Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049379/hg2312sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049379/hg2312Isup2.hkl |
CCDC reference: 667359
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.
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).
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).
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).
C14H18O9 | F(000) = 696 |
Mr = 330.28 | Dx = 1.330 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1048 reflections |
a = 5.5438 (9) Å | θ = 2.3–22.3° |
b = 12.234 (2) Å | µ = 0.11 mm−1 |
c = 24.312 (4) Å | T = 298 K |
V = 1649.0 (5) Å3 | Block, colourless |
Z = 4 | 0.50 × 0.40 × 0.20 mm |
Bruker SMART CCD area-detector diffractometer | 1716 independent reflections |
Radiation source: fine-focus sealed tube | 1624 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
φ and ω scans | θmax = 25.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −6→6 |
Tmin = 0.946, Tmax = 0.978 | k = −12→14 |
8312 measured reflections | l = −20→28 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-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 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C14H18O9 | V = 1649.0 (5) Å3 |
Mr = 330.28 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.5438 (9) Å | µ = 0.11 mm−1 |
b = 12.234 (2) Å | T = 298 K |
c = 24.312 (4) Å | 0.50 × 0.40 × 0.20 mm |
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 = 0.978 | Rint = 0.040 |
8312 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.19 e Å−3 |
1716 reflections | Δρmin = −0.17 e Å−3 |
211 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.1546 (3) | 0.13015 (13) | 0.14145 (7) | 0.0438 (4) | |
O2 | 0.5874 (4) | 0.19719 (13) | 0.09274 (7) | 0.0449 (5) | |
O3 | 0.8227 (4) | 0.18316 (14) | 0.01826 (7) | 0.0491 (5) | |
O4 | 0.0478 (3) | −0.05072 (13) | 0.07124 (7) | 0.0425 (4) | |
O5 | 0.2868 (5) | −0.1341 (3) | 0.01074 (10) | 0.0927 (9) | |
O6 | −0.0527 (4) | −0.19092 (14) | 0.15321 (8) | 0.0509 (5) | |
O7 | 0.2425 (6) | −0.3095 (2) | 0.16694 (17) | 0.1114 (12) | |
O8 | −0.2334 (3) | −0.03845 (15) | 0.22552 (7) | 0.0504 (5) | |
O9 | 0.0155 (4) | −0.1276 (2) | 0.28190 (9) | 0.0762 (8) | |
C1 | −0.0111 (5) | 0.0920 (2) | 0.17801 (9) | 0.0422 (6) | |
H1A | −0.1102 | 0.1428 | 0.1954 | 0.051* | |
C2 | −0.0403 (5) | −0.0118 (2) | 0.19047 (10) | 0.0401 (6) | |
C3 | 0.1064 (5) | −0.1017 (2) | 0.16562 (10) | 0.0410 (6) | |
H3A | 0.2289 | −0.1258 | 0.1920 | 0.049* | |
C4 | 0.2294 (5) | −0.05934 (19) | 0.11368 (10) | 0.0400 (6) | |
H4A | 0.3565 | −0.1101 | 0.1022 | 0.048* | |
C5 | 0.3366 (5) | 0.05263 (19) | 0.12544 (9) | 0.0391 (5) | |
H5A | 0.4521 | 0.0453 | 0.1557 | 0.047* | |
C6 | 0.4671 (6) | 0.0983 (2) | 0.07650 (9) | 0.0461 (6) | |
H6A | 0.5839 | 0.0457 | 0.0631 | 0.055* | |
H6B | 0.3534 | 0.1136 | 0.0472 | 0.055* | |
C7 | 0.7630 (5) | 0.23214 (19) | 0.05877 (9) | 0.0389 (6) | |
C8 | 0.8643 (7) | 0.3370 (2) | 0.07797 (10) | 0.0561 (8) | |
H8A | 1.0223 | 0.3469 | 0.0626 | 0.084* | |
H8B | 0.8750 | 0.3365 | 0.1174 | 0.084* | |
H8C | 0.7615 | 0.3959 | 0.0664 | 0.084* | |
C9 | 0.0957 (5) | −0.0947 (2) | 0.02159 (11) | 0.0489 (7) | |
C10 | −0.1142 (6) | −0.0863 (3) | −0.01573 (12) | 0.0622 (8) | |
H10A | −0.0748 | −0.1187 | −0.0505 | 0.093* | |
H10B | −0.1547 | −0.0107 | −0.0210 | 0.093* | |
H10C | −0.2492 | −0.1239 | 0.0001 | 0.093* | |
C11 | 0.0378 (7) | −0.2922 (2) | 0.15502 (15) | 0.0621 (8) | |
C12 | −0.1472 (9) | −0.3745 (3) | 0.14133 (18) | 0.0938 (13) | |
H12A | −0.0894 | −0.4459 | 0.1510 | 0.141* | |
H12B | −0.1804 | −0.3721 | 0.1026 | 0.141* | |
H12C | −0.2923 | −0.3591 | 0.1615 | 0.141* | |
C13 | −0.1823 (5) | −0.0986 (3) | 0.27069 (11) | 0.0563 (7) | |
C14 | −0.4027 (7) | −0.1204 (5) | 0.30325 (17) | 0.1029 (17) | |
H14A | −0.3586 | −0.1389 | 0.3403 | 0.154* | |
H14B | −0.4899 | −0.1801 | 0.2871 | 0.154* | |
H14C | −0.5027 | −0.0564 | 0.3035 | 0.154* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0481 (10) | 0.0396 (8) | 0.0436 (9) | 0.0013 (8) | 0.0102 (9) | 0.0063 (7) |
O2 | 0.0519 (11) | 0.0457 (9) | 0.0372 (8) | −0.0086 (9) | 0.0101 (8) | −0.0016 (7) |
O3 | 0.0548 (12) | 0.0531 (10) | 0.0395 (9) | −0.0080 (10) | 0.0113 (9) | −0.0041 (8) |
O4 | 0.0427 (10) | 0.0493 (9) | 0.0356 (8) | 0.0061 (9) | −0.0012 (8) | −0.0032 (7) |
O5 | 0.0618 (16) | 0.142 (3) | 0.0743 (15) | 0.0261 (18) | 0.0004 (13) | −0.0500 (16) |
O6 | 0.0466 (11) | 0.0427 (9) | 0.0634 (11) | −0.0056 (9) | −0.0067 (10) | 0.0089 (8) |
O7 | 0.0763 (19) | 0.0560 (14) | 0.202 (4) | 0.0119 (15) | −0.019 (2) | −0.0055 (18) |
O8 | 0.0378 (10) | 0.0674 (11) | 0.0460 (10) | 0.0031 (10) | 0.0053 (9) | 0.0194 (9) |
O9 | 0.0431 (12) | 0.132 (2) | 0.0534 (12) | 0.0056 (15) | −0.0001 (10) | 0.0421 (14) |
C1 | 0.0428 (15) | 0.0515 (13) | 0.0324 (11) | 0.0037 (12) | 0.0048 (11) | 0.0036 (10) |
C2 | 0.0355 (13) | 0.0512 (13) | 0.0338 (12) | −0.0007 (12) | 0.0005 (11) | 0.0076 (10) |
C3 | 0.0371 (14) | 0.0431 (12) | 0.0426 (13) | −0.0028 (12) | −0.0045 (11) | 0.0088 (10) |
C4 | 0.0361 (13) | 0.0401 (12) | 0.0439 (12) | 0.0044 (11) | −0.0010 (11) | 0.0041 (10) |
C5 | 0.0369 (13) | 0.0446 (12) | 0.0359 (11) | 0.0009 (11) | −0.0015 (11) | 0.0050 (10) |
C6 | 0.0491 (15) | 0.0527 (13) | 0.0364 (12) | −0.0108 (13) | 0.0061 (12) | −0.0028 (11) |
C7 | 0.0433 (14) | 0.0428 (12) | 0.0305 (11) | −0.0013 (12) | 0.0013 (11) | 0.0075 (10) |
C8 | 0.074 (2) | 0.0502 (14) | 0.0438 (14) | −0.0173 (16) | 0.0089 (15) | −0.0015 (11) |
C9 | 0.0456 (17) | 0.0523 (14) | 0.0487 (14) | −0.0064 (13) | 0.0074 (13) | −0.0148 (12) |
C10 | 0.0591 (19) | 0.0769 (19) | 0.0506 (15) | −0.0012 (17) | −0.0038 (15) | −0.0203 (15) |
C11 | 0.065 (2) | 0.0491 (16) | 0.072 (2) | −0.0006 (16) | −0.0018 (18) | 0.0035 (14) |
C12 | 0.102 (3) | 0.0527 (18) | 0.127 (3) | −0.016 (2) | −0.015 (3) | −0.003 (2) |
C13 | 0.0398 (16) | 0.0832 (19) | 0.0461 (14) | −0.0016 (15) | 0.0015 (13) | 0.0234 (15) |
C14 | 0.052 (2) | 0.160 (4) | 0.096 (3) | 0.009 (3) | 0.021 (2) | 0.072 (3) |
O1—C1 | 1.361 (3) | C5—C6 | 1.501 (3) |
O1—C5 | 1.438 (3) | C5—H5A | 0.9800 |
O2—C7 | 1.346 (3) | C6—H6A | 0.9700 |
O2—C6 | 1.436 (3) | C6—H6B | 0.9700 |
O3—C7 | 1.200 (3) | C7—C8 | 1.477 (4) |
O4—C9 | 1.348 (3) | C8—H8A | 0.9600 |
O4—C4 | 1.445 (3) | C8—H8B | 0.9600 |
O5—C9 | 1.193 (4) | C8—H8C | 0.9600 |
O6—C11 | 1.337 (4) | C9—C10 | 1.479 (4) |
O6—C3 | 1.436 (3) | C10—H10A | 0.9600 |
O7—C11 | 1.190 (4) | C10—H10B | 0.9600 |
O8—C13 | 1.352 (3) | C10—H10C | 0.9600 |
O8—C2 | 1.407 (3) | C11—C12 | 1.475 (5) |
O9—C13 | 1.184 (4) | C12—H12A | 0.9600 |
C1—C2 | 1.316 (4) | C12—H12B | 0.9600 |
C1—H1A | 0.9300 | C12—H12C | 0.9600 |
C2—C3 | 1.495 (4) | C13—C14 | 1.480 (4) |
C3—C4 | 1.526 (3) | C14—H14A | 0.9600 |
C3—H3A | 0.9800 | C14—H14B | 0.9600 |
C4—C5 | 1.520 (3) | C14—H14C | 0.9600 |
C4—H4A | 0.9800 | ||
C1—O1—C5 | 115.12 (18) | O3—C7—C8 | 126.1 (2) |
C7—O2—C6 | 115.74 (18) | O2—C7—C8 | 110.9 (2) |
C9—O4—C4 | 118.2 (2) | C7—C8—H8A | 109.5 |
C11—O6—C3 | 117.9 (2) | C7—C8—H8B | 109.5 |
C13—O8—C2 | 117.3 (2) | H8A—C8—H8B | 109.5 |
C2—C1—O1 | 124.3 (2) | C7—C8—H8C | 109.5 |
C2—C1—H1A | 117.8 | H8A—C8—H8C | 109.5 |
O1—C1—H1A | 117.8 | H8B—C8—H8C | 109.5 |
C1—C2—O8 | 117.2 (2) | O5—C9—O4 | 122.3 (3) |
C1—C2—C3 | 123.4 (2) | O5—C9—C10 | 126.2 (3) |
O8—C2—C3 | 119.2 (2) | O4—C9—C10 | 111.5 (2) |
O6—C3—C2 | 108.1 (2) | C9—C10—H10A | 109.5 |
O6—C3—C4 | 111.0 (2) | C9—C10—H10B | 109.5 |
C2—C3—C4 | 109.14 (19) | H10A—C10—H10B | 109.5 |
O6—C3—H3A | 109.5 | C9—C10—H10C | 109.5 |
C2—C3—H3A | 109.5 | H10A—C10—H10C | 109.5 |
C4—C3—H3A | 109.5 | H10B—C10—H10C | 109.5 |
O4—C4—C5 | 109.92 (18) | O7—C11—O6 | 122.0 (3) |
O4—C4—C3 | 107.7 (2) | O7—C11—C12 | 126.6 (3) |
C5—C4—C3 | 109.0 (2) | O6—C11—C12 | 111.4 (3) |
O4—C4—H4A | 110.1 | C11—C12—H12A | 109.5 |
C5—C4—H4A | 110.1 | C11—C12—H12B | 109.5 |
C3—C4—H4A | 110.1 | H12A—C12—H12B | 109.5 |
O1—C5—C6 | 107.9 (2) | C11—C12—H12C | 109.5 |
O1—C5—C4 | 111.8 (2) | H12A—C12—H12C | 109.5 |
C6—C5—C4 | 112.0 (2) | H12B—C12—H12C | 109.5 |
O1—C5—H5A | 108.3 | O9—C13—O8 | 122.9 (3) |
C6—C5—H5A | 108.3 | O9—C13—C14 | 126.0 (3) |
C4—C5—H5A | 108.3 | O8—C13—C14 | 111.1 (3) |
O2—C6—C5 | 108.64 (19) | C13—C14—H14A | 109.5 |
O2—C6—H6A | 110.0 | C13—C14—H14B | 109.5 |
C5—C6—H6A | 110.0 | H14A—C14—H14B | 109.5 |
O2—C6—H6B | 110.0 | C13—C14—H14C | 109.5 |
C5—C6—H6B | 110.0 | H14A—C14—H14C | 109.5 |
H6A—C6—H6B | 108.3 | H14B—C14—H14C | 109.5 |
O3—C7—O2 | 123.0 (2) | ||
C5—O1—C1—C2 | −13.4 (4) | C1—O1—C5—C6 | 167.4 (2) |
O1—C1—C2—O8 | −174.7 (2) | C1—O1—C5—C4 | 43.8 (3) |
O1—C1—C2—C3 | −0.1 (4) | O4—C4—C5—O1 | 57.5 (2) |
C13—O8—C2—C1 | −127.1 (3) | C3—C4—C5—O1 | −60.4 (2) |
C13—O8—C2—C3 | 58.0 (3) | O4—C4—C5—C6 | −63.8 (3) |
C11—O6—C3—C2 | −149.9 (2) | C3—C4—C5—C6 | 178.4 (2) |
C11—O6—C3—C4 | 90.5 (3) | C7—O2—C6—C5 | 162.6 (2) |
C1—C2—C3—O6 | −138.1 (3) | O1—C5—C6—O2 | 63.5 (3) |
O8—C2—C3—O6 | 36.4 (3) | C4—C5—C6—O2 | −173.1 (2) |
C1—C2—C3—C4 | −17.3 (4) | C6—O2—C7—O3 | −2.2 (4) |
O8—C2—C3—C4 | 157.2 (2) | C6—O2—C7—C8 | 176.9 (2) |
C9—O4—C4—C5 | 110.5 (2) | C4—O4—C9—O5 | −4.7 (4) |
C9—O4—C4—C3 | −130.9 (2) | C4—O4—C9—C10 | 175.8 (2) |
O6—C3—C4—O4 | 44.7 (3) | C3—O6—C11—O7 | 0.7 (5) |
C2—C3—C4—O4 | −74.3 (2) | C3—O6—C11—C12 | 180.0 (3) |
O6—C3—C4—C5 | 164.0 (2) | C2—O8—C13—O9 | 1.2 (5) |
C2—C3—C4—C5 | 44.9 (3) | C2—O8—C13—C14 | −179.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···O9i | 0.96 | 2.56 | 3.498 (3) | 165 |
C10—H10B···O3ii | 0.96 | 2.56 | 3.416 (4) | 149 |
C10—H10C···O5ii | 0.96 | 2.59 | 3.433 (5) | 147 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C14H18O9 |
Mr | 330.28 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 5.5438 (9), 12.234 (2), 24.312 (4) |
V (Å3) | 1649.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.50 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.946, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8312, 1716, 1624 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.105, 1.07 |
No. of reflections | 1716 |
No. of parameters | 211 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.17 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8B···O9i | 0.96 | 2.56 | 3.498 (3) | 165.4 |
C10—H10B···O3ii | 0.96 | 2.56 | 3.416 (4) | 148.6 |
C10—H10C···O5ii | 0.96 | 2.59 | 3.433 (5) | 146.9 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, y, z. |
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.