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The title compound, C14H18O9, adopt the half-chair conformation 4H5 in the crystalline state. The structure is stabilized by C—H...O hydrogen bonds, in addition to van der Waals forces.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049379/hg2312sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049379/hg2312Isup2.hkl
Contains datablock I

CCDC reference: 667359

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.039
  • wR factor = 0.105
  • Data-to-parameter ratio = 8.1

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.64 Ratio PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.62 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.28 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C9 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C13 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C10
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 25.01 From the CIF: _reflns_number_total 1716 Count of symmetry unique reflns 1717 Completeness (_total/calc) 99.94% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5 = . R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 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 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Saccharides are among the most important naturally occurring compounds, and play key roles in the metabolism. Glycal derivatives are a class of important and versatile compounds, which are often derived from saccharides and have found widespread applications in the synthesis of functionalized saccharides with various biological activities (Capozzi et al., 2002; Lin et al., 2005). We herein report the synthesis and crystal structure of a chiral glucal, 1,5-Anhydro-2,3,4,6-tetra-O-acetyl-D-lyxo-hex-1-entiol, which was synthesized from D-galactose. We report here the crystal structure of (I).

The absolute configuration of the title compound was assigned from a knowledge of the stereochemistry of its synthetic precursor. In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported previously (Vangehr et al., 1979). The ring adopt the half-chair conformation 4H5 in the crystalline state. The structure is stabilized by hydrogen bonds of C—H···O type, in addition to van der Waals forces.

Related literature top

For related literature, see: Capozzi et al. (2002); Lin et al. (2005); Vangehr et al. (1979).

Experimental top

Acetyl chloride (10 mmol) was added dropwise to the solution of 1,3-bis(4-fluorophenoxy)benzene (10 mmol), aluminium oxide (13 mmol), carbon sulfide (20 ml) and the mixture was heated under reflux for 2 h. Then the mixture was extracted with CS2 (15 ml) and the organic layer was washed with 50% NaOH solution and water. The excess CS2 was removed on a water vacuum pump to obtain the final product (80% yield). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.93 or 0.96 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C).

Structure description top

Saccharides are among the most important naturally occurring compounds, and play key roles in the metabolism. Glycal derivatives are a class of important and versatile compounds, which are often derived from saccharides and have found widespread applications in the synthesis of functionalized saccharides with various biological activities (Capozzi et al., 2002; Lin et al., 2005). We herein report the synthesis and crystal structure of a chiral glucal, 1,5-Anhydro-2,3,4,6-tetra-O-acetyl-D-lyxo-hex-1-entiol, which was synthesized from D-galactose. We report here the crystal structure of (I).

The absolute configuration of the title compound was assigned from a knowledge of the stereochemistry of its synthetic precursor. In (I) (Fig. 1), all bond lengths and angles are normal and in a good agreement with those reported previously (Vangehr et al., 1979). The ring adopt the half-chair conformation 4H5 in the crystalline state. The structure is stabilized by hydrogen bonds of C—H···O type, in addition to van der Waals forces.

For related literature, see: Capozzi et al. (2002); Lin et al. (2005); Vangehr et al. (1979).

Computing details top

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

Figures top
[Figure 1] Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.
[Figure 2] Fig. 2. A packing diagram of the molecule of the title compound. Hydrogen bonds are shown as dashed lines.
1,5-Anhydro-2,3,4,6-tetra-O-acetyl-D-lyxo-hex-1-enitol top
Crystal data top
C14H18O9F(000) = 696
Mr = 330.28Dx = 1.330 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1048 reflections
a = 5.5438 (9) Åθ = 2.3–22.3°
b = 12.234 (2) ŵ = 0.11 mm1
c = 24.312 (4) ÅT = 298 K
V = 1649.0 (5) Å3Block, colourless
Z = 40.50 × 0.40 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1716 independent reflections
Radiation source: fine-focus sealed tube1624 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
φ and ω scansθmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 66
Tmin = 0.946, Tmax = 0.978k = 1214
8312 measured reflectionsl = 2028
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.105H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0633P)2 + 0.2628P]
where P = (Fo2 + 2Fc2)/3
1716 reflections(Δ/σ)max < 0.001
211 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C14H18O9V = 1649.0 (5) Å3
Mr = 330.28Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.5438 (9) ŵ = 0.11 mm1
b = 12.234 (2) ÅT = 298 K
c = 24.312 (4) Å0.50 × 0.40 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1716 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
1624 reflections with I > 2σ(I)
Tmin = 0.946, Tmax = 0.978Rint = 0.040
8312 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.105H-atom parameters constrained
S = 1.07Δρmax = 0.19 e Å3
1716 reflectionsΔρmin = 0.17 e Å3
211 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.1546 (3)0.13015 (13)0.14145 (7)0.0438 (4)
O20.5874 (4)0.19719 (13)0.09274 (7)0.0449 (5)
O30.8227 (4)0.18316 (14)0.01826 (7)0.0491 (5)
O40.0478 (3)0.05072 (13)0.07124 (7)0.0425 (4)
O50.2868 (5)0.1341 (3)0.01074 (10)0.0927 (9)
O60.0527 (4)0.19092 (14)0.15321 (8)0.0509 (5)
O70.2425 (6)0.3095 (2)0.16694 (17)0.1114 (12)
O80.2334 (3)0.03845 (15)0.22552 (7)0.0504 (5)
O90.0155 (4)0.1276 (2)0.28190 (9)0.0762 (8)
C10.0111 (5)0.0920 (2)0.17801 (9)0.0422 (6)
H1A0.11020.14280.19540.051*
C20.0403 (5)0.0118 (2)0.19047 (10)0.0401 (6)
C30.1064 (5)0.1017 (2)0.16562 (10)0.0410 (6)
H3A0.22890.12580.19200.049*
C40.2294 (5)0.05934 (19)0.11368 (10)0.0400 (6)
H4A0.35650.11010.10220.048*
C50.3366 (5)0.05263 (19)0.12544 (9)0.0391 (5)
H5A0.45210.04530.15570.047*
C60.4671 (6)0.0983 (2)0.07650 (9)0.0461 (6)
H6A0.58390.04570.06310.055*
H6B0.35340.11360.04720.055*
C70.7630 (5)0.23214 (19)0.05877 (9)0.0389 (6)
C80.8643 (7)0.3370 (2)0.07797 (10)0.0561 (8)
H8A1.02230.34690.06260.084*
H8B0.87500.33650.11740.084*
H8C0.76150.39590.06640.084*
C90.0957 (5)0.0947 (2)0.02159 (11)0.0489 (7)
C100.1142 (6)0.0863 (3)0.01573 (12)0.0622 (8)
H10A0.07480.11870.05050.093*
H10B0.15470.01070.02100.093*
H10C0.24920.12390.00010.093*
C110.0378 (7)0.2922 (2)0.15502 (15)0.0621 (8)
C120.1472 (9)0.3745 (3)0.14133 (18)0.0938 (13)
H12A0.08940.44590.15100.141*
H12B0.18040.37210.10260.141*
H12C0.29230.35910.16150.141*
C130.1823 (5)0.0986 (3)0.27069 (11)0.0563 (7)
C140.4027 (7)0.1204 (5)0.30325 (17)0.1029 (17)
H14A0.35860.13890.34030.154*
H14B0.48990.18010.28710.154*
H14C0.50270.05640.30350.154*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0481 (10)0.0396 (8)0.0436 (9)0.0013 (8)0.0102 (9)0.0063 (7)
O20.0519 (11)0.0457 (9)0.0372 (8)0.0086 (9)0.0101 (8)0.0016 (7)
O30.0548 (12)0.0531 (10)0.0395 (9)0.0080 (10)0.0113 (9)0.0041 (8)
O40.0427 (10)0.0493 (9)0.0356 (8)0.0061 (9)0.0012 (8)0.0032 (7)
O50.0618 (16)0.142 (3)0.0743 (15)0.0261 (18)0.0004 (13)0.0500 (16)
O60.0466 (11)0.0427 (9)0.0634 (11)0.0056 (9)0.0067 (10)0.0089 (8)
O70.0763 (19)0.0560 (14)0.202 (4)0.0119 (15)0.019 (2)0.0055 (18)
O80.0378 (10)0.0674 (11)0.0460 (10)0.0031 (10)0.0053 (9)0.0194 (9)
O90.0431 (12)0.132 (2)0.0534 (12)0.0056 (15)0.0001 (10)0.0421 (14)
C10.0428 (15)0.0515 (13)0.0324 (11)0.0037 (12)0.0048 (11)0.0036 (10)
C20.0355 (13)0.0512 (13)0.0338 (12)0.0007 (12)0.0005 (11)0.0076 (10)
C30.0371 (14)0.0431 (12)0.0426 (13)0.0028 (12)0.0045 (11)0.0088 (10)
C40.0361 (13)0.0401 (12)0.0439 (12)0.0044 (11)0.0010 (11)0.0041 (10)
C50.0369 (13)0.0446 (12)0.0359 (11)0.0009 (11)0.0015 (11)0.0050 (10)
C60.0491 (15)0.0527 (13)0.0364 (12)0.0108 (13)0.0061 (12)0.0028 (11)
C70.0433 (14)0.0428 (12)0.0305 (11)0.0013 (12)0.0013 (11)0.0075 (10)
C80.074 (2)0.0502 (14)0.0438 (14)0.0173 (16)0.0089 (15)0.0015 (11)
C90.0456 (17)0.0523 (14)0.0487 (14)0.0064 (13)0.0074 (13)0.0148 (12)
C100.0591 (19)0.0769 (19)0.0506 (15)0.0012 (17)0.0038 (15)0.0203 (15)
C110.065 (2)0.0491 (16)0.072 (2)0.0006 (16)0.0018 (18)0.0035 (14)
C120.102 (3)0.0527 (18)0.127 (3)0.016 (2)0.015 (3)0.003 (2)
C130.0398 (16)0.0832 (19)0.0461 (14)0.0016 (15)0.0015 (13)0.0234 (15)
C140.052 (2)0.160 (4)0.096 (3)0.009 (3)0.021 (2)0.072 (3)
Geometric parameters (Å, º) top
O1—C11.361 (3)C5—C61.501 (3)
O1—C51.438 (3)C5—H5A0.9800
O2—C71.346 (3)C6—H6A0.9700
O2—C61.436 (3)C6—H6B0.9700
O3—C71.200 (3)C7—C81.477 (4)
O4—C91.348 (3)C8—H8A0.9600
O4—C41.445 (3)C8—H8B0.9600
O5—C91.193 (4)C8—H8C0.9600
O6—C111.337 (4)C9—C101.479 (4)
O6—C31.436 (3)C10—H10A0.9600
O7—C111.190 (4)C10—H10B0.9600
O8—C131.352 (3)C10—H10C0.9600
O8—C21.407 (3)C11—C121.475 (5)
O9—C131.184 (4)C12—H12A0.9600
C1—C21.316 (4)C12—H12B0.9600
C1—H1A0.9300C12—H12C0.9600
C2—C31.495 (4)C13—C141.480 (4)
C3—C41.526 (3)C14—H14A0.9600
C3—H3A0.9800C14—H14B0.9600
C4—C51.520 (3)C14—H14C0.9600
C4—H4A0.9800
C1—O1—C5115.12 (18)O3—C7—C8126.1 (2)
C7—O2—C6115.74 (18)O2—C7—C8110.9 (2)
C9—O4—C4118.2 (2)C7—C8—H8A109.5
C11—O6—C3117.9 (2)C7—C8—H8B109.5
C13—O8—C2117.3 (2)H8A—C8—H8B109.5
C2—C1—O1124.3 (2)C7—C8—H8C109.5
C2—C1—H1A117.8H8A—C8—H8C109.5
O1—C1—H1A117.8H8B—C8—H8C109.5
C1—C2—O8117.2 (2)O5—C9—O4122.3 (3)
C1—C2—C3123.4 (2)O5—C9—C10126.2 (3)
O8—C2—C3119.2 (2)O4—C9—C10111.5 (2)
O6—C3—C2108.1 (2)C9—C10—H10A109.5
O6—C3—C4111.0 (2)C9—C10—H10B109.5
C2—C3—C4109.14 (19)H10A—C10—H10B109.5
O6—C3—H3A109.5C9—C10—H10C109.5
C2—C3—H3A109.5H10A—C10—H10C109.5
C4—C3—H3A109.5H10B—C10—H10C109.5
O4—C4—C5109.92 (18)O7—C11—O6122.0 (3)
O4—C4—C3107.7 (2)O7—C11—C12126.6 (3)
C5—C4—C3109.0 (2)O6—C11—C12111.4 (3)
O4—C4—H4A110.1C11—C12—H12A109.5
C5—C4—H4A110.1C11—C12—H12B109.5
C3—C4—H4A110.1H12A—C12—H12B109.5
O1—C5—C6107.9 (2)C11—C12—H12C109.5
O1—C5—C4111.8 (2)H12A—C12—H12C109.5
C6—C5—C4112.0 (2)H12B—C12—H12C109.5
O1—C5—H5A108.3O9—C13—O8122.9 (3)
C6—C5—H5A108.3O9—C13—C14126.0 (3)
C4—C5—H5A108.3O8—C13—C14111.1 (3)
O2—C6—C5108.64 (19)C13—C14—H14A109.5
O2—C6—H6A110.0C13—C14—H14B109.5
C5—C6—H6A110.0H14A—C14—H14B109.5
O2—C6—H6B110.0C13—C14—H14C109.5
C5—C6—H6B110.0H14A—C14—H14C109.5
H6A—C6—H6B108.3H14B—C14—H14C109.5
O3—C7—O2123.0 (2)
C5—O1—C1—C213.4 (4)C1—O1—C5—C6167.4 (2)
O1—C1—C2—O8174.7 (2)C1—O1—C5—C443.8 (3)
O1—C1—C2—C30.1 (4)O4—C4—C5—O157.5 (2)
C13—O8—C2—C1127.1 (3)C3—C4—C5—O160.4 (2)
C13—O8—C2—C358.0 (3)O4—C4—C5—C663.8 (3)
C11—O6—C3—C2149.9 (2)C3—C4—C5—C6178.4 (2)
C11—O6—C3—C490.5 (3)C7—O2—C6—C5162.6 (2)
C1—C2—C3—O6138.1 (3)O1—C5—C6—O263.5 (3)
O8—C2—C3—O636.4 (3)C4—C5—C6—O2173.1 (2)
C1—C2—C3—C417.3 (4)C6—O2—C7—O32.2 (4)
O8—C2—C3—C4157.2 (2)C6—O2—C7—C8176.9 (2)
C9—O4—C4—C5110.5 (2)C4—O4—C9—O54.7 (4)
C9—O4—C4—C3130.9 (2)C4—O4—C9—C10175.8 (2)
O6—C3—C4—O444.7 (3)C3—O6—C11—O70.7 (5)
C2—C3—C4—O474.3 (2)C3—O6—C11—C12180.0 (3)
O6—C3—C4—C5164.0 (2)C2—O8—C13—O91.2 (5)
C2—C3—C4—C544.9 (3)C2—O8—C13—C14179.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8B···O9i0.962.563.498 (3)165
C10—H10B···O3ii0.962.563.416 (4)149
C10—H10C···O5ii0.962.593.433 (5)147
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x1, y, z.

Experimental details

Crystal data
Chemical formulaC14H18O9
Mr330.28
Crystal system, space groupOrthorhombic, P212121
Temperature (K)298
a, b, c (Å)5.5438 (9), 12.234 (2), 24.312 (4)
V3)1649.0 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.50 × 0.40 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.946, 0.978
No. of measured, independent and
observed [I > 2σ(I)] reflections
8312, 1716, 1624
Rint0.040
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.105, 1.07
No. of reflections1716
No. of parameters211
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.17

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8B···O9i0.962.563.498 (3)165.4
C10—H10B···O3ii0.962.563.416 (4)148.6
C10—H10C···O5ii0.962.593.433 (5)146.9
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x1, y, z.
 

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