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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1741.
Published online 2010 June 23. doi:  10.1107/S1600536810023214
PMCID: PMC3006906

2-O-tert-Butyl­dimethyl­silyl-4,6-O-ethyl­idene-myo-insitol 1,3,5-orthoformate

Abstract

In the title compound, C15H26O6Si, the dioxa six-membered ring bonded to the myo-inositol skeleton is in a boat conformation while the rest of the six-membered rings adopt chair conformations.

Related literature

myo-Inositol orthoesters have been used extensively for the synthesis of phospho­inositols and their derivatives, see: Das & Shashidhar (1997 [triangle]); Sureshan et al. (2003 [triangle]); Potter & Lampe (1995 [triangle]). For the synthesis of the title compound, see: Li & Vasella (1993 [triangle]). For a related structure, see: Angyal (2000 [triangle]).

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Object name is e-66-o1741-scheme1.jpg

Experimental

Crystal data

  • C15H26O6Si
  • M r = 330.45
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1741-efi1.jpg
  • a = 12.0170 (4) Å
  • b = 11.2808 (3) Å
  • c = 25.6942 (8) Å
  • V = 3483.14 (18) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.16 mm−1
  • T = 297 K
  • 0.22 × 0.21 × 0.17 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003 [triangle]) T min = 0.966, T max = 0.973
  • 55999 measured reflections
  • 4060 independent reflections
  • 2035 reflections with I > 2σ(I)
  • R int = 0.102

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.149
  • S = 1.00
  • 4060 reflections
  • 205 parameters
  • 18 restraints
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023214/pv2294sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023214/pv2294Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Henan Polytechnic University Foundation for Doctor Teachers (B2010–65) and the Henan Polytechnic University Foundation for the Youth (P051102). The authors thank Drs L. Yang, D. Zhao and Z. Z. Zhang for their assistance with the data collection and analysis.

supplementary crystallographic information

Comment

myo-inositol orthoesters have been used extensivedly for the synthesis of phosphoinositols (Das & Shashidhar, 1997; Sureshan et al., 2003), their derivatives and other compounds with interesting properties (Potter & Lampe, 1995). We present here the crystal structure of the title compound, which is a key intermediate for the synthesis of phosphorylated myo-inositol derivatives (Angyal, 2000).

The bond lengths and angles in the title compound (Fig. 1) are in normal range and agree well with the corresponding bond lengths and angles reported for a related structure (Angyal, 2000). In the title molecule, the six-membered ring containing O1 and O2 is in a boat conformation, the other six-membered rings are in chair conformations. The crystal packing is stabilized by van der Waals forces.

Experimental

The title compound was prepared according to the literature (Li & Vasella, 1993). Single crystals suitable for X-ray diffraction were prepared by slow evaperation from a solution of ethyl acetate and petroleum ether (1:4).

Refinement

All H atoms were placed in idealized positions (C—H = 0.98 and 0.96 Å for methyne and methyl H atoms, respectively) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(methyne C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of the title compound, with the atomic-numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
Fig. 2.
A partial packing diagram of the title compound, viewed down the b-axis.

Crystal data

C15H26O6SiF(000) = 1424
Mr = 330.45Dx = 1.260 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3612 reflections
a = 12.0170 (4) Åθ = 2.3–18.5°
b = 11.2808 (3) ŵ = 0.16 mm1
c = 25.6942 (8) ÅT = 297 K
V = 3483.14 (18) Å3Block, colorless
Z = 80.22 × 0.21 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer4060 independent reflections
Radiation source: fine-focus sealed tube2035 reflections with I > 2σ(I)
graphiteRint = 0.102
[var phi] and ω scansθmax = 27.6°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)h = −15→15
Tmin = 0.966, Tmax = 0.973k = −14→14
55999 measured reflectionsl = −33→32

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0588P)2 + 1.0231P] where P = (Fo2 + 2Fc2)/3
4060 reflections(Δ/σ)max = 0.001
205 parametersΔρmax = 0.24 e Å3
18 restraintsΔρmin = −0.23 e Å3

Special details

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)

xyzUiso*/Ueq
C11.0701 (3)0.6537 (3)0.59939 (13)0.0839 (10)
H1A1.13520.69000.58480.126*
H1B1.01120.71100.60130.126*
H1C1.04730.58860.57780.126*
C21.0960 (2)0.6094 (2)0.65278 (12)0.0623 (8)
H21.12260.67460.67470.075*
C31.2002 (2)0.4541 (3)0.69423 (11)0.0606 (8)
H31.27940.45780.70320.073*
C41.0113 (2)0.4980 (2)0.72188 (10)0.0525 (6)
H40.96410.53270.74900.063*
C51.1318 (2)0.4988 (3)0.73907 (11)0.0615 (7)
H51.15450.57970.74810.074*
C61.1663 (2)0.3251 (2)0.68424 (10)0.0565 (7)
H61.21340.29130.65690.068*
C70.9784 (2)0.3686 (2)0.71229 (10)0.0475 (6)
H70.89890.36410.70410.057*
C81.0450 (2)0.3186 (2)0.66778 (10)0.0477 (6)
H81.03330.36680.63650.057*
C91.1140 (3)0.3057 (3)0.77096 (12)0.0663 (8)
H91.12550.25700.80210.080*
C101.0905 (3)0.2103 (4)0.55151 (14)0.1063 (13)
H10A1.08590.29520.55340.160*
H10B1.07100.18470.51710.160*
H10C1.16510.18560.55930.160*
C111.0206 (3)−0.0159 (3)0.60583 (12)0.0748 (9)
H11A1.0988−0.02860.61110.112*
H11B0.9973−0.05610.57480.112*
H11C0.9800−0.04650.63510.112*
C120.8465 (3)0.1719 (3)0.57919 (11)0.0673 (8)
C130.8201 (3)0.1084 (3)0.52793 (12)0.0919 (11)
H13A0.74290.11900.51960.138*
H13B0.83590.02540.53150.138*
H13C0.86510.14110.50060.138*
C140.7693 (3)0.1210 (4)0.62207 (15)0.1046 (12)
H14A0.78340.16120.65430.157*
H14B0.78370.03780.62620.157*
H14C0.69300.13240.61220.157*
C150.8231 (4)0.3032 (3)0.57262 (19)0.141 (2)
H15A0.74740.31410.56180.212*
H15B0.87220.33540.54680.212*
H15C0.83510.34310.60520.212*
O10.99714 (14)0.56100 (14)0.67385 (7)0.0554 (5)
O21.18006 (14)0.52151 (17)0.64779 (7)0.0621 (5)
O31.14699 (17)0.42203 (18)0.78300 (7)0.0728 (6)
O41.00096 (16)0.30181 (15)0.75876 (7)0.0584 (5)
O51.18069 (15)0.25908 (18)0.73137 (8)0.0689 (6)
O61.01461 (16)0.19916 (15)0.65769 (7)0.0610 (5)
Si10.99324 (6)0.14381 (6)0.59918 (3)0.0530 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.081 (2)0.074 (2)0.096 (3)0.0003 (17)0.0099 (19)0.032 (2)
C20.0583 (17)0.0506 (16)0.078 (2)−0.0097 (14)0.0084 (15)0.0002 (15)
C30.0401 (15)0.077 (2)0.0650 (18)−0.0088 (14)−0.0059 (13)0.0029 (16)
C40.0549 (16)0.0477 (14)0.0550 (17)−0.0024 (12)0.0088 (13)−0.0084 (13)
C50.0650 (18)0.0632 (18)0.0563 (18)−0.0168 (15)−0.0026 (14)−0.0060 (15)
C60.0492 (15)0.0673 (18)0.0531 (17)0.0093 (14)0.0019 (13)−0.0007 (14)
C70.0458 (15)0.0451 (14)0.0515 (16)−0.0045 (11)−0.0005 (12)−0.0021 (12)
C80.0507 (15)0.0432 (14)0.0491 (16)−0.0002 (11)−0.0029 (12)−0.0048 (12)
C90.072 (2)0.070 (2)0.0565 (18)−0.0023 (16)−0.0084 (16)0.0069 (16)
C100.121 (3)0.112 (3)0.086 (3)−0.040 (2)0.038 (2)−0.020 (2)
C110.093 (2)0.0545 (17)0.077 (2)0.0151 (16)−0.0045 (17)−0.0142 (15)
C120.0784 (19)0.0668 (17)0.0567 (17)0.0118 (15)−0.0106 (15)−0.0052 (14)
C130.104 (2)0.096 (2)0.076 (2)0.0068 (19)−0.0219 (18)−0.0122 (18)
C140.072 (2)0.142 (3)0.100 (2)0.008 (2)0.0024 (19)−0.005 (2)
C150.178 (5)0.084 (3)0.162 (4)0.060 (3)−0.091 (4)−0.026 (3)
O10.0522 (10)0.0465 (10)0.0677 (12)−0.0015 (8)0.0059 (9)0.0021 (9)
O20.0495 (11)0.0730 (12)0.0639 (12)−0.0066 (9)0.0089 (9)0.0042 (11)
O30.0812 (14)0.0844 (15)0.0527 (12)−0.0182 (11)−0.0141 (10)−0.0024 (11)
O40.0626 (12)0.0582 (11)0.0544 (12)−0.0061 (9)0.0037 (9)0.0049 (9)
O50.0637 (12)0.0759 (13)0.0671 (14)0.0167 (10)−0.0079 (10)0.0074 (11)
O60.0870 (14)0.0419 (10)0.0543 (11)−0.0050 (9)−0.0042 (10)−0.0059 (8)
Si10.0636 (5)0.0452 (4)0.0502 (5)−0.0004 (4)0.0056 (4)−0.0067 (3)

Geometric parameters (Å, °)

C1—C21.493 (4)C9—O51.397 (3)
C1—H1A0.9600C9—O31.406 (3)
C1—H1B0.9600C9—H90.9800
C1—H1C0.9600C10—Si11.852 (3)
C2—O11.415 (3)C10—H10A0.9600
C2—O21.421 (3)C10—H10B0.9600
C2—H20.9800C10—H10C0.9600
C3—O21.436 (3)C11—Si11.840 (3)
C3—C51.502 (4)C11—H11A0.9600
C3—C61.533 (4)C11—H11B0.9600
C3—H30.9800C11—H11C0.9600
C4—O11.434 (3)C12—C151.516 (4)
C4—C51.513 (4)C12—C131.532 (4)
C4—C71.533 (3)C12—C141.550 (5)
C4—H40.9800C12—Si11.864 (3)
C5—O31.434 (3)C13—H13A0.9600
C5—H50.9800C13—H13B0.9600
C6—O51.432 (3)C13—H13C0.9600
C6—C81.520 (3)C14—H14A0.9600
C6—H60.9800C14—H14B0.9600
C7—O41.437 (3)C14—H14C0.9600
C7—C81.505 (3)C15—H15A0.9600
C7—H70.9800C15—H15B0.9600
C8—O61.420 (3)C15—H15C0.9600
C8—H80.9800O6—Si11.6480 (18)
C9—O41.395 (3)
C2—C1—H1A109.5O4—C9—H9107.7
C2—C1—H1B109.5O5—C9—H9107.7
H1A—C1—H1B109.5O3—C9—H9107.7
C2—C1—H1C109.5Si1—C10—H10A109.5
H1A—C1—H1C109.5Si1—C10—H10B109.5
H1B—C1—H1C109.5H10A—C10—H10B109.5
O1—C2—O2111.3 (2)Si1—C10—H10C109.5
O1—C2—C1107.8 (2)H10A—C10—H10C109.5
O2—C2—C1107.4 (2)H10B—C10—H10C109.5
O1—C2—H2110.1Si1—C11—H11A109.5
O2—C2—H2110.1Si1—C11—H11B109.5
C1—C2—H2110.1H11A—C11—H11B109.5
O2—C3—C5111.6 (2)Si1—C11—H11C109.5
O2—C3—C6108.6 (2)H11A—C11—H11C109.5
C5—C3—C6107.5 (2)H11B—C11—H11C109.5
O2—C3—H3109.7C15—C12—C13108.8 (3)
C5—C3—H3109.7C15—C12—C14109.3 (3)
C6—C3—H3109.7C13—C12—C14108.3 (3)
O1—C4—C5111.2 (2)C15—C12—Si1111.8 (3)
O1—C4—C7107.6 (2)C13—C12—Si1110.7 (2)
C5—C4—C7107.4 (2)C14—C12—Si1107.9 (2)
O1—C4—H4110.2C12—C13—H13A109.5
C5—C4—H4110.2C12—C13—H13B109.5
C7—C4—H4110.2H13A—C13—H13B109.5
O3—C5—C3109.3 (2)C12—C13—H13C109.5
O3—C5—C4110.4 (2)H13A—C13—H13C109.5
C3—C5—C4107.3 (2)H13B—C13—H13C109.5
O3—C5—H5109.9C12—C14—H14A109.5
C3—C5—H5109.9C12—C14—H14B109.5
C4—C5—H5109.9H14A—C14—H14B109.5
O5—C6—C8109.0 (2)C12—C14—H14C109.5
O5—C6—C3108.7 (2)H14A—C14—H14C109.5
C8—C6—C3110.3 (2)H14B—C14—H14C109.5
O5—C6—H6109.6C12—C15—H15A109.5
C8—C6—H6109.6C12—C15—H15B109.5
C3—C6—H6109.6H15A—C15—H15B109.5
O4—C7—C8109.6 (2)C12—C15—H15C109.5
O4—C7—C4108.5 (2)H15A—C15—H15C109.5
C8—C7—C4109.9 (2)H15B—C15—H15C109.5
O4—C7—H7109.6C2—O1—C4114.9 (2)
C8—C7—H7109.6C2—O2—C3114.5 (2)
C4—C7—H7109.6C9—O3—C5110.8 (2)
O6—C8—C7110.9 (2)C9—O4—C7110.8 (2)
O6—C8—C6110.0 (2)C9—O5—C6110.5 (2)
C7—C8—C6106.3 (2)C8—O6—Si1124.48 (16)
O6—C8—H8109.8O6—Si1—C11104.99 (12)
C7—C8—H8109.8O6—Si1—C10110.57 (14)
C6—C8—H8109.8C11—Si1—C10110.20 (17)
O4—C9—O5112.5 (2)O6—Si1—C12109.54 (12)
O4—C9—O3110.7 (2)C11—Si1—C12111.17 (15)
O5—C9—O3110.5 (2)C10—Si1—C12110.25 (17)
O2—C3—C5—O3174.7 (2)C1—C2—O2—C3−169.0 (2)
C6—C3—C5—O355.7 (3)C5—C3—O2—C2−4.0 (3)
O2—C3—C5—C454.9 (3)C6—C3—O2—C2114.4 (2)
C6—C3—C5—C4−64.1 (3)O4—C9—O3—C5−62.2 (3)
O1—C4—C5—O3−172.03 (19)O5—C9—O3—C563.1 (3)
C7—C4—C5—O3−54.5 (3)C3—C5—O3—C9−59.7 (3)
O1—C4—C5—C3−52.9 (3)C4—C5—O3—C958.1 (3)
C7—C4—C5—C364.6 (3)O5—C9—O4—C7−59.7 (3)
O2—C3—C6—O5−176.93 (19)O3—C9—O4—C764.4 (3)
C5—C3—C6—O5−56.1 (3)C8—C7—O4—C959.0 (3)
O2—C3—C6—C8−57.5 (3)C4—C7—O4—C9−61.0 (3)
C5—C3—C6—C863.4 (3)O4—C9—O5—C660.5 (3)
O1—C4—C7—O4175.20 (18)O3—C9—O5—C6−63.7 (3)
C5—C4—C7—O455.3 (3)C8—C6—O5—C9−59.9 (3)
O1—C4—C7—C855.4 (3)C3—C6—O5—C960.3 (3)
C5—C4—C7—C8−64.5 (3)C7—C8—O6—Si1135.56 (19)
O4—C7—C8—O661.8 (3)C6—C8—O6—Si1−107.1 (2)
C4—C7—C8—O6−179.1 (2)C8—O6—Si1—C11154.8 (2)
O4—C7—C8—C6−57.9 (3)C8—O6—Si1—C1035.9 (2)
C4—C7—C8—C661.2 (3)C8—O6—Si1—C12−85.8 (2)
O5—C6—C8—O6−61.8 (3)C15—C12—Si1—O665.4 (3)
C3—C6—C8—O6179.0 (2)C13—C12—Si1—O6−173.1 (2)
O5—C6—C8—C758.4 (3)C14—C12—Si1—O6−54.8 (2)
C3—C6—C8—C7−60.8 (3)C15—C12—Si1—C11−179.0 (3)
O2—C2—O1—C453.3 (3)C13—C12—Si1—C11−57.5 (3)
C1—C2—O1—C4170.8 (2)C14—C12—Si1—C1160.8 (3)
C5—C4—O1—C20.2 (3)C15—C12—Si1—C10−56.5 (3)
C7—C4—O1—C2−117.2 (2)C13—C12—Si1—C1065.0 (3)
O1—C2—O2—C3−51.2 (3)C14—C12—Si1—C10−176.7 (2)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2294).

References

  • Angyal, S. J. (2000). Carbohydr. Res.325, 313–320. [PubMed]
  • Bruker (2007). APEX2, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Das, T. & Shashidhar, M. S. (1997). Carbohydr. Res.297, 243–249.
  • Li, C. & Vasella, A. (1993). Helv. Chim. Acta, 76, 211–221.
  • Potter, B. V. L. & Lampe, D. (1995). Angew. Chem. Int. Ed. Engl.34, 1933–1972.
  • Sheldrick, G. M. (2003). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sureshan, K. M., Shashidhar, M. S., Praveen, T. & Das, T. (2003). Chem. Rev.103, 4477–4503. [PubMed]

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