1-O-Benzyl-2,3-O-iso-propyl-idene-6-O-tosyl-α-l-sorbo-furan-ose.

IN THE TITLE COMPOUND (SYSTEMATIC NAME: {(3aS,5S,6R,6aS)-3a-[(benz-yloxy)meth-yl]-6-hy-droxy-2,2-di-methyl-tetra-hydro-furo[2,3-d][1,3]dioxol-5-yl}methyl 4-methyl-benzene-sulfonate), C23H28O8S, the absolute structure and relative stereochemistry of the four chiral centres have been established by X-ray crystallography, with the absolute configuration inferred from the use of l-sorbose as the starting material. The central furan-ose ring adopts a slightly twisted envelope conformation (with the C atom bearing the methyl-benzene-sulfonate substituent as the flap) from which three substituents depart pseudo-axially (-CH2-O-benzyl, -OH and one acetonide O atom) and two substituents pseudo-equatorially (-CH2-O-tosyl and second acetonide O atom). The dioxalane ring is in a flattened envelope conformation with the fused CH C atom as the flap. In the crystal, mol-ecules pack in columns along [010] linked by O-H⋯O hydrogen bonds involving the furan-ose hy-droxy group and furan-ose ether O atom.

Related literature

The title compound is a novel inter­mediate in the synthesis of 1-de­oxy­nojirimycin (DNJ) analogues. For examples of the use of monosaccharide starting materials in imino­sugar syntheses, see: Compain & Martin (2001 ▶); Cipolla et al. (2003 ▶); Best, Wang et al. (2010 ▶); Wilkinson et al. (2010 ▶); Nash et al. (2011 ▶); Zhang et al. (2011 ▶); Lenagh-Snow et al. (2011 ▶); Simone et al. (2012 ▶); Soengas et al. (2012 ▶); Kato et al. (2012 ▶). For examples of the synthesis of other biologically active compounds from monosaccharides, see: Compain et al. (2009 ▶); Sridhar et al. (2012 ▶); Das et al. (2012 ▶); Dhavale & Matin (2005 ▶); Compain & Martin (2001 ▶); Derosa & Maffioli (2012 ▶); Lew et al. (2000 ▶); Itzstein et al. (1993 ▶). For glycosidase inhibitors, see: Houston & Blanchfield (2003 ▶). For imino­sugars as glycosidase inhibitors, see: Zechel et al. (2003 ▶); de Melo et al. (2006 ▶); Compain & Martin (2007 ▶). For examples of the clinical uses of imino­sugars, see: Cox et al. (2003 ▶); Venier et al. (2012 ▶); Derosa & Maffioli (2012 ▶). For imino­sugars in the treatment of cancer, cystic fibrosis and viral diseases, see: Nishimura (2003 ▶); Lawton & Witty (2011 ▶); Best, Jenkinson et al. (2010 ▶); Compain & Martin (2007 ▶); Pollock et al. (2008 ▶). For the syntheses of DNJ and its analogues from l-sorbose, see: Beaupere et al. (1989 ▶); Masson et al. (2000 ▶); Tamayo et al. (2010 ▶); O’Brien & Murphy (2011 ▶). For the synthesis of 1-O-benzoyl-2,3-O-iso­propyl­idene-6-O-tosyl-α-l-sorbo­furan­ose, which bears structural similarity to the title compound, see: Fehér & Vargha (1966 ▶).

Experimental

Crystal data

C23H28O8S

M = 464.51

Monoclinic,

a = 22.6192 (3) Å

b = 5.5649 (1) Å

c = 19.0631 (3) Å

β = 104.696 (2)°

V = 2321.04 (6) Å3

Z = 4

Cu Kα radiation

μ = 1.64 mm−1

T = 150 K

0.29 × 0.06 × 0.02 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.628, T max = 1.000

24544 measured reflections

4672 independent reflections

4541 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.127

S = 1.16

4672 reflections

293 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack (1983 ▶), 2165 Friedel pairs

Flack parameter: 0.000 (15)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Xtal3.6 (Hall et al., 1999 ▶), ORTEPII (Johnson, 1976 ▶), SHELXLE (Hübschle et al., 2011 ▶), Mercury (Macrae et al., 2006 ▶) and WinGX (Farrugia, 2012 ▶); software used to prepare material for publication: publCIF (Westrip, (2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813015638/lh5615sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015638/lh5615Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813015638/lh5615Isup3.cml

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

C23H28O8S	F(000) = 984
Mr = 464.51	Dx = 1.329 Mg m−3
Monoclinic, C2	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: C 2y	Cell parameters from 13737 reflections
a = 22.6192 (3) Å	θ = 4.0–76.2°
b = 5.5649 (1) Å	µ = 1.64 mm−1
c = 19.0631 (3) Å	T = 150 K
β = 104.696 (2)°	Blade, colourless
V = 2321.04 (6) Å3	0.29 × 0.06 × 0.02 mm
Z = 4

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	4672 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	4541 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.031
Detector resolution: 10.5861 pixels mm-1	θmax = 76.4°, θmin = 4.0°
ω scans	h = −28→28
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −7→6
Tmin = 0.628, Tmax = 1.000	l = −24→24
24544 measured reflections

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)] = 0.044	H-atom parameters constrained
wR(F2) = 0.127	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
S = 1.16	(Δ/σ)max = 0.001
4672 reflections	Δρmax = 0.48 e Å−3
293 parameters	Δρmin = −0.27 e Å−3
1 restraint	Absolute structure: Flack (1983), 2165 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.000 (15)

Experimental. Analysis: [α]D26 0.20° (c 0.2 in CHCl3); IR (KBr, cm-1): 3594-3205 (br, OH), 3095, 3046 (w, ArC-H), 2984, 2950, 2925, 2864 (st, alkyl C-H), 1369, 1178 (s, S=O); 1H NMR (CDCl3, 400 MHz, p.p.m.): 1.27, 1.46 [2 x 3H, 2 x s, C(CH3)2], 2.43 [3H, s, TsCH3], 3.49 [1H, d, JH3,H4 = 11.8 Hz, H3], 3.57 [1H, d, JH1,H1' = 10.1 Hz, H1], 3.76 [1H, d, JH1',H1 = 10.0 Hz, H1'], 4.05 [1H, dd, JH4,H3 = 11.5 Hz, JH4,H5 = 2.5 Hz, H4], 4.16 [1H, dd, JH6,H5 = 6.9 Hz, JH6,H6' = 10.6 Hz, H6], 4.30 [1H, dd, JH6',H5 = 4.9, JH6',H6 = 10.6 Hz, H6'], 4.36 [1H, s, OH], 4.40 [1H, ddd, JH5,H4 = 2.5 Hz, JH5,H6' = 4.7 Hz, JH5,H6 = 7.2 Hz, H5], 4.52 [1H, d, JCHAHB,CHAHB = 11.7 Hz, CHAHB (Bn)], 4.59 [1H, d, JCHAHB,CHAHB = 11.7 Hz, CHAHB (Bn)], 7.22-7.26 [2H, m, 2 x ArHs (Bn-o)], 7.30-7.37 [5H, m, 2 x ArHs (Ts) and 3 x ArHs (Bn-m,p)], 7.81 [2H, d, ArHs (Ts)]; 13C NMR (CDCl3, 100 MHz, p.p.m.): 21.7 [CH3 (Ts)], 26.1, 27.2 [2 x CH3], 68.1 [C6], 71.3 [C1], 74.2 [CH2(Bn)], 74.4 [C4], 79.8 [C5], 86.4 [C3], 112.8 [C2], 112.9 [Cq acetonide], 128.0 [2 x ArCs (Bn-o)], 128.2 [2 x ArCs (Ts)], 128.5 [1 x ArC (Bn-p)], 128.8, 129.9 [2 x ArCs (Bn-m) and 2 x ArCs (Ts)], 133.0 [Cq-CH3], 136.5 [Cq (Bn)], 144.9 [Cq-S]; HRMS (ESI+): found 487.13977 [M+Na]+ C23H28NaO8S, requires 487.13971. M.p.: 377-378K

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
S1	0.404262 (19)	0.50470 (8)	0.48560 (2)	0.02722 (14)
O1	0.44717 (7)	0.4027 (3)	0.17231 (8)	0.0355 (3)
O1'	0.34123 (8)	0.1296 (4)	0.09744 (8)	0.0438 (4)
O2	0.50981 (6)	0.0816 (3)	0.21233 (8)	0.0313 (3)
O3	0.39754 (6)	−0.1689 (3)	0.29897 (8)	0.0316 (3)
H3O	0.4000	−0.3170	0.2916	0.047*
O4	0.41584 (6)	0.3389 (2)	0.27843 (7)	0.0279 (3)
O5	0.43901 (6)	0.4404 (3)	0.42627 (7)	0.0289 (3)
O6	0.41714 (7)	0.7530 (3)	0.50128 (8)	0.0354 (3)
O7	0.41841 (7)	0.3306 (3)	0.54278 (7)	0.0345 (3)
C1	0.41496 (8)	0.2518 (4)	0.20750 (9)	0.0269 (4)
C1'	0.34827 (9)	0.2402 (5)	0.16634 (11)	0.0383 (5)
H1'A	0.3252	0.1477	0.1949	0.046*
H1'B	0.3312	0.4048	0.1596	0.046*
C2	0.45054 (8)	0.0140 (4)	0.21843 (9)	0.0259 (3)
H2	0.4311	−0.1123	0.1826	0.031*
C3	0.45313 (8)	−0.0559 (4)	0.29689 (10)	0.0270 (4)
H3	0.4895	−0.1575	0.3191	0.032*
C4	0.45641 (8)	0.1905 (3)	0.33235 (9)	0.0254 (4)
H4	0.4991	0.2542	0.3426	0.030*
C5	0.43459 (9)	0.1918 (4)	0.40058 (10)	0.0302 (4)
H5A	0.3918	0.1348	0.3904	0.036*
H5B	0.4605	0.0855	0.4376	0.036*
C6	0.32399 (13)	0.2890 (5)	0.03842 (12)	0.0436 (5)
H6A	0.3540	0.4216	0.0443	0.052*
H6B	0.2835	0.3594	0.0370	0.052*
C7	0.32113 (10)	0.1574 (5)	−0.03123 (11)	0.0365 (5)
C8	0.28553 (11)	0.2509 (6)	−0.09630 (12)	0.0459 (6)
H8	0.2630	0.3950	−0.0961	0.055*
C9	0.28292 (15)	0.1343 (7)	−0.16111 (13)	0.0602 (9)
H9	0.2589	0.1997	−0.2052	0.072*
C10	0.31489 (15)	−0.0766 (7)	−0.16223 (15)	0.0611 (9)
H10	0.3129	−0.1558	−0.2069	0.073*
C11	0.34979 (14)	−0.1721 (6)	−0.09822 (17)	0.0563 (7)
H11	0.3716	−0.3177	−0.0987	0.068*
C12	0.35291 (11)	−0.0536 (5)	−0.03250 (13)	0.0428 (5)
H12	0.3771	−0.1190	0.0115	0.051*
C13	0.50589 (9)	0.3003 (4)	0.17266 (11)	0.0313 (4)
C14	0.50694 (13)	0.2538 (6)	0.09465 (13)	0.0496 (6)
H14A	0.4735	0.1446	0.0721	0.074*
H14B	0.5461	0.1807	0.0934	0.074*
H14C	0.5019	0.4060	0.0679	0.074*
C15	0.55631 (12)	0.4642 (5)	0.21200 (15)	0.0481 (6)
H15A	0.5959	0.3946	0.2112	0.072*
H15B	0.5541	0.4834	0.2624	0.072*
H15C	0.5518	0.6215	0.1881	0.072*
C16	0.32657 (8)	0.4727 (4)	0.44051 (9)	0.0281 (4)
C17	0.29721 (10)	0.6518 (4)	0.39353 (11)	0.0324 (4)
H17	0.3195	0.7858	0.3828	0.039*
C18	0.23503 (10)	0.6319 (5)	0.36260 (11)	0.0355 (4)
H18	0.2147	0.7545	0.3308	0.043*
C19	0.20172 (9)	0.4365 (4)	0.37695 (10)	0.0329 (4)
C20	0.23236 (10)	0.2542 (4)	0.42171 (11)	0.0332 (4)
H20	0.2105	0.1161	0.4302	0.040*
C21	0.29487 (9)	0.2718 (4)	0.45432 (10)	0.0307 (4)
H21	0.3154	0.1482	0.4855	0.037*
C22	0.13348 (10)	0.4233 (6)	0.34609 (13)	0.0456 (6)
H22A	0.1234	0.4671	0.2946	0.068*
H22B	0.1133	0.5349	0.3723	0.068*
H22C	0.1194	0.2593	0.3513	0.068*

	U11	U22	U33	U12	U13	U23
S1	0.0334 (2)	0.0263 (3)	0.0226 (2)	−0.00197 (16)	0.00836 (15)	−0.00147 (16)
O1	0.0404 (7)	0.0297 (8)	0.0412 (7)	0.0075 (6)	0.0190 (6)	0.0082 (6)
O1'	0.0522 (9)	0.0409 (10)	0.0313 (7)	0.0102 (7)	−0.0020 (6)	−0.0056 (7)
O2	0.0278 (6)	0.0284 (8)	0.0400 (7)	0.0039 (5)	0.0129 (5)	0.0037 (6)
O3	0.0356 (7)	0.0208 (7)	0.0417 (7)	−0.0025 (5)	0.0161 (6)	−0.0016 (5)
O4	0.0374 (7)	0.0213 (7)	0.0243 (6)	0.0056 (5)	0.0067 (5)	−0.0019 (5)
O5	0.0347 (6)	0.0267 (8)	0.0275 (6)	−0.0050 (5)	0.0121 (5)	−0.0029 (5)
O6	0.0441 (7)	0.0297 (8)	0.0337 (6)	−0.0060 (6)	0.0123 (6)	−0.0082 (6)
O7	0.0395 (7)	0.0384 (9)	0.0246 (6)	−0.0005 (6)	0.0061 (5)	0.0043 (6)
C1	0.0299 (8)	0.0266 (10)	0.0246 (8)	0.0038 (7)	0.0075 (7)	−0.0011 (7)
C1'	0.0326 (9)	0.0459 (13)	0.0328 (9)	0.0097 (9)	0.0017 (8)	−0.0080 (9)
C2	0.0265 (7)	0.0232 (9)	0.0287 (8)	0.0022 (7)	0.0083 (6)	−0.0027 (7)
C3	0.0288 (8)	0.0225 (10)	0.0305 (8)	0.0028 (7)	0.0090 (6)	0.0013 (7)
C4	0.0292 (8)	0.0217 (9)	0.0249 (8)	0.0005 (7)	0.0059 (6)	−0.0003 (7)
C5	0.0380 (9)	0.0256 (10)	0.0291 (8)	−0.0023 (7)	0.0125 (7)	−0.0020 (7)
C6	0.0591 (13)	0.0344 (13)	0.0342 (10)	0.0076 (11)	0.0061 (9)	0.0002 (9)
C7	0.0381 (10)	0.0383 (12)	0.0337 (10)	−0.0063 (9)	0.0102 (8)	−0.0017 (9)
C8	0.0475 (12)	0.0535 (16)	0.0346 (10)	−0.0093 (11)	0.0065 (9)	0.0032 (10)
C9	0.0682 (17)	0.081 (2)	0.0319 (11)	−0.0281 (17)	0.0130 (11)	−0.0017 (13)
C10	0.0691 (17)	0.079 (2)	0.0430 (12)	−0.0328 (17)	0.0275 (12)	−0.0210 (14)
C11	0.0620 (15)	0.0521 (16)	0.0651 (16)	−0.0171 (13)	0.0350 (13)	−0.0228 (14)
C12	0.0424 (11)	0.0429 (15)	0.0447 (11)	−0.0075 (10)	0.0143 (9)	−0.0080 (10)
C13	0.0350 (9)	0.0299 (11)	0.0327 (9)	0.0028 (8)	0.0153 (7)	0.0020 (8)
C14	0.0604 (14)	0.0579 (17)	0.0359 (11)	0.0145 (13)	0.0223 (10)	0.0010 (11)
C15	0.0476 (12)	0.0399 (15)	0.0595 (14)	−0.0129 (10)	0.0182 (10)	−0.0004 (11)
C16	0.0327 (8)	0.0286 (11)	0.0247 (7)	0.0014 (7)	0.0105 (6)	−0.0002 (7)
C17	0.0405 (10)	0.0279 (11)	0.0305 (8)	−0.0002 (8)	0.0122 (7)	0.0037 (8)
C18	0.0419 (10)	0.0355 (12)	0.0287 (9)	0.0067 (9)	0.0081 (7)	0.0033 (8)
C19	0.0347 (9)	0.0385 (12)	0.0273 (8)	0.0014 (8)	0.0113 (7)	−0.0059 (8)
C20	0.0391 (10)	0.0307 (11)	0.0319 (9)	−0.0055 (8)	0.0127 (7)	−0.0024 (8)
C21	0.0385 (9)	0.0284 (11)	0.0264 (8)	−0.0018 (8)	0.0104 (7)	0.0022 (7)
C22	0.0367 (10)	0.0585 (16)	0.0400 (11)	−0.0008 (10)	0.0069 (8)	−0.0096 (11)

S1—O6	1.4278 (17)	C8—C9	1.384 (4)
S1—O7	1.4326 (16)	C8—H8	0.9500
S1—O5	1.5736 (13)	C9—C10	1.382 (6)
S1—C16	1.7585 (19)	C9—H9	0.9500
O1—C1	1.391 (2)	C10—C11	1.380 (5)
O1—C13	1.444 (2)	C10—H10	0.9500
O1'—C6	1.408 (3)	C11—C12	1.402 (4)
O1'—C1'	1.422 (3)	C11—H11	0.9500
O2—C13	1.424 (3)	C12—H12	0.9500
O2—C2	1.425 (2)	C13—C15	1.504 (3)
O3—C3	1.415 (2)	C13—C14	1.516 (3)
O3—H3O	0.8400	C14—H14A	0.9800
O4—C1	1.432 (2)	C14—H14B	0.9800
O4—C4	1.450 (2)	C14—H14C	0.9800
O5—C5	1.463 (2)	C15—H15A	0.9800
C1—C1'	1.515 (3)	C15—H15B	0.9800
C1—C2	1.535 (3)	C15—H15C	0.9800
C1'—H1'A	0.9900	C16—C21	1.389 (3)
C1'—H1'B	0.9900	C16—C17	1.391 (3)
C2—C3	1.532 (2)	C17—C18	1.385 (3)
C2—H2	1.0000	C17—H17	0.9500
C3—C4	1.522 (3)	C18—C19	1.389 (3)
C3—H3	1.0000	C18—H18	0.9500
C4—C5	1.504 (2)	C19—C20	1.392 (3)
C4—H4	1.0000	C19—C22	1.508 (3)
C5—H5A	0.9900	C20—C21	1.396 (3)
C5—H5B	0.9900	C20—H20	0.9500
C6—C7	1.503 (3)	C21—H21	0.9500
C6—H6A	0.9900	C22—H22A	0.9800
C6—H6B	0.9900	C22—H22B	0.9800
C7—C12	1.380 (4)	C22—H22C	0.9800
C7—C8	1.397 (3)
O6—S1—O7	120.05 (10)	C9—C8—C7	120.2 (3)
O6—S1—O5	104.95 (8)	C9—C8—H8	119.9
O7—S1—O5	109.71 (9)	C7—C8—H8	119.9
O6—S1—C16	109.01 (10)	C10—C9—C8	120.6 (3)
O7—S1—C16	107.82 (9)	C10—C9—H9	119.7
O5—S1—C16	104.19 (8)	C8—C9—H9	119.7
C1—O1—C13	110.70 (15)	C11—C10—C9	119.8 (3)
C6—O1'—C1'	114.1 (2)	C11—C10—H10	120.1
C13—O2—C2	109.61 (14)	C9—C10—H10	120.1
C3—O3—H3O	109.5	C10—C11—C12	119.8 (3)
C1—O4—C4	109.34 (14)	C10—C11—H11	120.1
C5—O5—S1	116.84 (11)	C12—C11—H11	120.1
O1—C1—O4	111.57 (16)	C7—C12—C11	120.5 (3)
O1—C1—C1'	110.53 (16)	C7—C12—H12	119.7
O4—C1—C1'	106.07 (14)	C11—C12—H12	119.7
O1—C1—C2	105.38 (14)	O2—C13—O1	105.86 (14)
O4—C1—C2	106.41 (14)	O2—C13—C15	108.44 (18)
C1'—C1—C2	116.89 (18)	O1—C13—C15	110.09 (19)
O1'—C1'—C1	111.11 (16)	O2—C13—C14	111.1 (2)
O1'—C1'—H1'A	109.4	O1—C13—C14	107.84 (18)
C1—C1'—H1'A	109.4	C15—C13—C14	113.2 (2)
O1'—C1'—H1'B	109.4	C13—C14—H14A	109.5
C1—C1'—H1'B	109.4	C13—C14—H14B	109.5
H1'A—C1'—H1'B	108.0	H14A—C14—H14B	109.5
O2—C2—C3	110.05 (14)	C13—C14—H14C	109.5
O2—C2—C1	103.47 (16)	H14A—C14—H14C	109.5
C3—C2—C1	103.91 (14)	H14B—C14—H14C	109.5
O2—C2—H2	112.9	C13—C15—H15A	109.5
C3—C2—H2	112.9	C13—C15—H15B	109.5
C1—C2—H2	112.9	H15A—C15—H15B	109.5
O3—C3—C4	109.35 (14)	C13—C15—H15C	109.5
O3—C3—C2	109.03 (15)	H15A—C15—H15C	109.5
C4—C3—C2	100.96 (15)	H15B—C15—H15C	109.5
O3—C3—H3	112.3	C21—C16—C17	120.91 (18)
C4—C3—H3	112.3	C21—C16—S1	119.27 (15)
C2—C3—H3	112.3	C17—C16—S1	119.78 (16)
O4—C4—C5	108.83 (15)	C18—C17—C16	119.0 (2)
O4—C4—C3	104.34 (13)	C18—C17—H17	120.5
C5—C4—C3	113.49 (16)	C16—C17—H17	120.5
O4—C4—H4	110.0	C17—C18—C19	121.5 (2)
C5—C4—H4	110.0	C17—C18—H18	119.3
C3—C4—H4	110.0	C19—C18—H18	119.3
O5—C5—C4	106.54 (15)	C18—C19—C20	118.72 (19)
O5—C5—H5A	110.4	C18—C19—C22	120.9 (2)
C4—C5—H5A	110.4	C20—C19—C22	120.3 (2)
O5—C5—H5B	110.4	C19—C20—C21	120.8 (2)
C4—C5—H5B	110.4	C19—C20—H20	119.6
H5A—C5—H5B	108.6	C21—C20—H20	119.6
O1'—C6—C7	109.9 (2)	C16—C21—C20	119.0 (2)
O1'—C6—H6A	109.7	C16—C21—H21	120.5
C7—C6—H6A	109.7	C20—C21—H21	120.5
O1'—C6—H6B	109.7	C19—C22—H22A	109.5
C7—C6—H6B	109.7	C19—C22—H22B	109.5
H6A—C6—H6B	108.2	H22A—C22—H22B	109.5
C12—C7—C8	119.1 (2)	C19—C22—H22C	109.5
C12—C7—C6	121.6 (2)	H22A—C22—H22C	109.5
C8—C7—C6	119.3 (2)	H22B—C22—H22C	109.5
O6—S1—O5—C5	178.98 (14)	C1'—O1'—C6—C7	176.95 (18)
O7—S1—O5—C5	48.72 (15)	O1'—C6—C7—C12	−22.5 (3)
C16—S1—O5—C5	−66.49 (15)	O1'—C6—C7—C8	157.6 (2)
C13—O1—C1—O4	103.77 (18)	C12—C7—C8—C9	−0.8 (4)
C13—O1—C1—C1'	−138.45 (17)	C6—C7—C8—C9	179.1 (2)
C13—O1—C1—C2	−11.3 (2)	C7—C8—C9—C10	0.6 (4)
C4—O4—C1—O1	−106.51 (17)	C8—C9—C10—C11	0.0 (4)
C4—O4—C1—C1'	133.06 (17)	C9—C10—C11—C12	−0.4 (4)
C4—O4—C1—C2	7.94 (19)	C8—C7—C12—C11	0.3 (4)
C6—O1'—C1'—C1	−109.0 (2)	C6—C7—C12—C11	−179.6 (2)
O1—C1—C1'—O1'	65.6 (2)	C10—C11—C12—C7	0.3 (4)
O4—C1—C1'—O1'	−173.29 (19)	C2—O2—C13—O1	16.1 (2)
C2—C1—C1'—O1'	−54.9 (3)	C2—O2—C13—C15	134.23 (18)
C13—O2—C2—C3	−132.90 (17)	C2—O2—C13—C14	−100.7 (2)
C13—O2—C2—C1	−22.38 (18)	C1—O1—C13—O2	−2.2 (2)
O1—C1—C2—O2	20.33 (18)	C1—O1—C13—C15	−119.2 (2)
O4—C1—C2—O2	−98.26 (16)	C1—O1—C13—C14	116.9 (2)
C1'—C1—C2—O2	143.52 (16)	O6—S1—C16—C21	−144.04 (16)
O1—C1—C2—C3	135.33 (15)	O7—S1—C16—C21	−12.19 (18)
O4—C1—C2—C3	16.74 (18)	O5—S1—C16—C21	104.34 (15)
C1'—C1—C2—C3	−101.48 (18)	O6—S1—C16—C17	33.81 (17)
O2—C2—C3—O3	−167.94 (15)	O7—S1—C16—C17	165.66 (15)
C1—C2—C3—O3	81.83 (18)	O5—S1—C16—C17	−77.81 (17)
O2—C2—C3—C4	76.98 (18)	C21—C16—C17—C18	2.5 (3)
C1—C2—C3—C4	−33.25 (16)	S1—C16—C17—C18	−175.36 (15)
C1—O4—C4—C5	−151.21 (16)	C16—C17—C18—C19	−0.6 (3)
C1—O4—C4—C3	−29.75 (18)	C17—C18—C19—C20	−2.0 (3)
O3—C3—C4—O4	−76.32 (17)	C17—C18—C19—C22	176.73 (19)
C2—C3—C4—O4	38.51 (16)	C18—C19—C20—C21	2.9 (3)
O3—C3—C4—C5	42.0 (2)	C22—C19—C20—C21	−175.87 (18)
C2—C3—C4—C5	156.83 (15)	C17—C16—C21—C20	−1.6 (3)
S1—O5—C5—C4	165.40 (12)	S1—C16—C21—C20	176.22 (14)
O4—C4—C5—O5	−62.69 (18)	C19—C20—C21—C16	−1.1 (3)
C3—C4—C5—O5	−178.38 (15)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O4i	0.84	1.98	2.812 (2)	174

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O4i	0.84	1.98	2.812 (2)	174

Symmetry code: (i) .