4-Methoxy-phenyl 2,3,4,6-tetra-O-acetyl-1-thio-α-d-mannopyran-oside.

The title compound, C(21)H(26)O(10)S, was synthesized in a single step from mannose penta-acetate. The mol-ecular structure confirms the α configuration of the anomeric thioaryl substituent. Spectroscopic and melting-point data obtained for the title compound are in disagreement with those previously reported, indicating the previously reported synthesis [Durette & Shen (1980 ▶). Carbohydr. Res. 81, 261-274] to be erroneous. The crystal structure is stabilized by weak inter-molecular C-H⋯O hydrogen bonds.

Related literature

For related literature, see: Altomare et al. (1994 ▶); Cao et al. (1998 ▶); Cosier & Glazer (1986 ▶); Drouin et al. (2007 ▶); Durette & Shen (1980 ▶); France et al. (2004 ▶); Mootoo et al. (1988 ▶); Poh (1982 ▶); Prince (1982 ▶); Roy et al. (1992 ▶); Watkin (1994 ▶).

Experimental

Crystal data

C21H26O10S

M = 470.50

Orthorhombic,

a = 8.6218 (2) Å

b = 15.2945 (3) Å

c = 17.5449 (3) Å

V = 2313.58 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 150 K

0.44 × 0.32 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶) T min = 0.94, T max = 0.96

18167 measured reflections

5253 independent reflections

4562 reflections with I > 2.0σ(I)

R int = 0.033

Refinement

R[F 2 > 3σ(F 2)] = 0.036

wR(F 2) = 0.035

S = 1.07

4305 reflections

290 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.26 e Å−3

Absolute structure: Flack (1983 ▶), 2269 Friedel pairs

Flack parameter: −0.06 (6)

Data collection: COLLECT (Nonius, 2001 ▶).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK and Hooft et al. (2008 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CRYSTALS.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019338/lh2646sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019338/lh2646Isup2.hkl

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

C21H26O10S1	Dx = 1.351 Mg m−3
Mr = 470.50	Melting point: not measured K
Orthorhombic, P212121	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 18167 reflections
a = 8.6218 (2) Å	θ = 5–28º
b = 15.2945 (3) Å	µ = 0.19 mm−1
c = 17.5449 (3) Å	T = 150 K
V = 2313.58 (8) Å3	Fragment, colourless
Z = 4	0.44 × 0.32 × 0.20 mm
F000 = 992

Area diffractometer	4562 reflections with I > 2.0σ(I)
Monochromator: graphite	Rint = 0.033
T = 150 K	θmax = 27.5º
ω scans	θmin = 5.2º
Absorption correction: multi-scanDENZO/SCALEPACK (Otwinowski & Minor, 1997)	h = −11→11
Tmin = 0.94, Tmax = 0.96	k = −19→19
18167 measured reflections	l = −22→22
5253 independent reflections

Refinement on F	H-atom parameters constrained
Least-squares matrix: full	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 0.350 0.808E-01 0.749E-01
R[F2 > 2σ(F2)] = 0.036	(Δ/σ)max = 0.001
wR(F2) = 0.035	Δρmax = 0.27 e Å−3
S = 1.07	Δρmin = −0.26 e Å−3
4305 reflections	Extinction correction: None
290 parameters	Absolute structure: Flack (1983), 2269 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.06 (6)
Hydrogen site location: inferred from neighbouring sites

Refinement. The hydrogen atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, N—H in the range 0.86–0.89, N—H to 0.86, O—H = 0.82 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints.

	x	y	z	Uiso*/Ueq
C1	0.42086 (19)	0.44662 (10)	0.48435 (10)	0.0278
C2	0.4623 (2)	0.51157 (10)	0.54678 (9)	0.0290
C3	0.3411 (2)	0.51009 (11)	0.60972 (9)	0.0293
C4	0.1802 (2)	0.52268 (11)	0.57752 (9)	0.0272
C5	0.15111 (19)	0.45186 (11)	0.51798 (10)	0.0276
C6	−0.0057 (2)	0.45811 (11)	0.48018 (11)	0.0333
O1	0.26620 (14)	0.45701 (8)	0.45874 (7)	0.0279
S1	0.46552 (6)	0.33607 (3)	0.51937 (3)	0.0339
C7	0.4854 (2)	0.27972 (11)	0.43134 (10)	0.0306
C8	0.3607 (2)	0.23433 (13)	0.40015 (12)	0.0390
C9	0.3778 (2)	0.19047 (13)	0.33162 (13)	0.0415
C10	0.5189 (2)	0.19112 (11)	0.29336 (10)	0.0336
C11	0.6441 (2)	0.23463 (12)	0.32488 (10)	0.0329
C12	0.6267 (2)	0.27925 (12)	0.39370 (11)	0.0317
O2	0.52304 (19)	0.14679 (9)	0.22609 (8)	0.0434
C13	0.6652 (3)	0.14715 (16)	0.18392 (12)	0.0527
O3	0.46128 (15)	0.59743 (7)	0.51222 (7)	0.0317
C14	0.5794 (2)	0.65171 (13)	0.52960 (12)	0.0401
O4	0.6831 (2)	0.63201 (11)	0.57186 (12)	0.0741
C15	0.5639 (3)	0.73699 (13)	0.48905 (13)	0.0471
O5	0.36891 (17)	0.58054 (9)	0.66273 (7)	0.0383
C16	0.4478 (3)	0.56208 (15)	0.72635 (11)	0.0448
O6	0.5010 (3)	0.49096 (12)	0.73892 (11)	0.0767
C17	0.4616 (4)	0.6411 (2)	0.77608 (14)	0.0696
O7	0.06770 (15)	0.50827 (8)	0.63709 (7)	0.0334
C18	0.0046 (2)	0.58014 (12)	0.67193 (10)	0.0374
O8	0.04098 (19)	0.65349 (8)	0.65627 (8)	0.0466
C19	−0.1121 (3)	0.55302 (15)	0.72963 (15)	0.0595
O9	−0.01388 (15)	0.54017 (8)	0.43982 (7)	0.0341
C20	−0.1484 (2)	0.55419 (14)	0.40247 (11)	0.0378
O10	−0.25415 (18)	0.50261 (13)	0.40449 (10)	0.0578
C21	−0.1459 (3)	0.63787 (15)	0.35898 (12)	0.0476
H11	0.4895	0.4569	0.4405	0.0329*
H21	0.5668	0.4991	0.5672	0.0352*
H31	0.3454	0.4533	0.6367	0.0357*
H41	0.1694	0.5812	0.5567	0.0321*
H51	0.1563	0.3935	0.5428	0.0332*
H61	−0.0883	0.4553	0.5182	0.0412*
H62	−0.0189	0.4084	0.4439	0.0426*
H81	0.2625	0.2331	0.4264	0.0476*
H91	0.2901	0.1590	0.3105	0.0504*
H111	0.7447	0.2344	0.2983	0.0390*
H121	0.7146	0.3117	0.4155	0.0391*
H131	0.6468	0.1130	0.1371	0.0801*
H132	0.7494	0.1231	0.2157	0.0787*
H133	0.6895	0.2084	0.1693	0.0802*
H152	0.6314	0.7806	0.5124	0.0710*
H151	0.4574	0.7570	0.4924	0.0705*
H153	0.5884	0.7284	0.4351	0.0710*
H172	0.5416	0.6301	0.8131	0.1035*
H171	0.3633	0.6515	0.7991	0.1058*
H173	0.4931	0.6909	0.7446	0.1044*
H192	−0.1471	0.6041	0.7564	0.0883*
H191	−0.0655	0.5113	0.7647	0.0876*
H193	−0.2004	0.5241	0.7047	0.0882*
H212	−0.2487	0.6498	0.3385	0.0716*
H211	−0.1161	0.6835	0.3930	0.0723*
H213	−0.0724	0.6340	0.3170	0.0725*

	U11	U22	U33	U12	U13	U23
C1	0.0262 (8)	0.0281 (8)	0.0291 (8)	0.0025 (6)	0.0019 (7)	0.0036 (7)
C2	0.0285 (8)	0.0272 (8)	0.0312 (8)	0.0019 (7)	−0.0038 (8)	0.0055 (6)
C3	0.0376 (9)	0.0248 (8)	0.0256 (8)	0.0018 (7)	−0.0030 (7)	0.0019 (6)
C4	0.0311 (9)	0.0255 (8)	0.0250 (8)	0.0008 (7)	0.0039 (7)	0.0025 (6)
C5	0.0281 (8)	0.0269 (8)	0.0277 (8)	−0.0001 (6)	0.0036 (7)	0.0005 (7)
C6	0.0315 (9)	0.0336 (8)	0.0349 (8)	−0.0036 (7)	−0.0019 (8)	0.0011 (8)
O1	0.0282 (6)	0.0299 (6)	0.0258 (6)	0.0020 (5)	0.0010 (5)	0.0012 (5)
S1	0.0391 (2)	0.03005 (19)	0.0327 (2)	0.00833 (19)	0.0037 (2)	0.00485 (18)
C7	0.0322 (9)	0.0244 (7)	0.0352 (9)	0.0038 (7)	−0.0009 (8)	0.0044 (6)
C8	0.0267 (9)	0.0412 (10)	0.0492 (11)	0.0006 (8)	0.0011 (8)	0.0039 (9)
C9	0.0348 (10)	0.0409 (10)	0.0488 (11)	−0.0048 (8)	−0.0094 (9)	−0.0022 (9)
C10	0.0397 (10)	0.0271 (8)	0.0342 (9)	0.0012 (8)	−0.0072 (8)	0.0003 (7)
C11	0.0325 (9)	0.0310 (9)	0.0354 (9)	−0.0011 (7)	0.0044 (8)	0.0002 (7)
C12	0.0310 (9)	0.0275 (8)	0.0367 (9)	−0.0022 (7)	−0.0006 (8)	0.0023 (7)
O2	0.0544 (9)	0.0377 (7)	0.0380 (7)	0.0002 (7)	−0.0072 (7)	−0.0076 (6)
C13	0.0666 (15)	0.0549 (13)	0.0365 (11)	0.0092 (12)	−0.0010 (11)	−0.0083 (10)
O3	0.0334 (6)	0.0279 (6)	0.0338 (6)	−0.0016 (5)	−0.0016 (6)	0.0066 (5)
C14	0.0412 (10)	0.0334 (9)	0.0457 (11)	−0.0063 (8)	−0.0018 (9)	−0.0007 (8)
O4	0.0709 (12)	0.0497 (10)	0.1018 (15)	−0.0241 (9)	−0.0468 (12)	0.0199 (10)
C15	0.0560 (13)	0.0304 (9)	0.0549 (12)	−0.0044 (9)	0.0132 (11)	0.0037 (9)
O5	0.0513 (8)	0.0370 (7)	0.0266 (6)	0.0028 (6)	−0.0104 (6)	−0.0042 (5)
C16	0.0469 (12)	0.0581 (13)	0.0293 (9)	−0.0087 (10)	−0.0104 (9)	0.0065 (9)
O6	0.1008 (16)	0.0624 (11)	0.0669 (11)	−0.0045 (11)	−0.0511 (12)	0.0164 (9)
C17	0.0801 (19)	0.0841 (18)	0.0445 (12)	−0.0086 (16)	−0.0198 (14)	−0.0186 (12)
O7	0.0412 (7)	0.0274 (6)	0.0316 (6)	0.0034 (5)	0.0126 (5)	−0.0009 (5)
C18	0.0477 (11)	0.0303 (9)	0.0341 (9)	0.0071 (8)	0.0074 (9)	−0.0021 (7)
O8	0.0655 (10)	0.0284 (6)	0.0460 (8)	0.0065 (7)	0.0131 (8)	0.0003 (6)
C19	0.0782 (17)	0.0413 (12)	0.0591 (14)	0.0126 (12)	0.0369 (14)	0.0011 (10)
O9	0.0268 (6)	0.0367 (6)	0.0387 (7)	0.0021 (5)	−0.0064 (5)	0.0006 (5)
C20	0.0249 (9)	0.0564 (12)	0.0321 (9)	0.0068 (9)	−0.0045 (8)	−0.0100 (8)
O10	0.0281 (7)	0.0905 (13)	0.0547 (10)	−0.0112 (7)	−0.0078 (7)	0.0022 (9)
C21	0.0476 (12)	0.0529 (13)	0.0423 (11)	0.0190 (10)	−0.0134 (10)	−0.0079 (9)

C1—C2	1.521 (2)	C12—H121	0.984
C1—O1	1.416 (2)	O2—C13	1.432 (3)
C1—S1	1.8398 (16)	C13—H131	0.985
C1—H11	0.984	C13—H132	0.987
C2—C3	1.520 (2)	C13—H133	0.994
C2—O3	1.4464 (18)	O3—C14	1.349 (2)
C2—H21	0.988	C14—O4	1.200 (3)
C3—C4	1.511 (2)	C14—C15	1.492 (3)
C3—O5	1.443 (2)	C15—H152	0.975
C3—H31	0.990	C15—H151	0.970
C4—C5	1.525 (2)	C15—H153	0.978
C4—O7	1.443 (2)	O5—C16	1.337 (2)
C4—H41	0.972	C16—O6	1.201 (3)
C5—C6	1.509 (2)	C16—C17	1.496 (3)
C5—O1	1.439 (2)	C17—H172	0.962
C5—H51	0.995	C17—H171	0.952
C6—O9	1.443 (2)	C17—H173	0.980
C6—H61	0.977	O7—C18	1.370 (2)
C6—H62	0.998	C18—O8	1.197 (2)
S1—C7	1.7770 (18)	C18—C19	1.486 (3)
C7—C8	1.392 (3)	C19—H192	0.961
C7—C12	1.385 (3)	C19—H191	0.973
C8—C9	1.385 (3)	C19—H193	0.983
C8—H81	0.965	O9—C20	1.350 (2)
C9—C10	1.390 (3)	C20—O10	1.206 (3)
C9—H91	0.969	C20—C21	1.490 (3)
C10—C11	1.384 (3)	C21—H212	0.973
C10—O2	1.362 (2)	C21—H211	0.953
C11—C12	1.395 (3)	C21—H213	0.974
C11—H111	0.984
C2—C1—O1	112.11 (13)	C12—C11—H111	120.4
C2—C1—S1	108.09 (12)	C11—C12—C7	120.66 (17)
O1—C1—S1	113.96 (11)	C11—C12—H121	120.0
C2—C1—H11	108.5	C7—C12—H121	119.3
O1—C1—H11	107.4	C10—O2—C13	117.93 (17)
S1—C1—H11	106.4	O2—C13—H131	106.9
C1—C2—C3	110.61 (14)	O2—C13—H132	109.7
C1—C2—O3	106.83 (13)	H131—C13—H132	113.0
C3—C2—O3	108.29 (13)	O2—C13—H133	108.5
C1—C2—H21	110.4	H131—C13—H133	108.5
C3—C2—H21	111.1	H132—C13—H133	110.1
O3—C2—H21	109.4	C2—O3—C14	117.36 (14)
C2—C3—C4	110.96 (14)	O3—C14—O4	123.21 (18)
C2—C3—O5	110.06 (14)	O3—C14—C15	111.29 (17)
C4—C3—O5	107.35 (14)	O4—C14—C15	125.49 (19)
C2—C3—H31	109.6	C14—C15—H152	110.1
C4—C3—H31	108.9	C14—C15—H151	109.4
O5—C3—H31	109.9	H152—C15—H151	108.9
C3—C4—C5	108.45 (13)	C14—C15—H153	109.0
C3—C4—O7	109.09 (13)	H152—C15—H153	111.7
C5—C4—O7	106.10 (13)	H151—C15—H153	107.8
C3—C4—H41	110.2	C3—O5—C16	117.69 (15)
C5—C4—H41	112.4	O5—C16—O6	122.6 (2)
O7—C4—H41	110.4	O5—C16—C17	110.9 (2)
C4—C5—C6	113.78 (14)	O6—C16—C17	126.5 (2)
C4—C5—O1	110.03 (13)	C16—C17—H172	108.0
C6—C5—O1	107.28 (14)	C16—C17—H171	108.1
C4—C5—H51	109.3	H172—C17—H171	112.4
C6—C5—H51	106.9	C16—C17—H173	108.7
O1—C5—H51	109.5	H172—C17—H173	108.6
C5—C6—O9	108.34 (13)	H171—C17—H173	110.9
C5—C6—H61	110.6	C4—O7—C18	117.88 (13)
O9—C6—H61	109.7	O7—C18—O8	123.04 (17)
C5—C6—H62	109.5	O7—C18—C19	110.42 (16)
O9—C6—H62	110.1	O8—C18—C19	126.54 (18)
H61—C6—H62	108.6	C18—C19—H192	108.6
C5—O1—C1	114.46 (13)	C18—C19—H191	109.5
C1—S1—C7	100.12 (8)	H192—C19—H191	110.7
S1—C7—C8	120.59 (14)	C18—C19—H193	110.3
S1—C7—C12	120.12 (14)	H192—C19—H193	109.9
C8—C7—C12	119.28 (17)	H191—C19—H193	107.8
C7—C8—C9	120.06 (18)	C6—O9—C20	114.75 (14)
C7—C8—H81	120.0	O9—C20—O10	122.1 (2)
C9—C8—H81	119.9	O9—C20—C21	111.87 (17)
C8—C9—C10	120.60 (18)	O10—C20—C21	126.01 (19)
C8—C9—H91	119.3	C20—C21—H212	109.7
C10—C9—H91	120.1	C20—C21—H211	108.2
C9—C10—C11	119.57 (17)	H212—C21—H211	109.9
C9—C10—O2	115.99 (17)	C20—C21—H213	110.2
C11—C10—O2	124.43 (18)	H212—C21—H213	108.9
C10—C11—C12	119.80 (18)	H211—C21—H213	110.0
C10—C11—H111	119.7

D—H···A	D—H	H···A	D···A	D—H···A
C1—H11···O10i	0.98	2.40	3.248 (3)	144
C19—H191···O2ii	0.97	2.54	3.362 (3)	142
C21—H213···O6iii	0.97	2.43	3.143 (3)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H11⋯O10i	0.98	2.40	3.248 (3)	144
C19—H191⋯O2ii	0.97	2.54	3.362 (3)	142
C21—H213⋯O6iii	0.97	2.43	3.143 (3)	130

Symmetry codes: (i) ; (ii) ; (iii) .