4-Formyl-phenyl 2,3,4,6-tetra-O-acetyl-β-d-allopyran-oside.

The title compound, C(21)H(24)O(11), crystallizes exclusively as the β-anomer. The substituent of the protected sugar at position C-3 is in the axial position, while all other groups are in equatorial positions. The pyran-oside ring adopts a stable chair conformation.

Related literature

For the synthesis see: Chen et al. (1981 ▶); Wen et al. (2008 ▶). For the pharmacological activities of helicid derivatives, see: Fan et al. (2008 ▶), Sha et al. (1987 ▶). For related structures, see: Burkhardt et al. (2007a ▶, 2007b ▶)

Experimental

Crystal data

C21H24O11

M = 452.40

Monoclinic,

a = 7.056 (4) Å

b = 17.758 (6) Å

c = 9.129 (3) Å

β = 102.80 (4)°

V = 1115.4 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 291 K

0.44 × 0.42 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none

4596 measured reflections

4149 independent reflections

2143 reflections with I > 2σ(I)

R int = 0.029

3 standard reflections every 150 reflections intensity decay: 3.7%

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.143

S = 0.95

4149 reflections

293 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.20 e Å−3

Data collection: DIFRAC (Gabe & White, 1993 ▶); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018248/bx2200sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018248/bx2200Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H24O11	F(000) = 476
Mr = 452.40	Dx = 1.347 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 33 reflections
a = 7.056 (4) Å	θ = 4.6–9.4°
b = 17.758 (6) Å	µ = 0.11 mm−1
c = 9.129 (3) Å	T = 291 K
β = 102.80 (4)°	Block, colourless
V = 1115.4 (8) Å3	0.44 × 0.42 × 0.20 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	Rint = 0.029
Radiation source: fine-focus sealed tube	θmax = 32.5°, θmin = 2.3°
graphite	h = −10→10
ω/2θ scans	k = −25→26
4596 measured reflections	l = −13→13
4149 independent reflections	3 standard reflections every 150 reflections
2143 reflections with I > 2σ(I)	intensity decay: 3.7%

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H-atom parameters constrained
S = 0.95	w = 1/[σ2(Fo2) + (0.0778P)2] where P = (Fo2 + 2Fc2)/3
4149 reflections	(Δ/σ)max < 0.001
293 parameters	Δρmax = 0.30 e Å−3
1 restraint	Δρmin = −0.20 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.4950 (3)	0.63276 (10)	0.1617 (2)	0.0399 (4)
O2	0.2064 (3)	0.55171 (14)	−0.0604 (2)	0.0526 (5)
O3	0.3692 (5)	0.62506 (18)	−0.1903 (3)	0.0857 (9)
O4	0.2271 (3)	0.48018 (11)	0.2871 (2)	0.0436 (4)
O5	−0.0540 (3)	0.52455 (15)	0.3289 (4)	0.0733 (8)
O6	0.5256 (3)	0.54679 (12)	0.5011 (2)	0.0446 (4)
O7	0.3283 (4)	0.48347 (14)	0.6212 (3)	0.0657 (7)
O8	0.5465 (3)	0.69998 (12)	0.5428 (2)	0.0468 (5)
O9	0.2909 (5)	0.7687 (2)	0.5597 (4)	0.1025 (12)
O10	0.6171 (3)	0.74339 (10)	0.2628 (2)	0.0415 (4)
O11	1.2834 (4)	0.88786 (18)	−0.0222 (3)	0.0780 (8)
C1	0.5854 (4)	0.66770 (14)	0.2979 (3)	0.0370 (5)
H1	0.7070	0.6424	0.3454	0.044*
C2	0.4428 (4)	0.67009 (15)	0.4018 (3)	0.0385 (6)
H2	0.3343	0.7036	0.3589	0.046*
C3	0.3648 (4)	0.59176 (16)	0.4229 (3)	0.0394 (6)
H3	0.2627	0.5944	0.4801	0.047*
C4	0.2873 (4)	0.55657 (15)	0.2697 (3)	0.0388 (6)
H4	0.1757	0.5858	0.2156	0.047*
C5	0.4441 (4)	0.55511 (15)	0.1781 (3)	0.0382 (6)
H5	0.5581	0.5283	0.2352	0.046*
C6	0.3858 (4)	0.52131 (17)	0.0245 (3)	0.0482 (7)
H6A	0.4876	0.5304	−0.0293	0.058*
H6B	0.3723	0.4673	0.0338	0.058*
C7	0.2171 (6)	0.6017 (2)	−0.1706 (4)	0.0620 (9)
C8	0.0234 (7)	0.6216 (3)	−0.2607 (5)	0.0897 (13)
H8A	0.0274	0.6713	−0.3014	0.135*
H8B	−0.0694	0.6204	−0.1981	0.135*
H8C	−0.0141	0.5862	−0.3412	0.135*
C9	0.0503 (4)	0.47285 (19)	0.3242 (4)	0.0528 (8)
C10	0.0162 (6)	0.3927 (2)	0.3635 (5)	0.0743 (11)
H10A	0.0886	0.3821	0.4634	0.111*
H10B	0.0578	0.3596	0.2937	0.111*
H10C	−0.1198	0.3851	0.3586	0.111*
C11	0.4840 (5)	0.49291 (18)	0.5944 (3)	0.0535 (8)
C12	0.6629 (7)	0.4484 (3)	0.6583 (6)	0.0856 (13)
H12A	0.7167	0.4648	0.7591	0.128*
H12B	0.7566	0.4557	0.5978	0.128*
H12C	0.6303	0.3959	0.6590	0.128*
C13	0.4540 (5)	0.75101 (18)	0.6110 (4)	0.0563 (8)
C14	0.5769 (7)	0.7780 (3)	0.7549 (5)	0.0842 (13)
H14A	0.5345	0.8273	0.7771	0.126*
H14B	0.7100	0.7804	0.7465	0.126*
H14C	0.5656	0.7439	0.8341	0.126*
C15	0.7685 (4)	0.75945 (14)	0.1960 (3)	0.0359 (5)
C16	0.8011 (4)	0.83541 (16)	0.1761 (3)	0.0430 (6)
H16	0.7223	0.8714	0.2069	0.052*
C17	0.9503 (4)	0.85760 (16)	0.1108 (3)	0.0453 (7)
H17	0.9704	0.9085	0.0961	0.054*
C18	1.0703 (4)	0.80472 (17)	0.0669 (3)	0.0417 (6)
C19	1.0361 (4)	0.72875 (17)	0.0863 (3)	0.0460 (7)
H19	1.1167	0.6930	0.0568	0.055*
C20	0.8838 (4)	0.70516 (16)	0.1487 (3)	0.0443 (6)
H20	0.8594	0.6542	0.1587	0.053*
C21	1.2373 (5)	0.8255 (2)	0.0018 (4)	0.0587 (8)
H21	1.3126	0.7864	−0.0224	0.070*

	U11	U22	U33	U12	U13	U23
O1	0.0456 (10)	0.0342 (9)	0.0435 (10)	−0.0048 (8)	0.0178 (8)	0.0015 (8)
O2	0.0535 (12)	0.0559 (12)	0.0508 (11)	−0.0077 (10)	0.0171 (10)	−0.0018 (10)
O3	0.101 (2)	0.085 (2)	0.0768 (18)	−0.0286 (18)	0.0309 (15)	0.0115 (15)
O4	0.0422 (10)	0.0337 (10)	0.0598 (11)	−0.0029 (8)	0.0218 (9)	0.0005 (9)
O5	0.0492 (13)	0.0593 (16)	0.121 (2)	0.0022 (12)	0.0392 (14)	0.0042 (15)
O6	0.0462 (11)	0.0442 (10)	0.0462 (10)	0.0045 (9)	0.0162 (8)	0.0099 (8)
O7	0.0768 (17)	0.0592 (15)	0.0691 (15)	−0.0078 (13)	0.0330 (13)	0.0151 (13)
O8	0.0454 (11)	0.0481 (11)	0.0502 (11)	−0.0016 (9)	0.0177 (9)	−0.0086 (9)
O9	0.102 (2)	0.109 (3)	0.097 (2)	0.049 (2)	0.0209 (18)	−0.0315 (19)
O10	0.0459 (10)	0.0294 (9)	0.0559 (11)	0.0004 (8)	0.0257 (9)	0.0009 (8)
O11	0.0760 (18)	0.0810 (19)	0.0855 (19)	−0.0344 (15)	0.0361 (15)	−0.0012 (15)
C1	0.0399 (13)	0.0320 (12)	0.0432 (13)	−0.0019 (10)	0.0176 (11)	0.0001 (11)
C2	0.0402 (14)	0.0360 (13)	0.0427 (13)	0.0008 (11)	0.0167 (11)	−0.0013 (11)
C3	0.0367 (13)	0.0387 (13)	0.0478 (14)	0.0010 (11)	0.0197 (11)	0.0035 (12)
C4	0.0374 (13)	0.0300 (12)	0.0521 (15)	−0.0012 (11)	0.0166 (11)	0.0027 (11)
C5	0.0399 (14)	0.0329 (13)	0.0465 (14)	−0.0001 (11)	0.0195 (11)	0.0010 (11)
C6	0.0526 (17)	0.0426 (15)	0.0540 (17)	−0.0005 (13)	0.0216 (14)	−0.0051 (13)
C7	0.086 (3)	0.0523 (19)	0.0521 (18)	−0.0007 (18)	0.0236 (18)	−0.0051 (15)
C8	0.099 (3)	0.102 (3)	0.063 (2)	0.017 (3)	0.006 (2)	0.004 (2)
C9	0.0444 (16)	0.0487 (18)	0.070 (2)	−0.0114 (15)	0.0227 (14)	−0.0075 (16)
C10	0.078 (3)	0.049 (2)	0.105 (3)	−0.0242 (19)	0.039 (2)	0.005 (2)
C11	0.068 (2)	0.0462 (17)	0.0481 (16)	0.0011 (15)	0.0168 (15)	0.0058 (14)
C12	0.089 (3)	0.079 (3)	0.088 (3)	0.020 (2)	0.018 (2)	0.032 (2)
C13	0.070 (2)	0.0432 (17)	0.0644 (19)	0.0026 (16)	0.0339 (17)	−0.0080 (15)
C14	0.096 (3)	0.090 (3)	0.077 (2)	−0.037 (3)	0.041 (2)	−0.036 (2)
C15	0.0365 (13)	0.0345 (13)	0.0379 (13)	−0.0017 (10)	0.0108 (10)	0.0020 (10)
C16	0.0446 (15)	0.0302 (13)	0.0559 (17)	−0.0023 (11)	0.0148 (13)	−0.0053 (12)
C17	0.0479 (16)	0.0354 (14)	0.0534 (16)	−0.0104 (12)	0.0132 (13)	−0.0016 (12)
C18	0.0395 (13)	0.0463 (16)	0.0408 (13)	−0.0058 (12)	0.0125 (11)	0.0022 (12)
C19	0.0489 (16)	0.0406 (15)	0.0530 (16)	0.0063 (13)	0.0210 (13)	0.0013 (12)
C20	0.0501 (15)	0.0312 (13)	0.0568 (16)	0.0019 (12)	0.0230 (13)	0.0011 (12)
C21	0.0525 (18)	0.070 (2)	0.0581 (18)	−0.0109 (17)	0.0212 (15)	0.0046 (17)

O1—C1	1.409 (3)	C7—C8	1.474 (6)
O1—C5	1.441 (3)	C8—H8A	0.9600
O2—C7	1.356 (4)	C8—H8B	0.9600
O2—C6	1.435 (4)	C8—H8C	0.9600
O3—C7	1.201 (5)	C9—C10	1.500 (5)
O4—C9	1.369 (4)	C10—H10A	0.9600
O4—C4	1.441 (3)	C10—H10B	0.9600
O5—C9	1.184 (4)	C10—H10C	0.9600
O6—C11	1.356 (4)	C11—C12	1.494 (5)
O6—C3	1.441 (4)	C12—H12A	0.9600
O7—C11	1.189 (4)	C12—H12B	0.9600
O8—C13	1.347 (4)	C12—H12C	0.9600
O8—C2	1.435 (3)	C13—C14	1.484 (5)
O9—C13	1.185 (5)	C14—H14A	0.9600
O10—C15	1.372 (3)	C14—H14B	0.9600
O10—C1	1.411 (3)	C14—H14C	0.9600
O11—C21	1.188 (5)	C15—C16	1.387 (4)
C1—C2	1.529 (3)	C15—C20	1.391 (4)
C1—H1	0.9800	C16—C17	1.377 (4)
C2—C3	1.524 (4)	C16—H16	0.9300
C2—H2	0.9800	C17—C18	1.382 (4)
C3—C4	1.519 (4)	C17—H17	0.9300
C3—H3	0.9800	C18—C19	1.389 (4)
C4—C5	1.528 (3)	C18—C21	1.479 (4)
C4—H4	0.9800	C19—C20	1.388 (4)
C5—C6	1.497 (4)	C19—H19	0.9300
C5—H5	0.9800	C20—H20	0.9300
C6—H6A	0.9700	C21—H21	0.9300
C6—H6B	0.9700
C1—O1—C5	113.85 (19)	H8B—C8—H8C	109.5
C7—O2—C6	117.3 (3)	O5—C9—O4	122.9 (3)
C9—O4—C4	115.1 (2)	O5—C9—C10	126.4 (3)
C11—O6—C3	116.5 (2)	O4—C9—C10	110.7 (3)
C13—O8—C2	117.4 (2)	C9—C10—H10A	109.5
C15—O10—C1	118.5 (2)	C9—C10—H10B	109.5
O1—C1—O10	106.5 (2)	H10A—C10—H10B	109.5
O1—C1—C2	109.2 (2)	C9—C10—H10C	109.5
O10—C1—C2	105.9 (2)	H10A—C10—H10C	109.5
O1—C1—H1	111.7	H10B—C10—H10C	109.5
O10—C1—H1	111.7	O7—C11—O6	124.5 (3)
C2—C1—H1	111.7	O7—C11—C12	125.8 (3)
O8—C2—C3	110.5 (2)	O6—C11—C12	109.7 (3)
O8—C2—C1	107.0 (2)	C11—C12—H12A	109.5
C3—C2—C1	111.0 (2)	C11—C12—H12B	109.5
O8—C2—H2	109.4	H12A—C12—H12B	109.5
C3—C2—H2	109.4	C11—C12—H12C	109.5
C1—C2—H2	109.4	H12A—C12—H12C	109.5
O6—C3—C4	108.2 (2)	H12B—C12—H12C	109.5
O6—C3—C2	107.6 (2)	O9—C13—O8	121.5 (3)
C4—C3—C2	109.0 (2)	O9—C13—C14	126.2 (3)
O6—C3—H3	110.7	O8—C13—C14	112.2 (3)
C4—C3—H3	110.7	C13—C14—H14A	109.5
C2—C3—H3	110.7	C13—C14—H14B	109.5
O4—C4—C3	109.9 (2)	H14A—C14—H14B	109.5
O4—C4—C5	108.1 (2)	C13—C14—H14C	109.5
C3—C4—C5	110.7 (2)	H14A—C14—H14C	109.5
O4—C4—H4	109.3	H14B—C14—H14C	109.5
C3—C4—H4	109.3	O10—C15—C16	115.4 (2)
C5—C4—H4	109.3	O10—C15—C20	124.1 (2)
O1—C5—C6	108.0 (2)	C16—C15—C20	120.5 (2)
O1—C5—C4	105.6 (2)	C17—C16—C15	120.0 (3)
C6—C5—C4	115.9 (2)	C17—C16—H16	120.0
O1—C5—H5	109.0	C15—C16—H16	120.0
C6—C5—H5	109.0	C16—C17—C18	120.5 (3)
C4—C5—H5	109.0	C16—C17—H17	119.8
O2—C6—C5	112.4 (2)	C18—C17—H17	119.8
O2—C6—H6A	109.1	C17—C18—C19	119.2 (3)
C5—C6—H6A	109.1	C17—C18—C21	122.7 (3)
O2—C6—H6B	109.1	C19—C18—C21	118.0 (3)
C5—C6—H6B	109.1	C20—C19—C18	121.2 (3)
H6A—C6—H6B	107.8	C20—C19—H19	119.4
O3—C7—O2	122.4 (4)	C18—C19—H19	119.4
O3—C7—C8	125.6 (4)	C19—C20—C15	118.6 (3)
O2—C7—C8	111.9 (4)	C19—C20—H20	120.7
C7—C8—H8A	109.5	C15—C20—H20	120.7
C7—C8—H8B	109.5	O11—C21—C18	125.6 (4)
H8A—C8—H8B	109.5	O11—C21—H21	117.2
C7—C8—H8C	109.5	C18—C21—H21	117.2
H8A—C8—H8C	109.5
C5—O1—C1—O10	−177.44 (19)	C3—C4—C5—C6	179.7 (2)
C5—O1—C1—C2	−63.6 (3)	C7—O2—C6—C5	104.7 (3)
C15—O10—C1—O1	−76.9 (3)	O1—C5—C6—O2	−68.4 (3)
C15—O10—C1—C2	167.0 (2)	C4—C5—C6—O2	49.8 (3)
C13—O8—C2—C3	−101.7 (3)	C6—O2—C7—O3	−6.0 (5)
C13—O8—C2—C1	137.3 (2)	C6—O2—C7—C8	173.2 (3)
O1—C1—C2—O8	175.1 (2)	C4—O4—C9—O5	6.4 (5)
O10—C1—C2—O8	−70.7 (3)	C4—O4—C9—C10	−171.0 (3)
O1—C1—C2—C3	54.4 (3)	C3—O6—C11—O7	−4.2 (5)
O10—C1—C2—C3	168.6 (2)	C3—O6—C11—C12	176.3 (3)
C11—O6—C3—C4	−94.4 (3)	C2—O8—C13—O9	2.7 (5)
C11—O6—C3—C2	148.0 (2)	C2—O8—C13—C14	−179.5 (3)
O8—C2—C3—O6	−53.2 (3)	C1—O10—C15—C16	−174.9 (2)
C1—C2—C3—O6	65.4 (3)	C1—O10—C15—C20	5.6 (4)
O8—C2—C3—C4	−170.2 (2)	O10—C15—C16—C17	179.6 (2)
C1—C2—C3—C4	−51.7 (3)	C20—C15—C16—C17	−0.8 (4)
C9—O4—C4—C3	78.4 (3)	C15—C16—C17—C18	−1.1 (4)
C9—O4—C4—C5	−160.6 (2)	C16—C17—C18—C19	1.5 (4)
O6—C3—C4—O4	58.7 (2)	C16—C17—C18—C21	−177.5 (3)
C2—C3—C4—O4	175.4 (2)	C17—C18—C19—C20	0.0 (4)
O6—C3—C4—C5	−60.7 (3)	C21—C18—C19—C20	179.1 (3)
C2—C3—C4—C5	56.0 (3)	C18—C19—C20—C15	−1.9 (4)
C1—O1—C5—C6	−169.3 (2)	O10—C15—C20—C19	−178.2 (3)
C1—O1—C5—C4	66.1 (3)	C16—C15—C20—C19	2.3 (4)
O4—C4—C5—O1	178.8 (2)	C17—C18—C21—O11	−1.5 (5)
C3—C4—C5—O1	−60.7 (3)	C19—C18—C21—O11	179.4 (3)
O4—C4—C5—C6	59.3 (3)