	0.0158 (19)
C12	0.081 (3)	0.059 (3)	0.099 (4)	−0.020 (2)	0.016 (3)	0.007 (2)
C13	0.152 (6)	0.099 (4)	0.052 (3)	−0.029 (4)	−0.004 (4)	−0.006 (3)
C14	0.209 (8)	0.121 (5)	0.081 (4)	−0.021 (5)	0.050 (5)	−0.032 (4)
C15	0.0416 (18)	0.049 (2)	0.0492 (19)	0.0038 (15)	0.0062 (15)	0.0104 (15)
C16	0.047 (2)	0.059 (2)	0.050 (2)	0.0088 (16)	0.0126 (16)	0.0149 (17)
C17	0.061 (2)	0.093 (3)	0.048 (2)	−0.001 (2)	0.0040 (18)	0.021 (2)
C18	0.069 (3)	0.121 (4)	0.053 (2)	0.005 (3)	0.006 (2)	0.028 (2)
C19	0.080 (3)	0.112 (4)	0.060 (3)	0.023 (3)	0.026 (2)	0.041 (2)
C20	0.067 (3)	0.086 (3)	0.078 (3)	0.004 (2)	0.031 (2)	0.034 (2)
C21	0.045 (2)	0.070 (2)	0.069 (2)	0.0069 (18)	0.0152 (18)	0.021 (2)

Geometric parameters (Å, º) top

O1—C1	1.405 (4)	C6—H6A	0.9700
O1—C5	1.430 (4)	C6—H6B	0.9700
O2—C7	1.326 (5)	C7—C8	1.485 (6)
O2—C6	1.432 (4)	C8—H8A	0.9600
O3—C7	1.203 (5)	C8—H8B	0.9600
O4—C9	1.356 (4)	C8—H8C	0.9600
O4—C4	1.447 (4)	C9—C10	1.478 (5)
O5—C9	1.194 (4)	C10—H10A	0.9600
O6—C11	1.316 (4)	C10—H10B	0.9600
O6—C3	1.441 (4)	C10—H10C	0.9600
O7—C11	1.257 (10)	C11—C12	1.472 (6)
O7'—C11	1.217 (9)	C12—H12A	0.9600
O8—C13	1.335 (6)	C12—H12B	0.9600
O8—C2	1.440 (5)	C12—H12C	0.9600
O9—C13	1.204 (17)	C12—H12D	0.9600
O9'—C13	1.169 (14)	C12—H12E	0.9600
O10—C15	1.364 (4)	C12—H12F	0.9600
O10—C1	1.409 (4)	C13—C14	1.526 (11)
O11—C15	1.206 (4)	C14—H14A	0.9600
N1—C21	1.357 (5)	C14—H14B	0.9600
N1—H1A	0.8600	C14—H14C	0.9600
N1—H1B	0.8600	C15—C16	1.456 (5)
C1—C2	1.500 (5)	C16—C17	1.404 (5)
C1—H1C	0.9800	C16—C21	1.410 (5)
C2—C3	1.515 (5)	C17—C18	1.368 (6)
C2—H2A	0.9800	C17—H17A	0.9300
C3—C4	1.522 (5)	C18—C19	1.388 (7)
C3—H3A	0.9800	C18—H18A	0.9300
C4—C5	1.530 (4)	C19—C20	1.342 (7)
C4—H4A	0.9800	C19—H19A	0.9300
C5—C6	1.497 (5)	C20—C21	1.403 (6)
C5—H5A	0.9800	C20—H20A	0.9300

C1—O1—C5	112.2 (2)	H10B—C10—H10C	109.5
C7—O2—C6	115.5 (3)	O7'—C11—O7	39.0 (6)
C9—O4—C4	118.9 (3)	O7'—C11—O6	119.0 (6)
C11—O6—C3	120.2 (3)	O7—C11—O6	119.4 (6)
C13—O8—C2	117.4 (4)	O7'—C11—C12	124.0 (7)
C15—O10—C1	117.7 (3)	O7—C11—C12	123.8 (6)
C21—N1—H1A	120.0	O6—C11—C12	112.6 (4)
C21—N1—H1B	120.0	C11—C12—H12A	109.5
H1A—N1—H1B	120.0	C11—C12—H12B	109.5
O1—C1—O10	106.7 (3)	H12A—C12—H12B	109.5
O1—C1—C2	109.6 (3)	C11—C12—H12C	109.5
O10—C1—C2	107.4 (3)	H12A—C12—H12C	109.5
O1—C1—H1C	111.0	H12B—C12—H12C	109.5
O10—C1—H1C	111.0	C11—C12—H12D	109.5
C2—C1—H1C	111.0	H12A—C12—H12D	141.1
O8—C2—C1	107.6 (3)	H12B—C12—H12D	56.3
O8—C2—C3	108.0 (3)	H12C—C12—H12D	56.3
C1—C2—C3	110.1 (3)	C11—C12—H12E	109.5
O8—C2—H2A	110.3	H12A—C12—H12E	56.3
C1—C2—H2A	110.3	H12B—C12—H12E	141.1
C3—C2—H2A	110.3	H12C—C12—H12E	56.3
O6—C3—C2	107.8 (3)	H12D—C12—H12E	109.5
O6—C3—C4	108.3 (3)	C11—C12—H12F	109.5
C2—C3—C4	111.6 (3)	H12A—C12—H12F	56.3
O6—C3—H3A	109.7	H12B—C12—H12F	56.3
C2—C3—H3A	109.7	H12C—C12—H12F	141.1
C4—C3—H3A	109.7	H12D—C12—H12F	109.5
O4—C4—C3	108.6 (3)	H12E—C12—H12F	109.5
O4—C4—C5	105.5 (2)	O9'—C13—O9	28 (2)
C3—C4—C5	112.4 (3)	O9'—C13—O8	128.1 (11)
O4—C4—H4A	110.1	O9—C13—O8	117.2 (13)
C3—C4—H4A	110.1	O9'—C13—C14	120.6 (12)
C5—C4—H4A	110.1	O9—C13—C14	131.9 (12)
O1—C5—C6	107.8 (3)	O8—C13—C14	109.1 (7)
O1—C5—C4	110.3 (2)	C13—C14—H14A	109.5
C6—C5—C4	109.7 (3)	C13—C14—H14B	109.5
O1—C5—H5A	109.7	H14A—C14—H14B	109.5
C6—C5—H5A	109.7	C13—C14—H14C	109.5
C4—C5—H5A	109.7	H14A—C14—H14C	109.5
O2—C6—C5	108.5 (3)	H14B—C14—H14C	109.5
O2—C6—H6A	110.0	O11—C15—O10	120.9 (3)
C5—C6—H6A	110.0	O11—C15—C16	126.9 (3)
O2—C6—H6B	110.0	O10—C15—C16	112.2 (3)
C5—C6—H6B	110.0	C17—C16—C21	118.7 (3)
H6A—C6—H6B	108.4	C17—C16—C15	120.6 (3)
O3—C7—O2	123.0 (4)	C21—C16—C15	120.7 (3)
O3—C7—C8	124.4 (4)	C18—C17—C16	121.6 (4)
O2—C7—C8	112.5 (4)	C18—C17—H17A	119.2
C7—C8—H8A	109.5	C16—C17—H17A	119.2
C7—C8—H8B	109.5	C17—C18—C19	119.3 (4)
H8A—C8—H8B	109.5	C17—C18—H18A	120.4
C7—C8—H8C	109.5	C19—C18—H18A	120.4
H8A—C8—H8C	109.5	C20—C19—C18	120.2 (4)
H8B—C8—H8C	109.5	C20—C19—H19A	119.9
O5—C9—O4	122.9 (3)	C18—C19—H19A	119.9
O5—C9—C10	126.6 (4)	C19—C20—C21	122.7 (4)
O4—C9—C10	110.5 (3)	C19—C20—H20A	118.6
C9—C10—H10A	109.5	C21—C20—H20A	118.6
C9—C10—H10B	109.5	N1—C21—C20	120.4 (4)
H10A—C10—H10B	109.5	N1—C21—C16	122.1 (4)
C9—C10—H10C	109.5	C20—C21—C16	117.5 (4)
H10A—C10—H10C	109.5

C5—O1—C1—O10	177.4 (2)	O1—C5—C6—O2	72.2 (3)
C5—O1—C1—C2	−66.6 (3)	C4—C5—C6—O2	−167.7 (3)
C15—O10—C1—O1	−84.7 (3)	C6—O2—C7—O3	−7.3 (6)
C15—O10—C1—C2	157.9 (3)	C6—O2—C7—C8	174.2 (4)
C13—O8—C2—C1	109.3 (4)	C4—O4—C9—O5	−1.8 (5)
C13—O8—C2—C3	−131.8 (4)	C4—O4—C9—C10	−180.0 (3)
O1—C1—C2—O8	177.5 (3)	C3—O6—C11—O7'	−21.7 (9)
O10—C1—C2—O8	−67.0 (3)	C3—O6—C11—O7	23.3 (8)
O1—C1—C2—C3	60.0 (3)	C3—O6—C11—C12	−179.0 (3)
O10—C1—C2—C3	175.5 (3)	C2—O8—C13—O9'	−7.0 (19)
C11—O6—C3—C2	−124.0 (3)	C2—O8—C13—O9	23.4 (19)
C11—O6—C3—C4	115.1 (4)	C2—O8—C13—C14	−170.0 (4)
O8—C2—C3—O6	73.9 (3)	C1—O10—C15—O11	−1.9 (5)
C1—C2—C3—O6	−168.8 (3)	C1—O10—C15—C16	177.2 (3)
O8—C2—C3—C4	−167.2 (3)	O11—C15—C16—C17	−175.7 (4)
C1—C2—C3—C4	−49.9 (4)	O10—C15—C16—C17	5.2 (5)
C9—O4—C4—C3	101.4 (3)	O11—C15—C16—C21	2.4 (6)
C9—O4—C4—C5	−137.9 (3)	O10—C15—C16—C21	−176.7 (3)
O6—C3—C4—O4	−79.8 (3)	C21—C16—C17—C18	1.2 (6)
C2—C3—C4—O4	161.6 (2)	C15—C16—C17—C18	179.3 (4)
O6—C3—C4—C5	163.8 (2)	C16—C17—C18—C19	−0.8 (7)
C2—C3—C4—C5	45.2 (3)	C17—C18—C19—C20	0.0 (8)
C1—O1—C5—C6	−179.8 (3)	C18—C19—C20—C21	0.3 (8)
C1—O1—C5—C4	60.5 (3)	C19—C20—C21—N1	178.9 (4)
O4—C4—C5—O1	−167.3 (2)	C19—C20—C21—C16	0.1 (7)
C3—C4—C5—O1	−49.1 (3)	C17—C16—C21—N1	−179.6 (4)
O4—C4—C5—C6	74.1 (3)	C15—C16—C21—N1	2.2 (6)
C3—C4—C5—C6	−167.7 (3)	C17—C16—C21—C20	−0.8 (5)
C7—O2—C6—C5	169.0 (3)	C15—C16—C21—C20	−178.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O11	0.86	2.06	2.704 (5)	131

Experimental details

Crystal data
Chemical formula	C₂₁H₂₅NO₁₁
M_r	467.42
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.8220 (12), 9.1210 (18), 11.131 (2)
α, β, γ (°)	98.94 (3), 94.53 (3), 90.22 (3)
V (Å³)	582.0 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2321, 2096, 1783
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.100, 1.04
No. of reflections	2096
No. of parameters	320
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	?, −0.13

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O11	0.86	2.06	2.704 (5)	130.6

Acknowledgements

We are grateful to the National Natural Science Foundation of China (No. 30701041)

References

Aspinall, S. R. (1941). J. Am. Chem. Soc. 63, 2843–2843. CrossRef CAS Google Scholar
Cao, S. D., Tropper, T. D. & Roy, R. (1995). Tetrahedron, 51, 6679–6686. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Robert, D. & Tabone, J. (1953). C. R. Acad. Sci. 236, 206–208. CAS Google Scholar
Saulius, G., Sabine, C., Olivier, R., Richard, L. M., Edith, D., Claude, L. & Pascal, D. (2005). Bioconjug. Chem. 16, 1149–1159. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, C. Z., Jiang, Y. Y., Liu, B. & Hu, L. Q. (2001). Tetrahedron Lett. 42, 1449–1452. Web of Science CrossRef CAS Google Scholar