Comparison of the two anomers of methyl 2-(N-benzyl­amino)-2,3-di­deoxy-4,6-O-phenyl­methyl­ene-3-C-phenyl­sulfonyl-D-gluco­pyran­oside

The title compounds, the [alpha] and [beta] anomers of methyl 2-(N-benzyl­amino)-2,3-di­deoxy-4,6-O-phenyl­methyl­ene-3-C-phenyl­sulfonyl-D-gluco­pyran­oside, C₂₇H₂₉NO₆S, belong to the class of deoxy­amino-­sugars prepared by the addition of amines at C2. The endocyclic bond lengths of the pyran­ose ring in the [alpha] anomer are shorter than the corresponding bonds in the [beta] anomer. The pyran­ose ring is in the chair form in the former, while it is in the boat form in the latter. These observed differences could be attributed to the C2 substitution of a bulky group. The phenyl­sulfonyl and benzyl­amino groups are in equatorial positions in the [alpha] anomer, while the benzyl­amino group is axial in the [beta] anomer.

S1. Comment

Aminosugars in general are one of the most important classes of carbohydrates. The C—N equatorial bonds at the C2 position of carbohydrates play a significant role because naturally occurring aminosugars such as D-glucosamine, D-galactosamine, D-lividosamine, etc. have their C—N bonds at C2 in equatorial configuration. Not many synthetic routes are available for the introduction of N-monoalkylated and N-dialkylated amines to C2 carbon of pyranoses in equatorial configurations. As part of an ongoing programme on the development of novel synthetic routes for the preparation of new classes of deoxyaminosugars, we have been studying the stereoselective addition of various amines to phenylsulfonyl-modified carbohydrates. In this context we have determined the structure of the α, (I), and β, (II), anomers of a phenylsulfonyl-modified monosaccharide with amino substitution at C2. \sch

When the geometry of the pyranose rings in the two molecules is compared, the average endocyclic C—C bond length is 1.528 Å in α and 1.537 Å in β. The value of the former is closer to whereas the latter is higher than the average values reported for glucopyranose rings (Jeffrey, 1990). The average of the endocyclic bond angles around carbon atoms is 111.1 and 111.6°, respectively. These values are higher than the reported average (Jeffrey, 1990). The bond angle around O5 in β anomer is wider than that in α.

The pyranose-dioxane double ring system in α anomer is in chair conformation. The dioxane ring alone has chair form in β anomer while the pyranose takes boat form. The conformation of pyranoses are thus symbolized as ⁴C₁ in α anomer and ^1,4B in β (Collins & Ferrier, 1995). In the α anomer, the two bulky groups of phenylsulfonyl and benzylamino attached to the pyranose ring as well as the phenyl group attached to dioxane are all equatorially positioned with respect to the double ring carbohydrate system, while the benzoylamino group is axial in β.

The main conformational difference between the pyranose rings in the two anomers corresponds to C1 puckering. The observed difference, the chair conformation of the pyranose in α form while its boat conformation in β, could presumably be the result of C2 substitution. In the β anomer, the observed boat conformation of the pyranose ring causes the benzylamino and the glycosidic O-methyl groups present in adjucent ring carbons to orient away from each other. In a chair conformation of the pyranose ring these groups would have come sterically more closer. Another difference between the anomers is in the disposition of phenyl ring of the phenylsulfonyl. This phenyl ring is positioned away from C2 benzylamino in the β anomer compared to its position in the α anomer. Among the three planar phenyl rings, the one of benzylamino is almost orthogonal to the other two in both the structures. Whereas, the phenyl rings of phenylmethylene and phenylsulfonyl makes 26.6 (2) and 63.5 (2)° to each other in the α and β anomers, respectively.

In the case of hexapyranoses, the presence of a hydroxyl group at C4 is expected to forbid the orientation of the primary alcohol group C6—OH in tg conformation (Jeffrey, 1990). However, in both the molecules reported here this group is in tg conformation, as a result of dioxan ring formation.

The C—O bond shortening at C1 of the pyranose and the preferred gauche conformations about the glycosidic bond (exo-anomeric effect) are known in carbohydrates (Perez & Marchessault, 1978). The structure of the α anomer reported here belongs to gauche-gauche class which is the allowed one for α anomers. The trans-gauche form is favourable in β anomers (Norrestam et al., 1981). Nevertheless, according to glycosodic torsion angles (Table 1), the β anomer has gauche-gauche conformation. Presumably, this not so common form of β anomers is found in this structure due to the boat form instead of the more common chair form of pyranose ring.

The crystal structures are stabilized by the stacking and hydrophobic interactions of phenyl rings. In the β anomer there is an intermolecular hydrogen bond involving amino nitrogen with sulfone oxygen O3 of the translated molecule along c. In the α anomer this nitrogen is involved in a weak intramolecular hydrogen bond with oxygen (O1) of the glycosidic O-methyl group.

S2. Experimental

Methyl 2,3-dideoxy-4,6-O-(phenylmethelene)-3 C– phenylsulfonyl-α-D-erythro-hex-2-enopyranoside and the corresponding -β-D-erythro-hex-2-enopyranoside were reacted separately with benzylamine at elevated temperatures (Ravindran et al., 2000). The desired aminosugars were recrystallized from methanol.

S3. Refinement

Hydrogen atoms were located using geometrical considerations and a difference Fourier map. They were treated as riding on the heavier atoms to which they are attached.

Computing details

Data collection: CAD-4-PC Software (Enraf-Nonius, 1993) for (Ia); Molecular Diffractometer Control Software (Molecular Structure Corporation, 1991) for (Ib). Cell refinement: CAD-4-PC Software for (Ia); Molecular Diffractometer Control Software for (Ib). Data reduction: NRCVAX DATRD2 (Gabe et al., 1989) for (Ia); Molecular Diffractometer Control Software for (Ib). For both compounds, program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEPII (Johnson, 1976) and PLUTO (Motherwell \& Clegg, 1978).

Figures

	Fig. 1. A perspective view of (I). Displacement ellipsoids are drawn at 50% probability level in this and next figure. H atoms are omitted for clarity.
	Fig. 2. A perspective view of (II).

(Ia) Methyl 2-N-Benzylamino −2,3-dideoxy −4,6-O-(phenyl methylene)- 3-C-phenylsulfonyl a\-D-glucopyranoside

Crystal data

C27H29NO6S	F(000) = 524
Mr = 495.57	Dx = 1.312 Mg m^−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54180 Å
a = 10.418 (2) Å	Cell parameters from 25 reflections
b = 8.880 (6) Å	θ = 10.0–30.0°
c = 13.560 (2) Å	µ = 1.50 mm^−1
β = 91.36 (1)°	T = 293 K
V = 1254.1 (9) Å^3	Needle, colourless
Z = 2	0.80 × 0.31 × 0.25 mm

Data collection

Enraf Nonius CAD4 diffractometer	2563 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 75.6°, θmin = 3.3°
ω–2θ scans	h = 0→13
Absorption correction: ψ scan North et al (1968)	k = 0→10
Tmin = 0.668, Tmax = 0.687	l = −16→16
2810 measured reflections	3 standard reflections every 60 min
2667 independent reflections	intensity decay: 0.1%

Refinement

Refinement on F^2	Calculated w = 1/[s^2(Fo^2) + ( 0.062P)^2 + 0.1489P] where P = (Fo^2 + 2Fc^2)/3
Least-squares matrix: full	(Δ/σ)max = 0.002
R[F^2 > 2σ(F^2)] = 0.033	Δρmax = 0.25 e Å^−3
wR(F^2) = 0.090	Δρmin = −0.34 e Å^−3
S = 1.06	Extinction correction: SHELXL93 (Sheldrick, 1993), Fc^*=kFc[1+0.001xFc^2l^3/sin(2q)]^-1/4
2667 reflections	Extinction coefficient: 0.0119 (8)
318 parameters	Absolute structure: Flack (1983)
1 restraint	Absolute structure parameter: 0.00 (2)
Only H-atom coordinates refined

Special details

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 on F² for all reflections except for 0 with very negative F² or flagged for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R_factor_obs 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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.71724 (5)	0.34878 (7)	0.14482 (4)	0.0410 (2)
O3	0.8189 (2)	0.3379 (3)	0.07602 (13)	0.0586 (5)
O2	0.6880 (2)	0.2195 (2)	0.2031 (2)	0.0565 (5)
O5	0.3539 (2)	0.2914 (2)	−0.03851 (12)	0.0431 (4)
C1	0.3316 (2)	0.3398 (3)	0.0592 (2)	0.0404 (5)
H1	0.2683	0.2720	0.0878	0.049*
O1	0.2819 (2)	0.4855 (2)	0.06068 (14)	0.0485 (4)
C7	0.1522 (3)	0.4935 (6)	0.0228 (4)	0.0845 (12)
H7A	0.1205	0.5943	0.0299	0.127*
H7B	0.0993	0.4255	0.0590	0.127*
H7C	0.1500	0.4660	−0.0457	0.127*
C2	0.4535 (2)	0.3364 (3)	0.12525 (15)	0.0374 (4)
H2	0.4732	0.2303	0.13850	0.045*
C3	0.5714 (2)	0.4046 (3)	0.0760 (2)	0.0347 (4)
H3	0.5643	0.5146	0.0771	0.042*
C4	0.5784 (2)	0.3525 (3)	−0.03071 (14)	0.0345 (4)
H4	0.5999	0.2451	−0.03307	0.041*
O4	0.67138 (15)	0.4379 (2)	−0.08186 (11)	0.0365 (3)
C8	0.6798 (2)	0.3848 (3)	−0.1792 (2)	0.0382 (5)
H8	0.6968	0.2763	−0.1784	0.046*
O6	0.5652 (2)	0.4132 (2)	−0.23290 (12)	0.0457 (4)
C6	0.4588 (2)	0.3367 (4)	−0.1907 (2)	0.0468 (6)
H6A	0.4703	0.2287	−0.1964	0.056*
H6B	0.3800	0.3641	−0.2258	0.056*
C5	0.4499 (2)	0.3802 (3)	−0.0827 (2)	0.0369 (5)
H5	0.4273	0.4870	−0.0776	0.044*
C9	0.7880 (2)	0.4648 (3)	−0.2279 (2)	0.0399 (5)
C10	0.8822 (2)	0.5347 (4)	−0.1716 (2)	0.0489 (6)
H10	0.8799	0.5299	−0.1031	0.059*
C11	0.9798 (3)	0.6116 (5)	−0.2161 (2)	0.0645 (8)
H11	1.0415	0.6612	−0.1775	0.077*
C12	0.9865 (3)	0.6155 (5)	−0.3166 (3)	0.0715 (10)
H12	1.0524	0.6681	−0.3464	0.086*
C13	0.8960 (3)	0.5415 (5)	−0.3735 (2)	0.0710 (10)
H13	0.9021	0.5412	−0.4418	0.085*
C14	0.7960 (3)	0.4678 (4)	−0.3296 (2)	0.0550 (7)
H14	0.7336	0.4199	−0.3684	0.066*
C15	0.7586 (2)	0.4968 (3)	0.2260 (2)	0.0451 (6)
C16	0.7076 (3)	0.5024 (4)	0.3182 (2)	0.0573 (7)
H16	0.6487	0.4302	0.3376	0.069*
C17	0.7448 (4)	0.6163 (6)	0.3821 (3)	0.0757 (11)
H17	0.7101	0.6213	0.4445	0.091*
C18	0.8311 (4)	0.7201 (5)	0.3545 (3)	0.0808 (11)
H18	0.8560	0.7958	0.3984	0.097*
C19	0.8819 (4)	0.7156 (5)	0.2637 (4)	0.0822 (11)
H19	0.9415	0.7879	0.2457	0.099*
C20	0.8455 (3)	0.6028 (4)	0.1964 (3)	0.0633 (8)
H20	0.8792	0.5998	0.1336	0.076*
N1	0.4354 (2)	0.4086 (3)	0.22024 (14)	0.0437 (5)
H1N1	0.4669	0.4956	0.23448	0.052*
C21	0.3596 (3)	0.3222 (4)	0.2895 (2)	0.0628 (8)
H21A	0.4041	0.2296	0.3066	0.075*
H21B	0.2774	0.2961	0.2590	0.075*
C22	0.3385 (3)	0.4128 (4)	0.3810 (2)	0.0513 (6)
C23	0.2379 (3)	0.5113 (5)	0.3856 (2)	0.0740 (10)
H23	0.1809	0.5200	0.3320	0.089*
C24	0.2196 (4)	0.5977 (6)	0.4683 (3)	0.0893 (13)
H24	0.1507	0.6642	0.4704	0.107*
C25	0.3031 (5)	0.5855 (6)	0.5474 (3)	0.0879 (14)
H25	0.2906	0.6437	0.6034	0.105*
C26	0.4032 (4)	0.4896 (6)	0.5445 (2)	0.0788 (12)
H26	0.4605	0.4831	0.5981	0.095*
C27	0.4213 (3)	0.4004 (5)	0.4618 (2)	0.0649 (9)
H27	0.4890	0.3323	0.4607	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0466 (3)	0.0358 (3)	0.0405 (3)	0.0081 (2)	−0.0038 (2)	0.0002 (2)
O3	0.0510 (9)	0.0735 (15)	0.0514 (9)	0.0202 (11)	−0.0002 (7)	−0.0052 (11)
O2	0.0724 (12)	0.0349 (10)	0.0614 (11)	0.0039 (9)	−0.0125 (9)	0.0115 (9)
O5	0.0484 (9)	0.0371 (9)	0.0439 (8)	−0.0139 (7)	0.0001 (7)	0.0012 (7)
C1	0.0448 (10)	0.0315 (12)	0.0452 (11)	−0.0045 (11)	0.0050 (8)	0.0047 (11)
O1	0.0438 (8)	0.0405 (11)	0.0614 (10)	0.0072 (8)	0.0050 (8)	0.0044 (8)
C7	0.0465 (15)	0.080 (3)	0.126 (3)	0.009 (2)	−0.007 (2)	0.027 (3)
C2	0.0496 (11)	0.0245 (11)	0.0382 (10)	−0.0006 (10)	0.0017 (8)	0.0003 (9)
C3	0.0411 (10)	0.0265 (11)	0.0366 (10)	0.0013 (8)	0.0011 (8)	−0.0009 (8)
C4	0.0431 (9)	0.0239 (10)	0.0366 (9)	−0.0033 (10)	0.0014 (7)	−0.0001 (9)
O4	0.0422 (7)	0.0306 (9)	0.0368 (7)	−0.0047 (6)	0.0015 (6)	−0.0021 (6)
C8	0.0466 (11)	0.0327 (14)	0.0352 (9)	−0.0002 (9)	−0.0009 (8)	−0.0032 (8)
O6	0.0452 (8)	0.0521 (11)	0.0395 (8)	−0.0078 (8)	−0.0030 (6)	0.0061 (8)
C6	0.0488 (11)	0.050 (2)	0.0412 (11)	−0.0146 (12)	−0.0024 (9)	−0.0013 (12)
C5	0.0412 (10)	0.0285 (13)	0.0410 (10)	−0.0061 (8)	−0.0006 (8)	0.0026 (8)
C9	0.0419 (11)	0.0352 (13)	0.0427 (11)	0.0034 (10)	0.0045 (9)	−0.0012 (10)
C10	0.0450 (11)	0.055 (2)	0.0468 (12)	−0.0030 (12)	0.0020 (10)	−0.0032 (12)
C11	0.0508 (14)	0.073 (2)	0.070 (2)	−0.017 (2)	0.0053 (13)	−0.003 (2)
C12	0.055 (2)	0.088 (3)	0.073 (2)	−0.012 (2)	0.0177 (14)	0.014 (2)
C13	0.063 (2)	0.102 (3)	0.0491 (14)	0.001 (2)	0.0138 (12)	0.011 (2)
C14	0.0523 (13)	0.071 (2)	0.0421 (12)	−0.0010 (14)	0.0045 (10)	−0.0030 (13)
C15	0.0477 (12)	0.0406 (15)	0.0464 (12)	0.0050 (10)	−0.0104 (10)	0.0021 (10)
C16	0.0638 (15)	0.061 (2)	0.0471 (13)	0.0041 (14)	−0.0063 (11)	−0.0067 (13)
C17	0.079 (2)	0.086 (3)	0.062 (2)	0.011 (2)	−0.017 (2)	−0.026 (2)
C18	0.086 (2)	0.063 (2)	0.092 (3)	0.005 (2)	−0.029 (2)	−0.027 (2)
C19	0.073 (2)	0.058 (2)	0.114 (3)	−0.016 (2)	−0.022 (2)	−0.002 (2)
C20	0.059 (2)	0.056 (2)	0.074 (2)	−0.0106 (14)	−0.0039 (14)	0.005 (2)
N1	0.0570 (11)	0.0326 (11)	0.0418 (10)	−0.0090 (9)	0.0100 (8)	−0.0055 (9)
C21	0.091 (2)	0.049 (2)	0.0487 (13)	−0.021 (2)	0.0229 (13)	−0.0054 (13)
C22	0.0637 (15)	0.047 (2)	0.0439 (12)	−0.0096 (13)	0.0144 (11)	−0.0005 (12)
C23	0.076 (2)	0.087 (3)	0.059 (2)	0.015 (2)	0.0115 (15)	0.004 (2)
C24	0.104 (3)	0.078 (3)	0.088 (3)	0.016 (2)	0.038 (2)	−0.003 (2)
C25	0.120 (3)	0.084 (3)	0.062 (2)	−0.029 (3)	0.037 (2)	−0.026 (2)
C26	0.081 (2)	0.108 (3)	0.0483 (15)	−0.032 (2)	0.0065 (15)	−0.001 (2)
C27	0.068 (2)	0.073 (2)	0.0537 (15)	−0.004 (2)	0.0099 (13)	0.0103 (15)

Geometric parameters (Å, º)

S1—O2	1.431 (2)	C11—C12	1.367 (5)
S1—O3	1.431 (2)	C11—H11	0.93
S1—C15	1.761 (3)	C12—C13	1.372 (5)
S1—C3	1.832 (2)	C12—H12	0.93
O5—C1	1.417 (3)	C13—C14	1.377 (4)
O5—C5	1.418 (3)	C13—H13	0.93
C1—O1	1.394 (4)	C14—H14	0.93
C1—C2	1.537 (3)	C15—C16	1.371 (4)
C1—H1	0.98	C15—C20	1.372 (4)
O1—C7	1.436 (3)	C16—C17	1.381 (5)
C7—H7A	0.96	C16—H16	0.93
C7—H7B	0.96	C17—C18	1.347 (6)
C7—H7C	0.96	C17—H17	0.93
C2—N1	1.455 (3)	C18—C19	1.352 (6)
C2—C3	1.537 (3)	C18—H18	0.93
C2—H2	0.98	C19—C20	1.401 (5)
C3—C4	1.522 (3)	C19—H19	0.93
C3—H3	0.98	C20—H20	0.93
C4—O4	1.424 (3)	N1—C21	1.459 (3)
C4—C5	1.518 (3)	N1—H1N1	0.86
C4—H4	0.98	C21—C22	1.499 (4)
O4—C8	1.407 (3)	C21—H21A	0.97
C8—O6	1.406 (3)	C21—H21B	0.97
C8—C9	1.499 (3)	C22—C23	1.368 (5)
C8—H8	0.98	C22—C27	1.383 (4)
O6—C6	1.431 (3)	C23—C24	1.376 (6)
C6—C5	1.518 (3)	C23—H23	0.93
C6—H6A	0.97	C24—C25	1.370 (6)
C6—H6B	0.97	C24—H24	0.93
C5—H5	0.98	C25—C26	1.348 (7)
C9—C10	1.378 (4)	C25—H25	0.93
C9—C14	1.383 (3)	C26—C27	1.391 (5)
C10—C11	1.376 (4)	C26—H26	0.93
C10—H10	0.93	C27—H27	0.93
O2—S1—O3	118.43 (15)	C11—C10—C9	120.3 (3)
O2—S1—C15	107.84 (13)	C11—C10—H10	119.8 (2)
O3—S1—C15	106.49 (13)	C9—C10—H10	119.84 (14)
O2—S1—C3	108.29 (12)	C12—C11—C10	120.4 (3)
O3—S1—C3	107.66 (10)	C12—C11—H11	119.8 (2)
C15—S1—C3	107.70 (11)	C10—C11—H11	119.8 (2)
C1—O5—C5	111.1 (2)	C11—C12—C13	119.8 (3)
O1—C1—O5	111.4 (2)	C11—C12—H12	120.1 (2)
O1—C1—C2	108.2 (2)	C13—C12—H12	120.1 (2)
O5—C1—C2	112.8 (2)	C12—C13—C14	120.1 (3)
O1—C1—H1	108.12 (12)	C12—C13—H13	120.0 (2)
O5—C1—H1	108.12 (13)	C14—C13—H13	120.0 (2)
C2—C1—H1	108.12 (12)	C13—C14—C9	120.3 (3)
C1—O1—C7	112.8 (3)	C13—C14—H14	119.9 (2)
O1—C7—H7A	109.5 (2)	C9—C14—H14	119.9 (2)
O1—C7—H7B	109.5 (2)	C16—C15—C20	120.9 (3)
H7A—C7—H7B	109.5	C16—C15—S1	120.2 (2)
O1—C7—H7C	109.5 (2)	C20—C15—S1	118.9 (2)
H7A—C7—H7C	109.5	C15—C16—C17	119.3 (3)
H7B—C7—H7C	109.5	C15—C16—H16	120.4 (2)
N1—C2—C3	109.5 (2)	C17—C16—H16	120.4 (2)
N1—C2—C1	112.6 (2)	C18—C17—C16	120.4 (4)
C3—C2—C1	113.4 (2)	C18—C17—H17	119.8 (2)
N1—C2—H2	107.01 (14)	C16—C17—H17	119.8 (2)
C3—C2—H2	107.01 (14)	C17—C18—C19	120.7 (4)
C1—C2—H2	107.01 (15)	C17—C18—H18	119.7 (2)
C4—C3—C2	110.5 (2)	C19—C18—H18	119.7 (2)
C4—C3—S1	110.17 (15)	C18—C19—C20	120.6 (4)
C2—C3—S1	109.5 (2)	C18—C19—H19	119.7 (2)
C4—C3—H3	108.89 (14)	C20—C19—H19	119.7 (2)
C2—C3—H3	108.89 (14)	C15—C20—C19	118.1 (3)
S1—C3—H3	108.89 (8)	C15—C20—H20	121.0 (2)
O4—C4—C5	106.8 (2)	C19—C20—H20	121.0 (2)
O4—C4—C3	110.5 (2)	C2—N1—C21	114.9 (2)
C5—C4—C3	109.4 (2)	C2—N1—H1N1	122.54 (13)
O4—C4—H4	110.04 (13)	C21—N1—H1N1	122.54 (15)
C5—C4—H4	110.04 (13)	N1—C21—C22	110.0 (2)
C3—C4—H4	110.04 (14)	N1—C21—H21A	109.7 (2)
C8—O4—C4	109.7 (2)	C22—C21—H21A	109.7 (2)
O6—C8—O4	110.8 (2)	N1—C21—H21B	109.7 (2)
O6—C8—C9	109.0 (2)	C22—C21—H21B	109.7 (2)
O4—C8—C9	108.6 (2)	H21A—C21—H21B	108.2
O6—C8—H8	109.49 (13)	C23—C22—C27	118.6 (3)
O4—C8—H8	109.49 (12)	C23—C22—C21	120.6 (3)
C9—C8—H8	109.49 (13)	C27—C22—C21	120.8 (3)
C8—O6—C6	111.3 (2)	C22—C23—C24	121.0 (4)
O6—C6—C5	109.3 (2)	C22—C23—H23	119.5 (2)
O6—C6—H6A	109.8 (2)	C24—C23—H23	119.5 (3)
C5—C6—H6A	109.8 (2)	C25—C24—C23	119.8 (4)
O6—C6—H6B	109.82 (13)	C25—C24—H24	120.1 (3)
C5—C6—H6B	109.82 (13)	C23—C24—H24	120.1 (3)
H6A—C6—H6B	108.3	C26—C25—C24	120.3 (3)
O5—C5—C4	109.6 (2)	C26—C25—H25	119.8 (2)
O5—C5—C6	109.0 (2)	C24—C25—H25	119.8 (3)
C4—C5—C6	109.5 (2)	C25—C26—C27	120.2 (4)
O5—C5—H5	109.56 (12)	C25—C26—H26	119.9 (2)
C4—C5—H5	109.56 (13)	C27—C26—H26	119.9 (2)
C6—C5—H5	109.6 (2)	C22—C27—C26	120.0 (3)
C10—C9—C14	119.0 (2)	C22—C27—H27	120.0 (2)
C10—C9—C8	120.2 (2)	C26—C27—H27	120.0 (2)
C14—C9—C8	120.8 (2)
C5—O5—C1—O1	64.4 (2)	O4—C8—C9—C10	19.4 (3)
C5—O5—C1—C2	−57.4 (3)	O6—C8—C9—C14	−40.8 (3)
O5—C1—O1—C7	70.5 (3)	O4—C8—C9—C14	−161.6 (3)
C2—C1—O1—C7	−165.0 (2)	C14—C9—C10—C11	2.7 (5)
O1—C1—C2—N1	47.0 (3)	C8—C9—C10—C11	−178.3 (3)
O5—C1—C2—N1	170.7 (2)	C9—C10—C11—C12	−2.1 (6)
O1—C1—C2—C3	−78.0 (2)	C10—C11—C12—C13	−0.4 (6)
O5—C1—C2—C3	45.7 (3)	C11—C12—C13—C14	2.2 (7)
N1—C2—C3—C4	−169.6 (2)	C12—C13—C14—C9	−1.5 (6)
C1—C2—C3—C4	−42.9 (3)	C10—C9—C14—C13	−0.9 (5)
N1—C2—C3—S1	68.9 (2)	C8—C9—C14—C13	−179.9 (3)
C1—C2—C3—S1	−164.4 (2)	O2—S1—C15—C16	−28.9 (3)
O2—S1—C3—C4	−102.2 (2)	O3—S1—C15—C16	−156.9 (2)
O3—S1—C3—C4	27.0 (2)	C3—S1—C15—C16	87.8 (2)
C15—S1—C3—C4	141.5 (2)	O2—S1—C15—C20	148.9 (2)
O2—S1—C3—C2	19.5 (2)	O3—S1—C15—C20	20.8 (3)
O3—S1—C3—C2	148.7 (2)	C3—S1—C15—C20	−94.4 (2)
C15—S1—C3—C2	−96.8 (2)	C20—C15—C16—C17	−0.1 (5)
C2—C3—C4—O4	168.4 (2)	S1—C15—C16—C17	177.6 (3)
S1—C3—C4—O4	−70.5 (2)	C15—C16—C17—C18	−0.6 (5)
C2—C3—C4—C5	51.1 (3)	C16—C17—C18—C19	0.6 (6)
S1—C3—C4—C5	172.2 (2)	C17—C18—C19—C20	0.1 (6)
C5—C4—O4—C8	−63.2 (2)	C16—C15—C20—C19	0.8 (5)
C3—C4—O4—C8	177.9 (2)	S1—C15—C20—C19	−177.0 (3)
C4—O4—C8—O6	66.5 (2)	C18—C19—C20—C15	−0.8 (6)
C4—O4—C8—C9	−173.9 (2)	C3—C2—N1—C21	−158.8 (2)
O4—C8—O6—C6	−61.8 (3)	C1—C2—N1—C21	74.1 (3)
C9—C8—O6—C6	178.8 (2)	C2—N1—C21—C22	−175.4 (2)
C8—O6—C6—C5	55.1 (3)	N1—C21—C22—C23	86.2 (4)
C1—O5—C5—C4	67.0 (2)	N1—C21—C22—C27	−92.8 (4)
C1—O5—C5—C6	−173.2 (2)	C27—C22—C23—C24	0.7 (6)
O4—C4—C5—O5	176.8 (2)	C21—C22—C23—C24	−178.4 (4)
C3—C4—C5—O5	−63.7 (2)	C22—C23—C24—C25	0.0 (7)
O4—C4—C5—C6	57.2 (3)	C23—C24—C25—C26	0.2 (7)
C3—C4—C5—C6	176.8 (2)	C24—C25—C26—C27	−1.1 (6)
O6—C6—C5—O5	−173.4 (2)	C23—C22—C27—C26	−1.6 (5)
O6—C6—C5—C4	−53.5 (3)	C21—C22—C27—C26	177.5 (3)
O6—C8—C9—C10	140.2 (2)	C25—C26—C27—C22	1.8 (6)

(Ib) Methyl 2-N-Benzylamino −2,3-dideoxy −4,6-O-(phenyl methylene)- 3-C-phenylsulfonyl b\-D-glucopyranoside

Crystal data

C27H29NO6S	Z = 1
Mr = 495.57	F(000) = 262
Triclinic, P1	Dx = 1.343 Mg m^−3
a = 8.319 (1) Å	Cu Kα radiation, λ = 1.54180 Å
b = 13.197 (2) Å	Cell parameters from 18 reflections
c = 5.750 (2) Å	θ = 29.5–46.0°
α = 100.84 (2)°	µ = 1.54 mm^−1
β = 98.61 (2)°	T = 293 K
γ = 89.43 (1)°	Irregular flakes, colourless
V = 612.9 (2) Å^3	0.40 × 0.14 × 0.06 mm

Data collection

AFC7S diffractometer	2407 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
Graphite monochromator	θmax = 70.1°, θmin = 3.4°
ω–2θ scans	h = 0→10
Absorption correction: for a sphere Weber(1969)	k = −16→16
Tmin = 0.709, Tmax = 0.722	l = −6→6
2739 measured reflections	3 standard reflections every 150 reflections
2425 independent reflections	intensity decay: 0.2%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.069	Calculated w = 1/[s^2(Fo^2) + (0.1392P)^2 + 0.4772P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.203	(Δ/σ)max = −0.005
S = 1.10	Δρmax = 0.20 e Å^−3
2425 reflections	Δρmin = −0.31 e Å^−3
318 parameters	Extinction correction: SHELXL93 (Sheldrick, 1993), Fc^*=kFc[1+0.001xFc^2l^3/sin(2q)]^-1/4
3 restraints	Extinction coefficient: 0.0995 (98)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (4)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	1.19100 (14)	0.78316 (11)	1.1315 (2)	0.0433 (4)
O2	1.3471 (6)	0.8294 (4)	1.1300 (10)	0.0590 (13)
O3	1.1226 (7)	0.8027 (4)	1.3479 (7)	0.0577 (12)
O5	0.7504 (6)	0.9418 (3)	0.8197 (8)	0.0488 (10)
C1	0.8750 (8)	0.9817 (4)	1.0096 (10)	0.0427 (13)
H1	0.8746 (8)	1.0570 (4)	1.0257 (10)	0.051*
O1	0.8472 (6)	0.9600 (4)	1.2263 (8)	0.0482 (10)
C7	0.7002 (11)	1.0069 (7)	1.2944 (15)	0.068 (2)
H7A	0.7080	1.0200	1.4657	0.102*
H7B	0.6093	0.9613	1.2250	0.102*
H7C	0.6852	1.0708	1.2378	0.102*
C2	1.0451 (8)	0.9462 (5)	0.9601 (11)	0.0438 (13)
H2	1.1206	0.9705	1.1078	0.053*
C3	1.0548 (8)	0.8251 (4)	0.9046 (11)	0.0437 (13)
H3	1.1018	0.8065	0.7561	0.052*
C4	0.8845 (7)	0.7772 (4)	0.8548 (10)	0.0392 (12)
H4	0.8442	0.7745	1.0052	0.047*
O4	0.8888 (5)	0.6748 (3)	0.7131 (7)	0.0442 (10)
C8	0.7299 (8)	0.6266 (5)	0.6607 (13)	0.0491 (14)
H8	0.6904	0.6204	0.8097	0.059*
O6	0.6191 (6)	0.6826 (4)	0.5259 (10)	0.0621 (13)
C6	0.6033 (9)	0.7863 (6)	0.6477 (15)	0.059 (2)
H6A	0.5594	0.7865	0.7948	0.071*
H6B	0.5300	0.8235	0.5475	0.071*
C5	0.7700 (8)	0.8374 (5)	0.7031 (10)	0.0425 (13)
H5	0.8116	0.8378	0.5525	0.051*
C9	0.7491 (8)	0.5210 (5)	0.5138 (13)	0.0495 (14)
C10	0.6689 (12)	0.4939 (7)	0.2817 (17)	0.073 (2)
H10	0.5997	0.5400	0.2147	0.087*
C11	0.6931 (14)	0.3969 (8)	0.1500 (18)	0.082 (3)
H11	0.6411	0.3781	−0.0070	0.098*
C12	0.7932 (12)	0.3290 (7)	0.251 (2)	0.080 (3)
H12	0.8074	0.2639	0.1615	0.096*
C13	0.8726 (12)	0.3550 (7)	0.479 (2)	0.076 (2)
H13	0.9420	0.3087	0.5452	0.092*
C14	0.8481 (11)	0.4522 (6)	0.6125 (16)	0.067 (2)
H14	0.8996	0.4703	0.7700	0.081*
C15	1.2099 (8)	0.6485 (5)	1.0514 (10)	0.0437 (13)
C16	1.2891 (9)	0.6096 (6)	0.8588 (12)	0.0527 (15)
H16	1.3271	0.6534	0.7689	0.063*
C17	1.3107 (12)	0.5018 (6)	0.8022 (15)	0.068 (2)
H17	1.3640	0.4737	0.6745	0.081*
C18	1.2531 (13)	0.4396 (6)	0.9359 (16)	0.073 (2)
H18	1.2672	0.3687	0.8978	0.087*
C19	1.1754 (13)	0.4789 (6)	1.1240 (16)	0.074 (2)
H19	1.1391	0.4350	1.2149	0.088*
C20	1.1499 (10)	0.5840 (6)	1.1813 (13)	0.058 (2)
H20	1.0929	0.6106	1.3059	0.069*
N1	1.0916 (7)	0.9987 (4)	0.7789 (9)	0.0470 (12)
H1N1	1.0211	1.0180	0.6713	0.056*
C21	1.2637 (9)	1.0162 (6)	0.7914 (15)	0.056 (2)
H21A	1.3126	0.9523	0.7251	0.068*
H21B	1.3121	1.0358	0.9581	0.068*
C22	1.3022 (8)	1.0988 (5)	0.6590 (11)	0.0471 (14)
C23	1.1897 (9)	1.1349 (5)	0.4954 (13)	0.055 (2)
H23	1.0826	1.1109	0.4707	0.066*
C24	1.2331 (12)	1.2068 (6)	0.3653 (17)	0.070 (2)
H24	1.1566	1.2289	0.2510	0.084*
C25	1.3930 (12)	1.2455 (6)	0.4087 (16)	0.066 (2)
H25	1.4238	1.2937	0.3238	0.079*
C26	1.5031 (11)	1.2119 (6)	0.5769 (17)	0.069 (2)
H26	1.6088	1.2388	0.6092	0.083*
C27	1.4603 (9)	1.1387 (6)	0.6995 (15)	0.060 (2)
H27	1.5380	1.1157	0.8107	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0471 (8)	0.0462 (7)	0.0341 (7)	−0.0098 (5)	0.0012 (5)	0.0045 (5)
O2	0.045 (2)	0.063 (3)	0.067 (3)	−0.020 (2)	−0.002 (2)	0.014 (2)
O3	0.083 (3)	0.071 (3)	0.021 (2)	0.000 (2)	0.019 (2)	0.004 (2)
O5	0.056 (3)	0.044 (2)	0.044 (2)	0.000 (2)	0.003 (2)	0.004 (2)
C1	0.058 (3)	0.041 (3)	0.031 (3)	−0.007 (2)	0.013 (2)	0.005 (2)
O1	0.054 (2)	0.059 (2)	0.034 (2)	0.008 (2)	0.012 (2)	0.010 (2)
C7	0.073 (5)	0.084 (5)	0.059 (4)	0.032 (4)	0.035 (4)	0.030 (4)
C2	0.051 (3)	0.043 (3)	0.037 (3)	−0.013 (2)	0.012 (2)	0.001 (2)
C3	0.053 (3)	0.037 (3)	0.040 (3)	−0.015 (2)	0.017 (2)	−0.003 (2)
C4	0.045 (3)	0.037 (3)	0.035 (3)	−0.004 (2)	0.002 (2)	0.006 (2)
O4	0.041 (2)	0.038 (2)	0.049 (2)	−0.010 (2)	0.001 (2)	0.000 (2)
C8	0.039 (3)	0.047 (3)	0.057 (4)	−0.008 (2)	0.001 (3)	0.006 (3)
O6	0.049 (3)	0.053 (3)	0.073 (3)	−0.003 (2)	−0.012 (2)	−0.001 (2)
C6	0.043 (4)	0.055 (4)	0.068 (4)	0.002 (3)	−0.011 (3)	0.000 (3)
C5	0.050 (3)	0.039 (3)	0.036 (3)	−0.001 (2)	0.004 (2)	0.003 (2)
C9	0.043 (3)	0.045 (3)	0.061 (4)	−0.013 (2)	0.008 (3)	0.008 (3)
C10	0.079 (6)	0.061 (4)	0.068 (5)	−0.015 (4)	−0.002 (4)	−0.002 (4)
C11	0.091 (7)	0.074 (5)	0.070 (5)	−0.016 (5)	0.009 (5)	−0.011 (4)
C12	0.079 (6)	0.054 (4)	0.101 (7)	−0.019 (4)	0.025 (5)	−0.015 (4)
C13	0.072 (5)	0.053 (4)	0.104 (7)	0.002 (4)	0.017 (5)	0.011 (4)
C14	0.068 (5)	0.057 (4)	0.073 (5)	−0.003 (3)	0.002 (4)	0.007 (4)
C15	0.049 (3)	0.046 (3)	0.037 (3)	−0.001 (2)	0.003 (2)	0.012 (2)
C16	0.052 (4)	0.063 (4)	0.043 (3)	−0.001 (3)	0.006 (3)	0.011 (3)
C17	0.078 (5)	0.058 (4)	0.062 (4)	0.008 (4)	0.004 (4)	0.001 (3)
C18	0.087 (6)	0.048 (4)	0.075 (6)	0.003 (4)	−0.011 (5)	0.006 (3)
C19	0.096 (6)	0.053 (4)	0.074 (5)	−0.011 (4)	−0.002 (5)	0.031 (4)
C20	0.068 (4)	0.054 (4)	0.054 (4)	−0.008 (3)	0.009 (3)	0.018 (3)
N1	0.057 (3)	0.047 (3)	0.041 (3)	−0.011 (2)	0.009 (2)	0.016 (2)
C21	0.056 (4)	0.051 (3)	0.066 (4)	−0.006 (3)	0.013 (3)	0.017 (3)
C22	0.054 (4)	0.040 (3)	0.049 (3)	−0.006 (3)	0.015 (3)	0.006 (2)
C23	0.057 (4)	0.051 (3)	0.057 (4)	−0.011 (3)	0.007 (3)	0.014 (3)
C24	0.082 (6)	0.062 (4)	0.072 (5)	−0.006 (4)	0.014 (4)	0.026 (4)
C25	0.090 (6)	0.047 (3)	0.074 (5)	−0.005 (3)	0.037 (4)	0.023 (3)
C26	0.065 (5)	0.056 (4)	0.086 (6)	−0.018 (4)	0.029 (4)	0.001 (4)
C27	0.049 (4)	0.066 (4)	0.067 (4)	−0.008 (3)	0.013 (3)	0.017 (3)

Geometric parameters (Å, º)

S1—O3	1.424 (4)	C11—C12	1.37 (2)
S1—O2	1.442 (5)	C11—H11	0.93
S1—C15	1.761 (6)	C12—C13	1.36 (2)
S1—C3	1.763 (7)	C12—H12	0.93
O5—C1	1.414 (7)	C13—C14	1.396 (12)
O5—C5	1.433 (7)	C13—H13	0.93
C1—O1	1.382 (7)	C14—H14	0.93
C1—C2	1.537 (9)	C15—C20	1.375 (9)
C1—H1	0.98	C15—C16	1.386 (9)
O1—C7	1.438 (8)	C16—C17	1.414 (11)
C7—H7A	0.96	C16—H16	0.93
C7—H7B	0.96	C17—C18	1.361 (14)
C7—H7C	0.96	C17—H17	0.93
C2—N1	1.453 (7)	C18—C19	1.360 (14)
C2—C3	1.574 (8)	C18—H18	0.93
C2—H2	0.98	C19—C20	1.386 (11)
C3—C4	1.522 (8)	C19—H19	0.93
C3—H3	0.98	C20—H20	0.93
C4—O4	1.444 (7)	N1—C21	1.442 (9)
C4—C5	1.516 (8)	N1—H1N1	0.86
C4—H4	0.98	C21—C22	1.504 (9)
O4—C8	1.439 (7)	C21—H21A	0.97
C8—O6	1.408 (8)	C21—H21B	0.97
C8—C9	1.508 (9)	C22—C23	1.372 (10)
C8—H8	0.98	C22—C27	1.392 (10)
O6—C6	1.430 (9)	C23—C24	1.395 (10)
C6—C5	1.511 (9)	C23—H23	0.93
C6—H6A	0.97	C24—C25	1.400 (13)
C6—H6B	0.97	C24—H24	0.93
C5—H5	0.98	C25—C26	1.364 (13)
C9—C14	1.365 (11)	C25—H25	0.93
C9—C10	1.383 (11)	C26—C27	1.376 (11)
C10—C11	1.389 (13)	C26—H26	0.93
C10—H10	0.93	C27—H27	0.93
O3—S1—O2	118.4 (3)	C9—C10—C11	119.1 (9)
O3—S1—C15	107.2 (3)	C9—C10—H10	120.4 (5)
O2—S1—C15	107.4 (3)	C11—C10—H10	120.4 (6)
O3—S1—C3	108.8 (3)	C12—C11—C10	120.1 (9)
O2—S1—C3	106.4 (3)	C12—C11—H11	119.9 (5)
C15—S1—C3	108.3 (3)	C10—C11—H11	119.9 (6)
C1—O5—C5	115.6 (4)	C13—C12—C11	121.2 (8)
O1—C1—O5	112.4 (5)	C13—C12—H12	119.4 (5)
O1—C1—C2	110.1 (5)	C11—C12—H12	119.4 (5)
O5—C1—C2	113.0 (5)	C12—C13—C14	118.9 (9)
O1—C1—H1	107.0 (3)	C12—C13—H13	120.6 (5)
O5—C1—H1	107.0 (3)	C14—C13—H13	120.6 (6)
C2—C1—H1	107.0 (3)	C9—C14—C13	120.5 (8)
C1—O1—C7	111.0 (5)	C9—C14—H14	119.7 (5)
O1—C7—H7A	109.5 (4)	C13—C14—H14	119.7 (6)
O1—C7—H7B	109.5 (5)	C20—C15—C16	121.1 (6)
H7A—C7—H7B	109.47 (10)	C20—C15—S1	120.3 (5)
O1—C7—H7C	109.5 (4)	C16—C15—S1	118.6 (5)
H7A—C7—H7C	109.5	C15—C16—C17	118.4 (7)
H7B—C7—H7C	109.47 (8)	C15—C16—H16	120.8 (4)
N1—C2—C1	108.5 (5)	C17—C16—H16	120.8 (5)
N1—C2—C3	115.6 (5)	C18—C17—C16	119.6 (8)
C1—C2—C3	111.5 (5)	C18—C17—H17	120.2 (5)
N1—C2—H2	106.9 (3)	C16—C17—H17	120.2 (5)
C1—C2—H2	106.9 (3)	C19—C18—C17	121.3 (8)
C3—C2—H2	106.9 (3)	C19—C18—H18	119.4 (5)
C4—C3—C2	110.1 (5)	C17—C18—H18	119.4 (5)
C4—C3—S1	116.0 (4)	C18—C19—C20	120.5 (7)
C2—C3—S1	109.8 (4)	C18—C19—H19	119.8 (5)
C4—C3—H3	106.8 (3)	C20—C19—H19	119.8 (5)
C2—C3—H3	106.8 (3)	C15—C20—C19	119.1 (7)
S1—C3—H3	106.8 (2)	C15—C20—H20	120.4 (4)
O4—C4—C5	105.8 (4)	C19—C20—H20	120.4 (5)
O4—C4—C3	109.0 (5)	C21—N1—C2	115.6 (5)
C5—C4—C3	110.4 (5)	C21—N1—H1N1	122.2 (4)
O4—C4—H4	110.5 (3)	C2—N1—H1N1	122.2 (3)
C5—C4—H4	110.5 (3)	N1—C21—C22	113.1 (6)
C3—C4—H4	110.5 (3)	N1—C21—H21A	109.0 (4)
C8—O4—C4	110.9 (4)	C22—C21—H21A	109.0 (4)
O6—C8—O4	111.2 (5)	N1—C21—H21B	109.0 (4)
O6—C8—C9	109.0 (5)	C22—C21—H21B	109.0 (4)
O4—C8—C9	106.2 (5)	H21A—C21—H21B	107.8
O6—C8—H8	110.1 (4)	C23—C22—C27	118.3 (6)
O4—C8—H8	110.1 (3)	C23—C22—C21	123.1 (6)
C9—C8—H8	110.1 (4)	C27—C22—C21	118.6 (7)
C8—O6—C6	112.2 (5)	C22—C23—C24	121.2 (7)
O6—C6—C5	108.1 (6)	C22—C23—H23	119.4 (4)
O6—C6—H6A	110.1 (4)	C24—C23—H23	119.4 (5)
C5—C6—H6A	110.1 (4)	C23—C24—C25	119.3 (8)
O6—C6—H6B	110.1 (3)	C23—C24—H24	120.4 (5)
C5—C6—H6B	110.1 (4)	C25—C24—H24	120.4 (5)
H6A—C6—H6B	108.4	C26—C25—C24	119.3 (7)
O5—C5—C6	107.0 (5)	C26—C25—H25	120.4 (4)
O5—C5—C4	113.1 (5)	C24—C25—H25	120.4 (5)
C6—C5—C4	109.6 (5)	C25—C26—C27	121.0 (8)
O5—C5—H5	109.0 (3)	C25—C26—H26	119.5 (5)
C6—C5—H5	109.0 (4)	C27—C26—H26	119.5 (5)
C4—C5—H5	109.0 (3)	C26—C27—C22	120.8 (8)
C14—C9—C10	120.1 (7)	C26—C27—H27	119.6 (5)
C14—C9—C8	119.1 (7)	C22—C27—H27	119.6 (4)
C10—C9—C8	120.8 (6)
C5—O5—C1—O1	−87.1 (6)	O4—C8—C9—C14	61.9 (8)
C5—O5—C1—C2	38.3 (7)	O6—C8—C9—C10	2.2 (9)
O5—C1—O1—C7	−62.2 (7)	O4—C8—C9—C10	−117.7 (7)
C2—C1—O1—C7	170.9 (6)	C14—C9—C10—C11	−1.2 (13)
O1—C1—C2—N1	−161.5 (5)	C8—C9—C10—C11	178.3 (8)
O5—C1—C2—N1	71.9 (6)	C9—C10—C11—C12	0.9 (15)
O1—C1—C2—C3	70.0 (6)	C10—C11—C12—C13	−0.9 (16)
O5—C1—C2—C3	−56.7 (6)	C11—C12—C13—C14	1.1 (15)
N1—C2—C3—C4	−110.7 (6)	C10—C9—C14—C13	1.5 (12)
C1—C2—C3—C4	14.0 (6)	C8—C9—C14—C13	−178.0 (8)
N1—C2—C3—S1	120.4 (5)	C12—C13—C14—C9	−1.5 (14)
C1—C2—C3—S1	−114.9 (5)	O3—S1—C15—C20	5.2 (7)
O3—S1—C3—C4	−57.4 (5)	O2—S1—C15—C20	133.4 (6)
O2—S1—C3—C4	174.0 (4)	C3—S1—C15—C20	−112.1 (6)
C15—S1—C3—C4	58.8 (5)	O3—S1—C15—C16	−173.6 (5)
O3—S1—C3—C2	68.2 (4)	O2—S1—C15—C16	−45.3 (6)
O2—S1—C3—C2	−60.5 (5)	C3—S1—C15—C16	69.2 (5)
C15—S1—C3—C2	−175.7 (4)	C20—C15—C16—C17	−1.6 (10)
C2—C3—C4—O4	156.6 (4)	S1—C15—C16—C17	177.1 (6)
S1—C3—C4—O4	−78.0 (5)	C15—C16—C17—C18	0.4 (12)
C2—C3—C4—C5	40.9 (6)	C16—C17—C18—C19	−0.3 (13)
S1—C3—C4—C5	166.2 (4)	C17—C18—C19—C20	1.4 (14)
C5—C4—O4—C8	−61.0 (6)	C16—C15—C20—C19	2.7 (11)
C3—C4—O4—C8	−179.8 (5)	S1—C15—C20—C19	−175.9 (6)
C4—O4—C8—O6	61.6 (7)	C18—C19—C20—C15	−2.6 (13)
C4—O4—C8—C9	−179.9 (5)	C1—C2—N1—C21	150.9 (6)
O4—C8—O6—C6	−59.1 (8)	C3—C2—N1—C21	−82.9 (7)
C9—C8—O6—C6	−175.9 (6)	C2—N1—C21—C22	−161.0 (5)
C8—O6—C6—C5	57.3 (8)	N1—C21—C22—C23	−15.5 (10)
C1—O5—C5—C6	141.3 (5)	N1—C21—C22—C27	166.2 (6)
C1—O5—C5—C4	20.5 (7)	C27—C22—C23—C24	2.4 (11)
O6—C6—C5—O5	178.6 (5)	C21—C22—C23—C24	−175.9 (7)
O6—C6—C5—C4	−58.4 (7)	C22—C23—C24—C25	−2.2 (12)
O4—C4—C5—O5	179.4 (5)	C23—C24—C25—C26	0.1 (12)
C3—C4—C5—O5	−62.8 (6)	C24—C25—C26—C27	1.7 (12)
O4—C4—C5—C6	60.1 (6)	C25—C26—C27—C22	−1.5 (12)
C3—C4—C5—C6	177.9 (5)	C23—C22—C27—C26	−0.6 (11)
O6—C8—C9—C14	−178.2 (6)	C21—C22—C27—C26	177.8 (7)