1-(2,3-Di-O-acetyl-4-chloro-4-de­oxy-6-O-tosyl-β-d-galactopyranos­yl)propan-2-one methanol 0.25-solvate

Yan, L.; Liu, F.-W.; Liu, H.-M.

doi:10.1107/S1600536808022253

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1558

doi:10.1107/S1600536808022253

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1-(2,3-Di-O-acetyl-4-chloro-4-deoxy-6-O-tosyl-β-D-galactopyranosyl)propan-2-one methanol 0.25-solvate

Lin Yan,^a ^* Feng-Wu Liu ^b and Hong-Min Liu ^b

^aInstitute of Pharmacy, Henan University, Kaifeng, Henan 475001, People's Republic of China, and ^bNew Drug Research and Development Center, Zhengzhou University, Zhengzhou, Henan 450052, People's Republic of China
^*Correspondence e-mail: yanlin0378@163.com

(Received 27 March 2008; accepted 16 July 2008; online 19 July 2008)

The asymmetric unit of the title solvate, C₂₀H₂₅ClO₉S·0.25CH₃OH, contains one galactopyranosyl derivative and one-quarter of a methanol solvent molecule. The galactopyranose ring is in the usual ⁴C₁ conformation, and the anomeric center of the sugar has a β configuration. The value of θ (3.44°) and the range of torsion angles [or 53.1 (5)–63.0 (5)°] reflect a slight distortion of the ⁴C₁ pyranose ring. A minor orientational disorder affects a carbonyl group, which was modeled with two sites for the O atom having occupancies of 0.79 (5) and 0.21 (5). The crystal studied exhibited inversion twinning.

Related literature

For related literature, see: Lewis et al. (1982 ); Nicolaou et al. (1995 ); Paterson & Mansuri (1985 ); Postema (1992 ); Tvaroška et al. (2002 ).

Experimental

Crystal data

C₂₀H₂₅ClO₉S·0.25CH₄O
M_r = 484.92
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.3300 (15) Å
b = 14.608 (3) Å
c = 22.329 (5) Å
V = 2390.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 291 (2) K
0.20 × 0.17 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.944, T_max = 0.954
7242 measured reflections
4129 independent reflections
3274 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.154
S = 1.00
4129 reflections
304 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ), 1683 Friedel pairs
Flack parameter: 0.42 (11)

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022253/bh2169sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808022253/bh2169Isup2.hkl

checkCIF report

Comment top

Due to their unique chemical and enzymatic hydrolysis stability, C-glycosides are becoming useful building blocks (Postema, 1992) for the total synthesis of various types of natural products such as palytoxin (Lewis et al., 1982), brevetoxin (Nicolaou et al., 1995) and polyether antibiotics (Paterson & Mansuri, 1985), and are used as a model in enzymatic and metabolic studies as well. Despite this attractive applications, structural investigations by using single-crystal X-ray analysis, which provides unambiguous structural data, are rare. Herein we report the design and synthesis of an acylated C-glycosidic analog, which would be of great interest in order to get additional crystallographic information about the substrate.

In the orthorhombic crystals of the title compound, the asymmetric unit contains one molecule and 0.25 methanol solvate. No significant hydrogen bonds exist in the crystal. The value of θ (3.44°) and the magnitude of the torsion angles in the ring (52.9–63.6°) reveal that the ⁴C₁ pyranose ring presents a slight distortion. The primary hydroxyl group in the title compound is in the gt position [O1—C5—C6—O7 = 74.9 (5)°], which is known to be the favored orientation for pyranose with the galacto configuration (Tvaroška et al., 2002).

Related literature top

For related literature, see: Lewis et al. (1982); Nicolaou et al. (1995); Paterson & Mansuri (1985); Postema (1992); Tvaroška et al. (2002).

Experimental top

All reagents were commercially available and of analytical grade. Sulfonylation of 1-(4-chloro-4-deoxy-β-D-galactopyranosyl)-propan-2-one with toluene-4-sulfonyl chloride in dry pyridine afforded the 6-toluenesulfonylated intermediate. Further acetylation with acetyl anhydride in pyridine and subsequent purification by chromatography on silica gel furnished the title compound as a white solid. White crystals suitable for X-ray crystallographic analysis were obtained by recrystallization from methanol.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing atom displacement ellipsoids drawn at the 50% probability level.

1-(2,3-Di-O-acetyl-4-chloro-4-deoxy-6-O-tosyl-β-D- galactopyranosyl)propan-2-one methanol 0.25-solvate top

Crystal data top

C₂₀H₂₅ClO₉S·0.25CH₄O	F(000) = 1018
M_r = 484.92	D_x = 1.347 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 399 reflections
a = 7.3300 (15) Å	θ = 2–25.1°
b = 14.608 (3) Å	µ = 0.29 mm⁻¹
c = 22.329 (5) Å	T = 291 K
V = 2390.9 (8) Å³	Prism, colourless
Z = 4	0.20 × 0.17 × 0.16 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4129 independent reflections
Radiation source: fine-focus sealed tube	3274 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
0.3° wide ω scans	θ_max = 25.3°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
T_min = 0.944, T_max = 0.954	k = −17→17
7242 measured reflections	l = −26→26

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)] = 0.062	H-atom parameters constrained
wR(F²) = 0.154	w = 1/[σ²(F_o²) + (0.0873P)² + 0.6536P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4129 reflections	Δρ_max = 0.19 e Å⁻³
304 parameters	Δρ_min = −0.29 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1683 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.42 (11)

Crystal data top

C₂₀H₂₅ClO₉S·0.25CH₄O	V = 2390.9 (8) Å³
M_r = 484.92	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.3300 (15) Å	µ = 0.29 mm⁻¹
b = 14.608 (3) Å	T = 291 K
c = 22.329 (5) Å	0.20 × 0.17 × 0.16 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4129 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3274 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.954	R_int = 0.052
7242 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	H-atom parameters constrained
wR(F²) = 0.154	Δρ_max = 0.19 e Å⁻³
S = 1.00	Δρ_min = −0.29 e Å⁻³
4129 reflections	Absolute structure: Flack (1983), 1683 Friedel pairs
304 parameters	Absolute structure parameter: 0.42 (11)
2 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.32977 (15)	0.92085 (8)	0.03975 (5)	0.0411 (3)
Cl1	0.65974 (18)	1.05079 (11)	0.24709 (5)	0.0662 (4)
O1	0.7356 (4)	1.1010 (2)	0.11261 (14)	0.0425 (7)
O2	0.8839 (8)	1.1761 (3)	−0.01365 (18)	0.0918 (16)
O3	1.1793 (4)	1.1764 (2)	0.16930 (14)	0.0481 (8)
O4	1.113 (5)	1.3083 (19)	0.2077 (18)	0.054 (11)	0.21 (5)
O4'	1.132 (2)	1.2846 (17)	0.2385 (15)	0.137 (9)	0.79 (5)
O5	1.0691 (4)	1.0491 (2)	0.25895 (13)	0.0512 (8)
O6	1.2341 (6)	0.9227 (3)	0.2414 (2)	0.0779 (12)
O7	0.5241 (4)	0.9533 (2)	0.06115 (13)	0.0453 (8)
O8	0.3338 (5)	0.9324 (2)	−0.02346 (13)	0.0599 (9)
O9	0.1958 (4)	0.9671 (2)	0.07483 (15)	0.0507 (8)
O10	1.184 (7)	1.295 (3)	0.3532 (19)	0.205 (15)*	0.25
H10	1.1133	1.2916	0.3250	0.308*	0.25
C1	0.9128 (6)	1.1430 (3)	0.1106 (2)	0.0389 (10)
H1A	0.9924	1.1071	0.0843	0.047*
C2	0.9930 (6)	1.1440 (3)	0.17380 (19)	0.0384 (10)
H2A	0.9211	1.1834	0.2003	0.046*
C3	1.0018 (6)	1.0463 (3)	0.19808 (18)	0.0400 (10)
H3A	1.0880	1.0112	0.1736	0.048*
C4	0.8168 (7)	1.0005 (3)	0.19472 (19)	0.0425 (10)
H4A	0.8316	0.9356	0.2047	0.051*
C5	0.7433 (7)	1.0076 (3)	0.1312 (2)	0.0423 (11)
H5A	0.8257	0.9745	0.1043	0.051*
C6	0.5551 (7)	0.9680 (4)	0.1250 (2)	0.0528 (13)
H6A	0.5464	0.9105	0.1466	0.063*
H6B	0.4649	1.0100	0.1410	0.063*
C7	0.8895 (7)	1.2381 (3)	0.0847 (2)	0.0525 (12)
H7A	0.9911	1.2757	0.0979	0.063*
H7B	0.7790	1.2647	0.1012	0.063*
C8	0.8787 (7)	1.2427 (4)	0.0170 (2)	0.0544 (13)
C9	0.8655 (10)	1.3370 (4)	−0.0087 (3)	0.0760 (18)
H9A	0.8524	1.3331	−0.0514	0.114*
H9B	0.9742	1.3706	0.0008	0.114*
H9C	0.7615	1.3677	0.0080	0.114*
C10	1.2286 (8)	1.2513 (4)	0.1997 (4)	0.0768 (19)
C11	1.4220 (9)	1.2763 (5)	0.1873 (4)	0.101 (3)
H11A	1.4464	1.3363	0.2029	0.152*
H11B	1.4430	1.2759	0.1449	0.152*
H11C	1.5014	1.2327	0.2063	0.152*
C12	1.1872 (7)	0.9807 (4)	0.2751 (2)	0.0527 (12)
C13	1.2456 (10)	0.9929 (6)	0.3384 (3)	0.093 (2)
H13A	1.3539	0.9577	0.3457	0.139*
H13B	1.1502	0.9726	0.3647	0.139*
H13C	1.2705	1.0565	0.3458	0.139*
C14	0.3198 (6)	0.8038 (3)	0.05653 (18)	0.0417 (10)
C15	0.2354 (7)	0.7735 (3)	0.1088 (2)	0.0492 (12)
H15A	0.1912	0.8151	0.1368	0.059*
C16	0.2191 (8)	0.6808 (3)	0.1182 (2)	0.0557 (13)
H16A	0.1628	0.6605	0.1531	0.067*
C17	0.2823 (7)	0.6174 (3)	0.0783 (2)	0.0524 (13)
C18	0.3687 (7)	0.6498 (4)	0.0270 (3)	0.0593 (14)
H18A	0.4158	0.6077	−0.0002	0.071*
C19	0.3868 (7)	0.7414 (4)	0.0151 (2)	0.0547 (13)
H19A	0.4429	0.7613	−0.0199	0.066*
C20	0.2580 (10)	0.5161 (4)	0.0872 (3)	0.0769 (18)
H20A	0.2353	0.5037	0.1288	0.115*
H20B	0.3666	0.4847	0.0748	0.115*
H20D	0.1565	0.4952	0.0637	0.115*
C21	1.292 (6)	1.229 (3)	0.3514 (17)	0.135 (14)*	0.25
H21A	1.2769	1.1924	0.3866	0.202*	0.25
H21B	1.4149	1.2518	0.3496	0.202*	0.25
H21C	1.2672	1.1930	0.3164	0.202*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0419 (6)	0.0444 (6)	0.0369 (5)	−0.0053 (5)	−0.0003 (5)	−0.0019 (5)
Cl1	0.0561 (7)	0.1008 (11)	0.0417 (6)	−0.0185 (8)	0.0082 (6)	−0.0121 (6)
O1	0.0387 (16)	0.0413 (18)	0.0476 (18)	−0.0039 (13)	−0.0022 (14)	0.0046 (14)
O2	0.167 (5)	0.053 (2)	0.055 (2)	−0.008 (3)	−0.020 (3)	0.002 (2)
O3	0.0376 (16)	0.0496 (18)	0.0570 (19)	−0.0041 (16)	0.0007 (15)	−0.0052 (15)
O4	0.062 (14)	0.026 (14)	0.07 (2)	−0.006 (9)	−0.013 (12)	−0.011 (12)
O4'	0.086 (6)	0.121 (12)	0.20 (2)	−0.026 (7)	0.017 (10)	−0.107 (14)
O5	0.0522 (18)	0.065 (2)	0.0363 (18)	0.0044 (17)	−0.0092 (14)	−0.0027 (16)
O6	0.078 (3)	0.083 (3)	0.073 (3)	0.026 (2)	−0.012 (2)	−0.003 (2)
O7	0.0475 (17)	0.057 (2)	0.0314 (16)	−0.0150 (16)	0.0000 (13)	−0.0044 (15)
O8	0.069 (2)	0.075 (2)	0.0353 (17)	−0.013 (2)	−0.0064 (16)	0.0054 (15)
O9	0.0485 (18)	0.0431 (18)	0.060 (2)	0.0050 (15)	0.0037 (16)	−0.0022 (15)
C1	0.041 (2)	0.032 (2)	0.044 (3)	−0.0023 (19)	0.0048 (19)	0.005 (2)
C2	0.035 (2)	0.042 (3)	0.039 (2)	0.0004 (19)	0.0023 (18)	−0.002 (2)
C3	0.044 (2)	0.046 (3)	0.030 (2)	0.000 (2)	0.0017 (18)	−0.002 (2)
C4	0.051 (3)	0.037 (2)	0.039 (2)	−0.006 (2)	0.002 (2)	−0.0006 (18)
C5	0.046 (3)	0.043 (3)	0.037 (2)	−0.006 (2)	0.0000 (19)	0.0007 (19)
C6	0.055 (3)	0.061 (3)	0.042 (3)	−0.024 (3)	0.002 (2)	−0.004 (2)
C7	0.058 (3)	0.043 (3)	0.056 (3)	−0.001 (2)	0.000 (2)	−0.002 (2)
C8	0.056 (3)	0.045 (3)	0.062 (3)	−0.008 (2)	−0.009 (2)	0.014 (3)
C9	0.089 (4)	0.054 (3)	0.085 (4)	0.001 (3)	−0.020 (4)	0.027 (3)
C10	0.051 (3)	0.054 (4)	0.125 (6)	−0.007 (3)	−0.004 (4)	−0.033 (4)
C11	0.060 (4)	0.079 (5)	0.166 (8)	−0.026 (3)	−0.006 (4)	−0.015 (5)
C12	0.040 (3)	0.069 (3)	0.049 (3)	0.004 (3)	−0.003 (2)	0.012 (3)
C13	0.089 (5)	0.139 (6)	0.050 (3)	0.041 (5)	−0.013 (3)	0.006 (4)
C14	0.037 (2)	0.048 (2)	0.040 (2)	−0.006 (2)	−0.001 (2)	−0.0071 (19)
C15	0.061 (3)	0.047 (3)	0.040 (3)	0.000 (2)	−0.001 (2)	−0.004 (2)
C16	0.077 (4)	0.044 (3)	0.046 (3)	−0.002 (2)	−0.004 (3)	0.000 (2)
C17	0.056 (3)	0.043 (3)	0.059 (3)	0.001 (2)	−0.021 (3)	−0.006 (2)
C18	0.048 (3)	0.052 (3)	0.077 (4)	0.008 (2)	0.000 (3)	−0.030 (3)
C19	0.051 (3)	0.055 (3)	0.059 (3)	−0.004 (2)	0.010 (2)	−0.019 (3)
C20	0.090 (4)	0.041 (3)	0.099 (5)	0.003 (3)	−0.032 (4)	−0.003 (3)

Geometric parameters (Å, º) top

S1—O8	1.422 (3)	C7—H7A	0.9700
S1—O9	1.427 (3)	C7—H7B	0.9700
S1—O7	1.576 (3)	C8—C9	1.496 (7)
S1—C14	1.753 (5)	C9—H9A	0.9600
Cl1—C4	1.798 (5)	C9—H9B	0.9600
O1—C5	1.426 (5)	C9—H9C	0.9600
O1—C1	1.437 (5)	C10—C11	1.490 (8)
O2—C8	1.189 (7)	C11—H11A	0.9600
O3—C10	1.337 (6)	C11—H11B	0.9600
O3—C2	1.449 (5)	C11—H11C	0.9600
O4—C10	1.20 (4)	C12—C13	1.488 (8)
O4'—C10	1.222 (16)	C13—H13A	0.9600
O5—C12	1.370 (6)	C13—H13B	0.9600
O5—C3	1.447 (5)	C13—H13C	0.9600
O6—C12	1.184 (6)	C14—C19	1.388 (6)
O7—C6	1.459 (6)	C14—C15	1.393 (6)
O10—C21	1.24 (5)	C15—C16	1.375 (7)
O10—H10	0.8200	C15—H15A	0.9300
C1—C7	1.515 (6)	C16—C17	1.367 (7)
C1—C2	1.530 (6)	C16—H16A	0.9300
C1—H1A	0.9800	C17—C18	1.392 (7)
C2—C3	1.527 (6)	C17—C20	1.503 (8)
C2—H2A	0.9800	C18—C19	1.371 (8)
C3—C4	1.514 (7)	C18—H18A	0.9300
C3—H3A	0.9800	C19—H19A	0.9300
C4—C5	1.521 (6)	C20—H20A	0.9600
C4—H4A	0.9800	C20—H20B	0.9600
C5—C6	1.503 (6)	C20—H20D	0.9600
C5—H5A	0.9800	C21—H21A	0.9600
C6—H6A	0.9700	C21—H21B	0.9600
C6—H6B	0.9700	C21—H21C	0.9600
C7—C8	1.516 (7)

O8—S1—O9	120.2 (2)	C8—C9—H9B	109.5
O8—S1—O7	104.3 (2)	H9A—C9—H9B	109.5
O9—S1—O7	108.28 (18)	C8—C9—H9C	109.5
O8—S1—C14	109.2 (2)	H9A—C9—H9C	109.5
O9—S1—C14	108.4 (2)	H9B—C9—H9C	109.5
O7—S1—C14	105.4 (2)	O4—C10—O4'	37.7 (13)
C5—O1—C1	112.4 (3)	O4—C10—O3	116.9 (17)
C10—O3—C2	119.2 (4)	O4'—C10—O3	122.0 (8)
C12—O5—C3	116.3 (4)	O4—C10—C11	121.9 (16)
C6—O7—S1	118.8 (3)	O4'—C10—C11	125.9 (8)
C21—O10—H10	109.5	O3—C10—C11	111.3 (6)
O1—C1—C7	107.6 (4)	C10—C11—H11A	109.5
O1—C1—C2	108.8 (3)	C10—C11—H11B	109.5
C7—C1—C2	112.7 (4)	H11A—C11—H11B	109.5
O1—C1—H1A	109.2	C10—C11—H11C	109.5
C7—C1—H1A	109.2	H11A—C11—H11C	109.5
C2—C1—H1A	109.2	H11B—C11—H11C	109.5
O3—C2—C3	106.9 (3)	O6—C12—O5	122.5 (5)
O3—C2—C1	107.6 (3)	O6—C12—C13	127.3 (5)
C3—C2—C1	109.5 (3)	O5—C12—C13	110.1 (5)
O3—C2—H2A	110.9	C12—C13—H13A	109.5
C3—C2—H2A	110.9	C12—C13—H13B	109.5
C1—C2—H2A	110.9	H13A—C13—H13B	109.5
O5—C3—C4	111.4 (3)	C12—C13—H13C	109.5
O5—C3—C2	108.8 (3)	H13A—C13—H13C	109.5
C4—C3—C2	111.0 (4)	H13B—C13—H13C	109.5
O5—C3—H3A	108.6	C19—C14—C15	120.5 (4)
C4—C3—H3A	108.6	C19—C14—S1	118.9 (4)
C2—C3—H3A	108.6	C15—C14—S1	120.5 (3)
C3—C4—C5	109.5 (4)	C16—C15—C14	118.6 (5)
C3—C4—Cl1	111.1 (3)	C16—C15—H15A	120.7
C5—C4—Cl1	110.6 (3)	C14—C15—H15A	120.7
C3—C4—H4A	108.5	C17—C16—C15	122.6 (5)
C5—C4—H4A	108.5	C17—C16—H16A	118.7
Cl1—C4—H4A	108.5	C15—C16—H16A	118.7
O1—C5—C6	107.8 (4)	C16—C17—C18	117.5 (5)
O1—C5—C4	110.5 (4)	C16—C17—C20	122.7 (6)
C6—C5—C4	112.7 (4)	C18—C17—C20	119.8 (5)
O1—C5—H5A	108.6	C19—C18—C17	122.3 (4)
C6—C5—H5A	108.6	C19—C18—H18A	118.8
C4—C5—H5A	108.6	C17—C18—H18A	118.8
O7—C6—C5	106.9 (4)	C18—C19—C14	118.6 (5)
O7—C6—H6A	110.4	C18—C19—H19A	120.7
C5—C6—H6A	110.4	C14—C19—H19A	120.7
O7—C6—H6B	110.4	C17—C20—H20A	109.5
C5—C6—H6B	110.4	C17—C20—H20B	109.5
H6A—C6—H6B	108.6	H20A—C20—H20B	109.5
C1—C7—C8	115.2 (4)	C17—C20—H20D	109.5
C1—C7—H7A	108.5	H20A—C20—H20D	109.5
C8—C7—H7A	108.5	H20B—C20—H20D	109.5
C1—C7—H7B	108.5	O10—C21—H21A	109.5
C8—C7—H7B	108.5	O10—C21—H21B	109.5
H7A—C7—H7B	107.5	H21A—C21—H21B	109.5
O2—C8—C9	122.3 (5)	O10—C21—H21C	109.5
O2—C8—C7	122.5 (5)	H21A—C21—H21C	109.5
C9—C8—C7	115.2 (5)	H21B—C21—H21C	109.5
C8—C9—H9A	109.5

O8—S1—O7—C6	167.7 (4)	O1—C5—C6—O7	74.9 (5)
O9—S1—O7—C6	38.6 (4)	C4—C5—C6—O7	−162.9 (4)
C14—S1—O7—C6	−77.2 (4)	O1—C1—C7—C8	−81.7 (5)
C5—O1—C1—C7	174.6 (4)	C2—C1—C7—C8	158.4 (4)
C5—O1—C1—C2	−63.0 (5)	C1—C7—C8—O2	1.7 (8)
C10—O3—C2—C3	−121.1 (5)	C1—C7—C8—C9	−177.0 (5)
C10—O3—C2—C1	121.3 (5)	C2—O3—C10—O4	−31 (2)
O1—C1—C2—O3	173.3 (3)	C2—O3—C10—O4'	12 (2)
C7—C1—C2—O3	−67.5 (5)	C2—O3—C10—C11	−177.5 (5)
O1—C1—C2—C3	57.5 (4)	C3—O5—C12—O6	0.8 (7)
C7—C1—C2—C3	176.7 (4)	C3—O5—C12—C13	179.5 (5)
C12—O5—C3—C4	96.5 (4)	O8—S1—C14—C19	25.0 (5)
C12—O5—C3—C2	−140.9 (4)	O9—S1—C14—C19	157.6 (4)
O3—C2—C3—O5	66.7 (4)	O7—S1—C14—C19	−86.6 (4)
C1—C2—C3—O5	−177.1 (3)	O8—S1—C14—C15	−151.0 (4)
O3—C2—C3—C4	−170.5 (3)	O9—S1—C14—C15	−18.4 (4)
C1—C2—C3—C4	−54.3 (5)	O7—S1—C14—C15	97.4 (4)
O5—C3—C4—C5	174.4 (4)	C19—C14—C15—C16	−0.5 (7)
C2—C3—C4—C5	53.1 (5)	S1—C14—C15—C16	175.4 (4)
O5—C3—C4—Cl1	52.0 (5)	C14—C15—C16—C17	0.0 (8)
C2—C3—C4—Cl1	−69.4 (4)	C15—C16—C17—C18	1.1 (8)
C1—O1—C5—C6	−173.7 (4)	C15—C16—C17—C20	−177.5 (5)
C1—O1—C5—C4	62.8 (5)	C16—C17—C18—C19	−1.8 (8)
C3—C4—C5—O1	−56.3 (5)	C20—C17—C18—C19	176.8 (5)
Cl1—C4—C5—O1	66.5 (4)	C17—C18—C19—C14	1.3 (8)
C3—C4—C5—C6	−176.9 (4)	C15—C14—C19—C18	−0.2 (7)
Cl1—C4—C5—C6	−54.2 (5)	S1—C14—C19—C18	−176.2 (4)
S1—O7—C6—C5	−174.1 (3)

Experimental details

Crystal data
Chemical formula	C₂₀H₂₅ClO₉S·0.25CH₄O
M_r	484.92
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	291
a, b, c (Å)	7.3300 (15), 14.608 (3), 22.329 (5)
V (Å³)	2390.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.20 × 0.17 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.944, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	7242, 4129, 3274
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.154, 1.00
No. of reflections	4129
No. of parameters	304
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.29
Absolute structure	Flack (1983), 1683 Friedel pairs
Absolute structure parameter	0.42 (11)

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Acknowledgements

This work was financially supported by the NNSF of the People's Republic of China (No. 20572103).

References

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