Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041244/bt2451sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041244/bt2451Isup2.hkl |
CCDC reference: 662416
The title compound was obtained accidentally as the sole product on the attempted preparation of an orthocarbonate by the reaction of dichlorodiphenoxymethane, (PhO)2CCl2, with 1,2:5,6-di-O-isopropylidene-D-mannitol in analogy to a literature procedure (Mues & Buysch, 1990). The crude product was recrystallized from boiling ethyl acetate.
All H atoms were located in a difference map and refined as riding on their parent atoms. One common isotropic displacement parameter for all H atoms was refined to Uiso(H) = 0.059 (2) Å2.
Due to the absence of significant anomalous scattering the absolute structure factor (Flack, 1983), which is 2.9 with an estimated standard deviation of 1.8 for the unmerged data set, is meaningless. Thus, Friedel opposites (1329 pairs) have been merged. The absolute structure has been assigned to match the known sterochemistry of the starting material 1,2:5,6-di-O-isopropylidene-D-mannitol.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
The title compound, C13H20O7, the carbonate of a partially protected sugar alcohol, 1,2:5,6-di-O-isopropylidene-D-mannitol, was obtained accidentally on the attempted preparation of an orthocarbonate thereof.
The molecular structure is shown in Fig. 1. The 5-membered 1,3-dioxolane ring O1–C1–C2–O2–C12 adopts a twist conformation on O1—C1 (Q2 = 0.324 (3) Å, φ2 = 16.7 (6)°), whereas O5–C5–C6–O6–C22 (Q2 = 0.302 (3) Å, φ2 = 319.3 (6)°) shows an envelope conformation on C22. The dioxolane ring O3–C3–C4–O4–C10, which contains the carbonate group, is twisted on C3—C4 (Q2 = 0.165 (3) Å, φ2 = 57.8 (11)°). Ring puckering parameters (Cremer & Pople, 1975) were calculated with PLATON (Spek, 2003).
The molecular packing is shown in Fig. 2.
For related literature, see: Hough et al. (1962); Baker & Sachdev (1963); Mues & Buysch (1990). For analysis tools, see: Cremer & Pople (1975); Flack (1983).
Data collection: COLLECT (Nonius, 2004); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).
C13H20O7 | F(000) = 616 |
Mr = 288.29 | Dx = 1.367 (1) Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 13166 reflections |
a = 6.0863 (3) Å | θ = 3.1–27.5° |
b = 11.6958 (4) Å | µ = 0.11 mm−1 |
c = 19.6816 (8) Å | T = 200 K |
V = 1401.02 (10) Å3 | Needle, colourless |
Z = 4 | 0.16 × 0.04 × 0.04 mm |
Nonius KappaCCD area-detector diffractometer | 1153 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.059 |
MONTEL, graded multilayered X-ray optics monochromator | θmax = 27.5°, θmin = 3.5° |
Detector resolution: 9 pixels mm-1 | h = −7→7 |
φ and ω scans | k = −15→15 |
3191 measured reflections | l = −25→25 |
1858 independent reflections |
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)] = 0.045 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.114 | Only H-atom displacement parameters refined |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0615P)2] where P = (Fo2 + 2Fc2)/3 |
1858 reflections | (Δ/σ)max < 0.001 |
186 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C13H20O7 | V = 1401.02 (10) Å3 |
Mr = 288.29 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.0863 (3) Å | µ = 0.11 mm−1 |
b = 11.6958 (4) Å | T = 200 K |
c = 19.6816 (8) Å | 0.16 × 0.04 × 0.04 mm |
Nonius KappaCCD area-detector diffractometer | 1153 reflections with I > 2σ(I) |
3191 measured reflections | Rint = 0.059 |
1858 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.114 | Only H-atom displacement parameters refined |
S = 1.00 | Δρmax = 0.16 e Å−3 |
1858 reflections | Δρmin = −0.26 e Å−3 |
186 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 > 2σ(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 | 0.3167 (4) | 0.4262 (2) | 0.04204 (11) | 0.0471 (6) | |
O2 | 0.0435 (4) | 0.4772 (2) | 0.11497 (10) | 0.0442 (6) | |
O3 | 0.4588 (4) | 0.52808 (19) | 0.24498 (11) | 0.0447 (6) | |
O4 | 0.2177 (4) | 0.64536 (16) | 0.29075 (10) | 0.0392 (6) | |
O5 | 0.1688 (4) | 0.43473 (18) | 0.35795 (10) | 0.0410 (6) | |
O6 | −0.0359 (4) | 0.28634 (17) | 0.32210 (11) | 0.0440 (6) | |
O10 | 0.5768 (5) | 0.6762 (2) | 0.30616 (13) | 0.0634 (8) | |
C1 | 0.4190 (6) | 0.4462 (3) | 0.10539 (15) | 0.0433 (8) | |
H11 | 0.5558 | 0.4911 | 0.0998 | 0.059 (2)* | |
H12 | 0.4537 | 0.3735 | 0.1288 | 0.059 (2)* | |
C2 | 0.2473 (6) | 0.5135 (2) | 0.14394 (14) | 0.0361 (8) | |
H2 | 0.2686 | 0.5972 | 0.1360 | 0.059 (2)* | |
C3 | 0.2486 (5) | 0.4882 (2) | 0.22009 (15) | 0.0370 (8) | |
H3 | 0.2329 | 0.4042 | 0.2282 | 0.059 (2)* | |
C4 | 0.0853 (5) | 0.5539 (3) | 0.26282 (14) | 0.0342 (7) | |
H4 | −0.0350 | 0.5856 | 0.2338 | 0.059 (2)* | |
C5 | −0.0096 (6) | 0.4859 (2) | 0.32170 (15) | 0.0389 (8) | |
H5 | −0.0949 | 0.5374 | 0.3525 | 0.059 (2)* | |
C6 | −0.1529 (6) | 0.3852 (3) | 0.29908 (17) | 0.0461 (9) | |
H61 | −0.3003 | 0.3893 | 0.3202 | 0.059 (2)* | |
H62 | −0.1696 | 0.3842 | 0.2491 | 0.059 (2)* | |
C10 | 0.4302 (6) | 0.6218 (3) | 0.28301 (16) | 0.0420 (8) | |
C11 | −0.0367 (7) | 0.4552 (3) | −0.00416 (16) | 0.0527 (10) | |
H111 | 0.0049 | 0.4136 | −0.0454 | 0.059 (2)* | |
H112 | −0.0033 | 0.5366 | −0.0099 | 0.059 (2)* | |
H113 | −0.1944 | 0.4456 | 0.0041 | 0.059 (2)* | |
C12 | 0.0902 (6) | 0.4089 (3) | 0.05523 (15) | 0.0400 (8) | |
C13 | 0.0364 (7) | 0.2857 (3) | 0.0715 (2) | 0.0542 (10) | |
H131 | 0.1349 | 0.2582 | 0.1073 | 0.059 (2)* | |
H132 | 0.0554 | 0.2389 | 0.0307 | 0.059 (2)* | |
H133 | −0.1162 | 0.2803 | 0.0871 | 0.059 (2)* | |
C21 | 0.3026 (7) | 0.2459 (3) | 0.37563 (17) | 0.0499 (9) | |
H211 | 0.4105 | 0.2747 | 0.4084 | 0.059 (2)* | |
H212 | 0.3679 | 0.2451 | 0.3301 | 0.059 (2)* | |
H213 | 0.2590 | 0.1681 | 0.3883 | 0.059 (2)* | |
C22 | 0.1052 (6) | 0.3218 (3) | 0.37579 (15) | 0.0370 (8) | |
C23 | −0.0157 (7) | 0.3221 (3) | 0.44255 (17) | 0.0547 (10) | |
H231 | 0.0792 | 0.3541 | 0.4780 | 0.059 (2)* | |
H232 | −0.0564 | 0.2437 | 0.4547 | 0.059 (2)* | |
H233 | −0.1488 | 0.3688 | 0.4384 | 0.059 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0490 (16) | 0.0524 (14) | 0.0398 (12) | 0.0003 (13) | 0.0080 (12) | −0.0053 (11) |
O2 | 0.0397 (14) | 0.0545 (14) | 0.0383 (12) | 0.0032 (12) | 0.0004 (11) | −0.0122 (11) |
O3 | 0.0407 (15) | 0.0514 (14) | 0.0421 (12) | 0.0062 (12) | −0.0042 (11) | −0.0051 (11) |
O4 | 0.0464 (15) | 0.0292 (11) | 0.0420 (12) | −0.0005 (10) | 0.0015 (11) | −0.0011 (10) |
O5 | 0.0485 (15) | 0.0343 (10) | 0.0403 (11) | −0.0035 (11) | −0.0062 (12) | 0.0049 (9) |
O6 | 0.0522 (16) | 0.0317 (11) | 0.0482 (13) | −0.0018 (11) | −0.0116 (12) | 0.0008 (10) |
O10 | 0.0551 (18) | 0.0756 (17) | 0.0595 (16) | −0.0169 (17) | −0.0102 (15) | −0.0074 (14) |
C1 | 0.041 (2) | 0.0480 (19) | 0.0414 (17) | −0.0007 (18) | 0.0032 (17) | −0.0082 (16) |
C2 | 0.040 (2) | 0.0349 (15) | 0.0335 (15) | −0.0019 (16) | 0.0010 (15) | −0.0020 (13) |
C3 | 0.042 (2) | 0.0303 (14) | 0.0391 (16) | 0.0002 (15) | −0.0035 (15) | −0.0001 (13) |
C4 | 0.0383 (19) | 0.0305 (15) | 0.0337 (15) | 0.0013 (15) | −0.0015 (15) | 0.0024 (13) |
C5 | 0.045 (2) | 0.0350 (16) | 0.0369 (16) | 0.0025 (16) | 0.0006 (15) | 0.0012 (14) |
C6 | 0.045 (2) | 0.0381 (16) | 0.056 (2) | −0.0002 (16) | −0.0038 (18) | 0.0109 (16) |
C10 | 0.046 (2) | 0.0435 (18) | 0.0367 (17) | −0.0026 (19) | −0.0040 (18) | 0.0036 (16) |
C11 | 0.062 (3) | 0.057 (2) | 0.0394 (17) | 0.002 (2) | −0.0045 (19) | 0.0043 (16) |
C12 | 0.043 (2) | 0.0441 (19) | 0.0327 (16) | 0.0011 (17) | 0.0027 (16) | −0.0075 (13) |
C13 | 0.060 (3) | 0.0416 (18) | 0.061 (2) | −0.0052 (19) | −0.008 (2) | −0.0011 (17) |
C21 | 0.055 (2) | 0.0486 (18) | 0.0464 (18) | 0.0096 (19) | −0.0025 (19) | 0.0013 (17) |
C22 | 0.045 (2) | 0.0330 (15) | 0.0333 (16) | −0.0022 (16) | −0.0008 (15) | 0.0006 (13) |
C23 | 0.064 (3) | 0.057 (2) | 0.043 (2) | −0.002 (2) | 0.0130 (19) | 0.0072 (16) |
O1—C1 | 1.413 (4) | C4—H4 | 1.0000 |
O1—C12 | 1.417 (4) | C5—C6 | 1.531 (4) |
O2—C2 | 1.429 (4) | C5—H5 | 1.0000 |
O2—C12 | 1.449 (4) | C6—H61 | 0.9900 |
O3—C10 | 1.339 (4) | C6—H62 | 0.9900 |
O3—C3 | 1.447 (4) | C11—C12 | 1.502 (5) |
O4—C10 | 1.331 (4) | C11—H111 | 0.9800 |
O4—C4 | 1.448 (4) | C11—H112 | 0.9800 |
O5—C22 | 1.420 (4) | C11—H113 | 0.9800 |
O5—C5 | 1.430 (4) | C12—C13 | 1.512 (5) |
O6—C22 | 1.424 (4) | C13—H131 | 0.9800 |
O6—C6 | 1.431 (4) | C13—H132 | 0.9800 |
O10—C10 | 1.187 (4) | C13—H133 | 0.9800 |
C1—C2 | 1.512 (4) | C21—C22 | 1.494 (5) |
C1—H11 | 0.9900 | C21—H211 | 0.9800 |
C1—H12 | 0.9900 | C21—H212 | 0.9800 |
C2—C3 | 1.528 (4) | C21—H213 | 0.9800 |
C2—H2 | 1.0000 | C22—C23 | 1.506 (5) |
C3—C4 | 1.512 (4) | C23—H231 | 0.9800 |
C3—H3 | 1.0000 | C23—H232 | 0.9800 |
C4—C5 | 1.520 (4) | C23—H233 | 0.9800 |
C1—O1—C12 | 106.9 (2) | H61—C6—H62 | 108.9 |
C2—O2—C12 | 108.5 (2) | O10—C10—O4 | 125.2 (3) |
C10—O3—C3 | 109.8 (3) | O10—C10—O3 | 123.8 (4) |
C10—O4—C4 | 110.2 (2) | O4—C10—O3 | 111.1 (3) |
C22—O5—C5 | 107.8 (2) | C12—C11—H111 | 109.5 |
C22—O6—C6 | 107.4 (2) | C12—C11—H112 | 109.5 |
O1—C1—C2 | 103.0 (3) | H111—C11—H112 | 109.5 |
O1—C1—H11 | 111.2 | C12—C11—H113 | 109.5 |
C2—C1—H11 | 111.2 | H111—C11—H113 | 109.5 |
O1—C1—H12 | 111.2 | H112—C11—H113 | 109.5 |
C2—C1—H12 | 111.2 | O1—C12—O2 | 105.1 (3) |
H11—C1—H12 | 109.1 | O1—C12—C11 | 107.8 (3) |
O2—C2—C1 | 104.2 (2) | O2—C12—C11 | 109.4 (3) |
O2—C2—C3 | 109.8 (2) | O1—C12—C13 | 112.7 (3) |
C1—C2—C3 | 112.8 (3) | O2—C12—C13 | 108.1 (3) |
O2—C2—H2 | 110.0 | C11—C12—C13 | 113.4 (3) |
C1—C2—H2 | 110.0 | C12—C13—H131 | 109.5 |
C3—C2—H2 | 110.0 | C12—C13—H132 | 109.5 |
O3—C3—C4 | 103.2 (2) | H131—C13—H132 | 109.5 |
O3—C3—C2 | 105.9 (2) | C12—C13—H133 | 109.5 |
C4—C3—C2 | 116.3 (3) | H131—C13—H133 | 109.5 |
O3—C3—H3 | 110.3 | H132—C13—H133 | 109.5 |
C4—C3—H3 | 110.3 | C22—C21—H211 | 109.5 |
C2—C3—H3 | 110.3 | C22—C21—H212 | 109.5 |
O4—C4—C3 | 102.7 (3) | H211—C21—H212 | 109.5 |
O4—C4—C5 | 108.0 (2) | C22—C21—H213 | 109.5 |
C3—C4—C5 | 114.1 (3) | H211—C21—H213 | 109.5 |
O4—C4—H4 | 110.6 | H212—C21—H213 | 109.5 |
C3—C4—H4 | 110.6 | O5—C22—O6 | 104.6 (2) |
C5—C4—H4 | 110.6 | O5—C22—C21 | 109.5 (3) |
O5—C5—C4 | 108.1 (3) | O6—C22—C21 | 108.1 (2) |
O5—C5—C6 | 104.8 (2) | O5—C22—C23 | 110.3 (2) |
C4—C5—C6 | 113.4 (3) | O6—C22—C23 | 110.7 (3) |
O5—C5—H5 | 110.1 | C21—C22—C23 | 113.4 (3) |
C4—C5—H5 | 110.1 | C22—C23—H231 | 109.5 |
C6—C5—H5 | 110.1 | C22—C23—H232 | 109.5 |
O6—C6—C5 | 104.2 (2) | H231—C23—H232 | 109.5 |
O6—C6—H61 | 110.9 | C22—C23—H233 | 109.5 |
C5—C6—H61 | 110.9 | H231—C23—H233 | 109.5 |
O6—C6—H62 | 110.9 | H232—C23—H233 | 109.5 |
C5—C6—H62 | 110.9 | ||
C12—O1—C1—C2 | −35.9 (3) | O4—C4—C5—C6 | −179.6 (2) |
C12—O2—C2—C1 | −9.5 (3) | C3—C4—C5—C6 | −66.0 (4) |
C12—O2—C2—C3 | −130.6 (2) | C22—O6—C6—C5 | 22.0 (3) |
O1—C1—C2—O2 | 27.4 (3) | O5—C5—C6—O6 | −2.6 (3) |
O1—C1—C2—C3 | 146.5 (3) | C4—C5—C6—O6 | 115.1 (3) |
C10—O3—C3—C4 | −13.6 (3) | C4—O4—C10—O10 | −173.1 (3) |
C10—O3—C3—C2 | 109.1 (3) | C4—O4—C10—O3 | 7.3 (3) |
O2—C2—C3—O3 | −179.7 (2) | C3—O3—C10—O10 | −175.1 (3) |
C1—C2—C3—O3 | 64.6 (3) | C3—O3—C10—O4 | 4.6 (3) |
O2—C2—C3—C4 | −65.6 (3) | C1—O1—C12—O2 | 30.4 (3) |
C1—C2—C3—C4 | 178.6 (3) | C1—O1—C12—C11 | 147.0 (3) |
C10—O4—C4—C3 | −15.2 (3) | C1—O1—C12—C13 | −87.0 (3) |
C10—O4—C4—C5 | 105.7 (3) | C2—O2—C12—O1 | −11.9 (3) |
O3—C3—C4—O4 | 16.7 (3) | C2—O2—C12—C11 | −127.5 (3) |
C2—C3—C4—O4 | −98.9 (3) | C2—O2—C12—C13 | 108.6 (3) |
O3—C3—C4—C5 | −99.9 (3) | C5—O5—C22—O6 | 31.8 (3) |
C2—C3—C4—C5 | 144.5 (3) | C5—O5—C22—C21 | 147.4 (3) |
C22—O5—C5—C4 | −139.1 (2) | C5—O5—C22—C23 | −87.3 (3) |
C22—O5—C5—C6 | −17.8 (3) | C6—O6—C22—O5 | −33.6 (3) |
O4—C4—C5—O5 | −63.8 (3) | C6—O6—C22—C21 | −150.1 (3) |
C3—C4—C5—O5 | 49.7 (3) | C6—O6—C22—C23 | 85.2 (3) |
Experimental details
Crystal data | |
Chemical formula | C13H20O7 |
Mr | 288.29 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 200 |
a, b, c (Å) | 6.0863 (3), 11.6958 (4), 19.6816 (8) |
V (Å3) | 1401.02 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.16 × 0.04 × 0.04 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3191, 1858, 1153 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.114, 1.00 |
No. of reflections | 1858 |
No. of parameters | 186 |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.16, −0.26 |
Computer programs: COLLECT (Nonius, 2004), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).
The title compound, C13H20O7, the carbonate of a partially protected sugar alcohol, 1,2:5,6-di-O-isopropylidene-D-mannitol, was obtained accidentally on the attempted preparation of an orthocarbonate thereof.
The molecular structure is shown in Fig. 1. The 5-membered 1,3-dioxolane ring O1–C1–C2–O2–C12 adopts a twist conformation on O1—C1 (Q2 = 0.324 (3) Å, φ2 = 16.7 (6)°), whereas O5–C5–C6–O6–C22 (Q2 = 0.302 (3) Å, φ2 = 319.3 (6)°) shows an envelope conformation on C22. The dioxolane ring O3–C3–C4–O4–C10, which contains the carbonate group, is twisted on C3—C4 (Q2 = 0.165 (3) Å, φ2 = 57.8 (11)°). Ring puckering parameters (Cremer & Pople, 1975) were calculated with PLATON (Spek, 2003).
The molecular packing is shown in Fig. 2.