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The mol­ecule of the title compound, C24H26O7S, (I), is an important building block in the synthesis of oligosaccharides. Non-classical C—H...O hydrogen bonds link the mol­ecules in the crystal structure into infinite sheets.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039176/hg6274sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039176/hg6274Isup2.hkl
Contains datablock I

CCDC reference: 296570

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.088
  • wR factor = 0.163
  • Data-to-parameter ratio = 11.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C6 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C14 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16 PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 8
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.28 From the CIF: _reflns_number_total 4688 Count of symmetry unique reflns 2795 Completeness (_total/calc) 167.73% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1893 Fraction of Friedel pairs measured 0.677 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Carbohydrates often exist on cell surface as glycoprotein or glycolipid conjugates, and play important structural and functional roles in numerous biological recognition processes. The synthesis of saccharides has attracted much more interest in recent years. As part of a program to construct a phenylpropanoid glycosides library, our group has synthesized several monosaccharide building blocks. We report here the crystal structure of one of them, (I).

The molecular structure of (I) is shown in Fig. 1. In the crystal structure, non-classical C—H···O hydrogen bonds link the moleculese into infinite sheets (Fig. 2).

Experimental top

To a vigorously stirred solution of p-tolylsulfanyl-β-d-glucopyronoside (0.286 g, 1 mmol) in acetonitrile (20 ml) was added dropwise benzaldehyde dimethyl acetal (0.30 ml, 2 mmol) and p-tolylsulfonic acid (0.018 g, 0.1 mmol) in turn at room temperature. The reaction solution was stirred for 30 min at this temperature and concentrated. The resulting mixture was dissolved in CH2Cl2 (20 ml), washed with saturated NaHCO3 and water, then dried over anhydrous Na2SO4 and concentrated. The crude residue was dissolved in pyridine (10 ml) and acetic anhydride (7.5 ml) and stirred overnight at room temperature. The resulting mixture was concentrated, dissolved with CH2Cl2 (20 ml), washed with saturated aqueous NaHCO3 and water. The organic phase was dried over Na2SO4. After removal of the solvent in vacuo, the solid was purified by silica-gel column chromatography (hexane/ethyl acetate 4:1) to give the desired product (yield 83% over two steps). Colorless crystals were obtained from acetone solution after allowing it to stand for 4 d. 1H NMR (500 MHz, CDCl3): δ 7.38 (m, 8H), 7.16 (d, J = 8.0 Hz, 2H), 5.50 (s, 1H), 5.34 (t, J = 9.5 Hz, 1H), 4.99 (t, J = 9.0 Hz, 1H), 4.75 (d, J = 10.0 Hz, 1H), 4.39 (m, 1H), 3.79 (t, J = 10.0 Hz, 1H), 3.65 (t, J = 9.5 Hz, 1H), 3.57 (m, 1H), 2.37 (s, 3H), 2.12 (s, 3H), 2.04 (s, 3H). 13C NMR (125 MHz, CDCl3): δ 170.3, 169.7, 139.0, 137.0, 133.9, 130.0, 129.4, 128.5, 127.9, 126.4, 101.7, 87.0, 78.3, 73.2, 71.0, 70.9, 68.7, 21.4, 21.0. MS (EI): m/z = 481 [M + Na]+.

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.96–0.98 Å, and were refined as riding on their carrier atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (V1.06; Rigaku,1998); cell refinement: PROCESS-AUTO (V1.06; Rigaku,1998); data reduction: CrystalStructure (Version 3.60; Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Version 3.60; Rigaku/MSC, 2004) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecule of compound (I) in the crystal. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. The molecular packing of (I). Dashed lines indicate hydrogen-bonding interactions. H atoms not involved in hydrogen bonds have been omitted. [Symmetry codes: (i) −1 + x, −1 + y, z; (ii) 1 + x, y, z.]
2-Phenyl-6-(p-tolylsulfanyl)-4,4a,6,7,8,8a-hexahydro-2H- pyrano[3,2-d][1,3]dioxine-7,8-diyl diacetate top
Crystal data top
C24H26O7SF(000) = 484.00
Mr = 458.53Dx = 1.316 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2ybCell parameters from 8131 reflections
a = 5.6530 (7) Åθ = 2.5–27.3°
b = 8.0292 (9) ŵ = 0.18 mm1
c = 25.490 (3) ÅT = 295 K
β = 90.906 (5)°Block, colorless
V = 1156.8 (2) Å30.31 × 0.19 × 0.14 mm
Z = 2
Data collection top
Rigaku R-AXISRAPID
diffractometer
3140 reflections with F2 > 2.0σ(F2)
Detector resolution: 10.00 pixels mm-1Rint = 0.097
ω scansθmax = 27.3°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 77
Tmin = 0.893, Tmax = 0.975k = 1010
8608 measured reflectionsl = 3232
4688 independent reflections
Refinement top
Refinement on F2 w = 1/[0.0006Fo2 + 3σ(Fo2) + 0.5]/(4Fo2)
R[F2 > 2σ(F2)] = 0.088(Δ/σ)max < 0.001
wR(F2) = 0.163Δρmax = 0.55 e Å3
S = 1.00Δρmin = 0.47 e Å3
4583 reflectionsAbsolute structure: Flack (1983), 1922 Friedel Pairs
390 parametersAbsolute structure parameter: 0.04 (2)
H-atom parameters constrained
Crystal data top
C24H26O7SV = 1156.8 (2) Å3
Mr = 458.53Z = 2
Monoclinic, P21Mo Kα radiation
a = 5.6530 (7) ŵ = 0.18 mm1
b = 8.0292 (9) ÅT = 295 K
c = 25.490 (3) Å0.31 × 0.19 × 0.14 mm
β = 90.906 (5)°
Data collection top
Rigaku R-AXISRAPID
diffractometer
4688 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
3140 reflections with F2 > 2.0σ(F2)
Tmin = 0.893, Tmax = 0.975Rint = 0.097
8608 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.088H-atom parameters constrained
wR(F2) = 0.163Δρmax = 0.55 e Å3
S = 1.00Δρmin = 0.47 e Å3
4583 reflectionsAbsolute structure: Flack (1983), 1922 Friedel Pairs
390 parametersAbsolute structure parameter: 0.04 (2)
Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.4063 (2)0.3771 (2)0.36505 (5)0.0603 (4)
O10.6612 (7)0.5070 (5)0.2901 (1)0.062 (1)
O20.4861 (6)0.0705 (5)0.2913 (1)0.058 (1)
O30.0915 (7)0.0660 (6)0.2976 (2)0.085 (2)
O40.4337 (5)0.1658 (5)0.1823 (1)0.053 (1)
O50.684 (1)0.0286 (7)0.1530 (2)0.110 (2)
O60.8052 (6)0.4040 (4)0.1557 (1)0.050 (1)
O71.0129 (8)0.6417 (5)0.1809 (1)0.075 (1)
C10.6060 (9)0.3449 (7)0.3113 (2)0.052 (2)
C20.4858 (9)0.2389 (6)0.2711 (2)0.046 (1)
C30.6061 (9)0.2360 (7)0.2182 (2)0.048 (1)
C40.6724 (8)0.4055 (7)0.2017 (2)0.048 (1)
C50.810 (1)0.4889 (7)0.2457 (2)0.053 (2)
C60.884 (2)0.6606 (9)0.2278 (2)0.094 (3)
C70.593 (1)0.4348 (6)0.4180 (2)0.051 (2)
C80.800 (1)0.5245 (8)0.4132 (2)0.062 (2)
C90.936 (1)0.5605 (8)0.4575 (2)0.067 (2)
C100.868 (1)0.5128 (7)0.5072 (2)0.057 (2)
C111.022 (1)0.5562 (9)0.5544 (2)0.078 (2)
C120.662 (1)0.4294 (7)0.5114 (2)0.063 (2)
C130.5194 (9)0.3892 (8)0.4679 (2)0.061 (2)
C140.281 (1)0.0029 (8)0.3051 (2)0.060 (2)
C150.322 (1)0.1642 (8)0.3293 (3)0.087 (2)
C160.493 (1)0.0309 (8)0.1530 (2)0.064 (2)
C170.290 (1)0.0244 (9)0.1196 (3)0.082 (2)
C180.873 (1)0.5648 (7)0.1409 (2)0.055 (2)
C191.0189 (9)0.5586 (7)0.0926 (2)0.050 (1)
C201.218 (1)0.4636 (7)0.0904 (2)0.061 (2)
C211.356 (1)0.4627 (8)0.0473 (3)0.074 (2)
C221.297 (1)0.5600 (8)0.0043 (2)0.079 (2)
C231.098 (1)0.6599 (8)0.0066 (2)0.073 (2)
C240.956 (1)0.6575 (8)0.0501 (2)0.064 (2)
H10.75040.28920.32380.063*
H20.32290.27830.26620.054*
H30.74710.16530.22050.057*
H40.52690.46960.19570.057*
H50.95030.42290.25470.064*
H60.98120.71590.25430.113*
H70.74280.72580.22090.113*
H90.84700.56430.37860.075*
H101.08610.62020.45330.080*
H111.13210.46690.56050.093*
H120.92610.57060.58480.093*
H131.10730.65720.54780.093*
H140.60820.39720.54640.076*
H150.36870.33040.47170.073*
H160.32260.24840.30260.105*
H170.19880.18740.35370.105*
H180.47220.16360.34740.105*
H190.19790.10400.13850.099*
H200.34340.07360.08760.099*
H210.19540.07170.11170.099*
H221.26040.39270.12040.073*
H231.49980.39420.04710.089*
H241.39500.55820.02710.095*
H251.05870.73220.02320.088*
H260.81300.72650.05080.076*
H270.73180.63260.13410.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0555 (7)0.079 (1)0.0467 (7)0.0000 (8)0.0074 (6)0.0003 (8)
O10.091 (3)0.051 (2)0.045 (2)0.012 (2)0.014 (2)0.000 (2)
O20.060 (2)0.051 (2)0.062 (2)0.004 (2)0.006 (2)0.006 (2)
O30.057 (3)0.092 (4)0.108 (3)0.016 (2)0.005 (2)0.010 (3)
O40.051 (2)0.050 (2)0.059 (2)0.001 (2)0.003 (2)0.004 (2)
O50.102 (4)0.097 (4)0.130 (4)0.022 (3)0.004 (3)0.061 (3)
O60.065 (2)0.050 (2)0.036 (2)0.013 (2)0.006 (1)0.001 (2)
O70.109 (3)0.070 (3)0.048 (2)0.040 (2)0.010 (2)0.004 (2)
C10.051 (3)0.058 (4)0.048 (3)0.005 (3)0.008 (2)0.005 (3)
C20.053 (3)0.032 (3)0.052 (3)0.005 (2)0.002 (2)0.005 (2)
C30.041 (3)0.058 (4)0.044 (3)0.000 (2)0.004 (2)0.000 (2)
C40.048 (3)0.054 (3)0.041 (2)0.001 (3)0.004 (2)0.004 (2)
C50.063 (3)0.056 (4)0.041 (3)0.010 (3)0.005 (2)0.001 (2)
C60.168 (7)0.071 (5)0.043 (3)0.054 (5)0.022 (4)0.006 (3)
C70.063 (3)0.047 (3)0.044 (3)0.004 (3)0.010 (2)0.002 (2)
C80.072 (4)0.073 (4)0.041 (3)0.005 (3)0.012 (3)0.003 (3)
C90.064 (4)0.071 (4)0.066 (4)0.017 (3)0.011 (3)0.001 (3)
C100.066 (4)0.055 (4)0.051 (3)0.008 (3)0.003 (3)0.007 (3)
C110.089 (4)0.086 (5)0.058 (3)0.002 (4)0.002 (3)0.011 (3)
C120.075 (4)0.071 (4)0.043 (3)0.000 (3)0.008 (3)0.002 (3)
C130.061 (3)0.067 (4)0.056 (3)0.006 (3)0.012 (2)0.005 (3)
C140.070 (4)0.062 (4)0.049 (3)0.020 (3)0.005 (3)0.001 (3)
C150.119 (6)0.070 (5)0.073 (4)0.009 (4)0.006 (4)0.004 (4)
C160.084 (4)0.049 (4)0.059 (3)0.012 (3)0.012 (3)0.003 (3)
C170.097 (5)0.077 (5)0.073 (4)0.030 (4)0.002 (4)0.004 (4)
C180.069 (3)0.057 (4)0.040 (3)0.012 (3)0.001 (2)0.002 (3)
C190.051 (3)0.058 (3)0.040 (3)0.011 (3)0.000 (2)0.002 (2)
C200.062 (4)0.066 (4)0.056 (3)0.002 (3)0.003 (3)0.002 (3)
C210.066 (4)0.073 (5)0.083 (4)0.004 (3)0.018 (3)0.014 (4)
C220.098 (5)0.087 (5)0.053 (4)0.016 (4)0.026 (3)0.011 (4)
C230.083 (4)0.091 (5)0.045 (3)0.019 (4)0.006 (3)0.012 (3)
C240.066 (4)0.075 (4)0.050 (3)0.004 (3)0.006 (3)0.013 (3)
Geometric parameters (Å, º) top
S1—C11.807 (5)C19—C201.359 (8)
S1—C71.761 (5)C19—C241.385 (7)
O1—C11.446 (7)C20—C211.360 (9)
O1—C51.427 (6)C21—C221.385 (9)
O2—C21.447 (6)C22—C231.383 (9)
O2—C141.334 (7)C23—C241.378 (8)
O3—C141.196 (8)C1—H10.9800
O4—C31.442 (6)C2—H20.9800
O4—C161.359 (7)C3—H30.9800
O5—C161.182 (9)C4—H40.9800
O6—C41.403 (5)C5—H50.9800
O6—C181.400 (7)C6—H60.9700
O7—C61.416 (7)C6—H70.9700
O7—C181.421 (6)C8—H90.9800
C1—C21.488 (7)C9—H100.9800
C2—C31.519 (7)C11—H110.9600
C3—C41.474 (8)C11—H120.9600
C4—C51.509 (7)C11—H130.9600
C5—C61.515 (9)C12—H140.9800
C7—C81.384 (8)C13—H150.9800
C7—C131.393 (7)C15—H160.9600
C8—C91.386 (8)C15—H170.9600
C9—C101.385 (8)C15—H180.9600
C10—C111.516 (8)C17—H190.9600
C10—C121.348 (8)C17—H200.9600
C12—C131.398 (7)C17—H210.9600
C14—C151.494 (9)C18—H270.9800
C16—O41.359 (7)C20—H220.9800
C16—O51.182 (9)C21—H230.9800
C16—C171.484 (9)C22—H240.9800
C17—C161.484 (9)C23—H250.9800
C18—C191.493 (7)C24—H260.9800
S1—C1—O1107.2 (3)O6—C4—H4109.4365
S1—C1—C2108.7 (3)O6—C18—H27109.4544
C7—S1—C1104.2 (2)O7—C6—H6110.1562
S1—C7—C8124.5 (4)O7—C6—H7109.8343
S1—C7—C13116.6 (4)O7—C18—H27109.1342
O1—C1—C2110.9 (4)H1—C1—C2109.4260
C5—O1—C1109.7 (4)C1—C2—H2108.7816
O1—C5—C4109.4 (4)H2—C2—C3108.8829
O1—C5—C6108.4 (4)C2—C3—H3109.2629
O2—C2—C1106.9 (4)H3—C3—C4110.0142
C14—O2—C2118.5 (4)C3—C4—H4108.2282
O2—C2—C3107.7 (4)H4—C4—C5107.6374
O2—C14—O3124.5 (6)C4—C5—H5109.9155
O2—C14—C15110.1 (5)H5—C5—C6109.4749
O3—C14—C15125.4 (6)C5—C6—H6111.3337
O4—C3—C2105.2 (4)C5—C6—H7108.2020
O4—C3—C4110.6 (4)H7—C6—H6109.4630
C16—O4—C3119.4 (4)C7—C8—H9119.3896
O4—C16—O5123.7 (6)C7—C13—H15119.1234
O4—C16—C17111.1 (5)H9—C8—C9120.7555
O5—C16—C17125.1 (6)C8—C9—H10118.8550
O6—C4—C3111.9 (4)H10—C9—C10119.3694
O6—C4—C5110.4 (4)C10—C11—H11108.6084
C18—O6—C4111.7 (4)C10—C11—H12110.0558
O6—C18—O7111.1 (4)C10—C11—H13109.7317
O6—C18—C19110.4 (4)C10—C12—H14118.9514
O7—C6—C5107.8 (5)H12—C11—H11109.4781
C18—O7—C6111.4 (5)H13—C11—H11109.4722
O7—C18—C19107.4 (4)H13—C11—H12109.4775
C1—C2—C3114.5 (4)C12—C13—H15121.6936
C2—C3—C4111.0 (4)H14—C12—C13118.4209
C3—C4—C5109.1 (4)C14—C15—H16109.9696
C4—C5—C6108.8 (4)C14—C15—H17109.3972
C13—C7—C8118.8 (5)C14—C15—H18109.0354
C7—C8—C9119.8 (5)H17—C15—H16109.4742
C7—C13—C12119.2 (5)H18—C15—H16109.4671
C8—C9—C10121.8 (5)H18—C15—H17109.4824
C9—C10—C12117.7 (5)C16—C17—H19109.3788
C9—C10—C11119.8 (5)C16—C17—H20111.3354
C12—C10—C11122.5 (5)C16—C17—H21107.6749
C10—C12—C13122.6 (5)H20—C17—H19109.4703
C18—C19—C20121.3 (5)H21—C17—H19109.4672
C18—C19—C24119.2 (5)H21—C17—H20109.4800
C24—C19—C20119.4 (5)H27—C18—C19109.3413
C19—C20—C21121.6 (5)C19—C20—H22119.2273
C19—C24—C23119.4 (5)C19—C24—H26120.7072
C20—C21—C22120.1 (6)H22—C20—C21119.1854
C21—C22—C23118.6 (6)C20—C21—H23119.7209
C22—C23—C24120.8 (5)H23—C21—C22120.1962
S1—C1—H1110.2219C21—C22—H24120.3011
O1—C1—H1110.3858C22—C23—H25118.9026
O1—C5—H5110.7066H24—C22—C23121.0484
O2—C2—H2110.0478C23—C24—H26119.8778
O4—C3—H3110.6427H25—C23—C24120.3155
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C17—H19···O7i0.962.543.487 (8)168
C20—H22···O4ii0.982.593.550 (6)166
Symmetry codes: (i) x1, y1, z; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC24H26O7S
Mr458.53
Crystal system, space groupMonoclinic, P21
Temperature (K)295
a, b, c (Å)5.6530 (7), 8.0292 (9), 25.490 (3)
β (°) 90.906 (5)
V3)1156.8 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.31 × 0.19 × 0.14
Data collection
DiffractometerRigaku R-AXISRAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.893, 0.975
No. of measured, independent and
observed [F2 > 2.0σ(F2)] reflections
8608, 4688, 3140
Rint0.097
(sin θ/λ)max1)0.645
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.088, 0.163, 1.00
No. of reflections4583
No. of parameters390
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.55, 0.47
Absolute structureFlack (1983), 1922 Friedel Pairs
Absolute structure parameter0.04 (2)

Computer programs: PROCESS-AUTO (V1.06; Rigaku,1998), SIR97 (Altomare et al., 1999), CRYSTALS (Watkin et al., 1996), ORTEP-3 for Windows (Farrugia, 1997), CrystalStructure (Version 3.60; Rigaku/MSC, 2004) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C17—H19···O7i0.962.543.487 (8)168
C20—H22···O4ii0.982.593.550 (6)166
Symmetry codes: (i) x1, y1, z; (ii) x+1, y, z.
 

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