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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o498.
Published online 2008 January 23. doi:  10.1107/S1600536808001785
PMCID: PMC2960158

6,10,16,19-Tetra­oxatrispiro­[4.2.2.4.2.2]nona­deca­ne

Abstract

The asymmetric unit of the title compound, C15H24O4, contains one half-mol­ecule; a twofold rotation axis passes through the central C atom. The non-planar six- and five-membered rings adopt chair and envelope conformations, respectively. In the crystal structure, inter­molecular C—H(...)O hydrogen bonds link the mol­ecules.

Related literature

For general background, see: Jermy & Pandurangan (2005 [triangle]). For related literature, see: Sun et al. (2001 [triangle]). For ring conformation puckering parameters, see: Cremer & Pople (1975 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-0o498-scheme1.jpg

Experimental

Crystal data

  • C15H24O4
  • M r = 268.34
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o498-efi1.jpg
  • a = 25.605 (5) Å
  • b = 5.5820 (11) Å
  • c = 10.337 (2) Å
  • β = 90.22 (3)°
  • V = 1477.4 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 294 (2) K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.965, T max = 0.982
  • 1547 measured reflections
  • 1457 independent reflections
  • 864 reflections with I > 2σ(I)
  • R int = 0.050
  • 3 standard reflections frequency: 120 min intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.067
  • wR(F 2) = 0.173
  • S = 0.93
  • 1457 reflections
  • 87 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); 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: PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001785/hk2414sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001785/hk2414Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

The title compound, (I), is an important intermediate in the synthesis of pesticides (Jermy & Pandurangan, 2005). The crystal structure determination of (I) has been carried out in order to elucidate the molecular conformation.

The asymmetric unit of the title compound, (I), contains one-half molecule (Fig. 1), in which the bond lengths are within normal ranges (Allen et al., 1987).

Ring B (O1/O2/C5—C8) is not planar, having total puckering amplitude, QT, of 0.943 (3) Å. It adopts chair conformation [[var phi] = -32.96 (2)° and θ = 58.52 (3)°] (Cremer & Pople, 1975). Ring A has envelope conformation with atom C1 displaced by -0.222 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure.

Experimental

The title compound was prepared from a mixture of 2,2-bis-(hydroxymethyl) propane-1,3-diol (0.68 g, 5 mmol), cyclopentanone (10 mmol), freshly activated catalyst TiO2/SO4(2-)(0.6 g, 0.32 mmol) and cyclohexane (80 ml), heated with stirring at refluxing temperature for 2 h, using a Dean-Stark apparatus in a nitrogen atmosphere (Sun et al., 2001). The progress of the reaction was monitored by thin-layer chromatography. After cooling to room temperature, the catalyst was filtered off, the crude product was isolated by distillation and the solid was recrystallized from ethanol. Crystals of (I) were obtained by dissolving the title compound (1.0 g) in toluene (15 ml) and evaporating the solvent slowly at room temperature for about 7 d.

Refinement

H atoms were positioned geometrically, with C—H = 0.97 Å for methylene H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title molecule, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (A) 1 - x, y, 1/2 - z.]
Fig. 2.
A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C15H24O4F000 = 584
Mr = 268.34Dx = 1.206 Mg m3
Monoclinic, C2/cMelting point: 401 K
Hall symbol: -C 2ycMo Kα radiation λ = 0.71073 Å
a = 25.605 (5) ÅCell parameters from 25 reflections
b = 5.5820 (11) Åθ = 10–13º
c = 10.337 (2) ŵ = 0.09 mm1
β = 90.22 (3)ºT = 294 (2) K
V = 1477.4 (5) Å3Block, colorless
Z = 40.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.050
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 1.6º
T = 294(2) Kh = −31→31
ω/2θ scansk = 0→6
Absorption correction: ψ scan(North et al., 1968)l = 0→12
Tmin = 0.965, Tmax = 0.9823 standard reflections
1547 measured reflections every 120 min
1457 independent reflections intensity decay: none
864 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.067H-atom parameters constrained
wR(F2) = 0.173  w = 1/[σ2(Fo2) + (0.06P)2 + 4.5P] where P = (Fo2 + 2Fc2)/3
S = 0.93(Δ/σ)max < 0.001
1457 reflectionsΔρmax = 0.26 e Å3
87 parametersΔρmin = −0.21 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
O10.43380 (7)0.3857 (4)0.41870 (16)0.0381 (5)
O20.42692 (7)0.0861 (3)0.26166 (16)0.0324 (5)
C10.30826 (17)0.3438 (9)0.3294 (5)0.0889 (15)
H1A0.28190.31250.26380.107*
H1B0.29740.48160.37970.107*
C20.31481 (15)0.1237 (9)0.4179 (4)0.0803 (13)
H2A0.29730.15140.49960.096*
H2B0.2993−0.01590.37730.096*
C30.36848 (12)0.0842 (7)0.4393 (3)0.0503 (9)
H3A0.3768−0.08350.42620.060*
H3B0.37770.12710.52740.060*
C40.35773 (13)0.3897 (7)0.2697 (3)0.0567 (10)
H4A0.36620.55880.27500.068*
H4B0.35670.34360.17920.068*
C50.39900 (11)0.2397 (5)0.3435 (3)0.0336 (7)
C60.46853 (11)0.5234 (5)0.3396 (2)0.0342 (7)
H6A0.49220.61380.39450.041*
H6B0.44840.63660.28840.041*
C70.50000.3637 (7)0.25000.0278 (8)
C80.46173 (10)0.2072 (5)0.1738 (2)0.0337 (7)
H8A0.44170.30600.11450.040*
H8B0.48090.09010.12350.040*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0461 (12)0.0405 (12)0.0275 (9)0.0017 (10)−0.0016 (8)−0.0038 (9)
O20.0368 (10)0.0236 (10)0.0368 (10)−0.0008 (9)0.0005 (8)−0.0038 (8)
C10.076 (3)0.098 (4)0.093 (3)0.005 (3)−0.001 (2)0.016 (3)
C20.069 (3)0.089 (3)0.083 (3)−0.005 (3)0.006 (2)0.009 (3)
C30.052 (2)0.053 (2)0.0460 (17)−0.0121 (17)0.0100 (15)−0.0008 (16)
C40.057 (2)0.052 (2)0.061 (2)0.0252 (18)−0.0165 (17)−0.0025 (17)
C50.0338 (14)0.0256 (15)0.0413 (15)0.0057 (12)−0.0035 (12)−0.0032 (12)
C60.0469 (16)0.0252 (15)0.0306 (13)−0.0021 (13)−0.0012 (12)−0.0044 (11)
C70.040 (2)0.023 (2)0.0204 (16)0.000−0.0036 (15)0.000
C80.0393 (15)0.0322 (16)0.0296 (13)−0.0017 (13)−0.0019 (12)−0.0004 (12)

Geometric parameters (Å, °)

O1—C51.434 (3)C3—H3B0.9700
O1—C61.434 (3)C4—C51.547 (4)
O2—C51.402 (3)C4—H4A0.9700
O2—C81.443 (3)C4—H4B0.9700
C1—C41.434 (5)C6—C71.519 (3)
C1—C21.540 (6)C6—H6A0.9700
C1—H1A0.9700C6—H6B0.9700
C1—H1B0.9700C7—C6i1.519 (3)
C2—C31.408 (5)C7—C81.529 (3)
C2—H2A0.9700C7—C8i1.529 (3)
C2—H2B0.9700C8—H8A0.9700
C3—C51.533 (4)C8—H8B0.9700
C3—H3A0.9700
C5—O1—C6112.37 (19)H4A—C4—H4B108.6
C5—O2—C8114.2 (2)O2—C5—O1110.9 (2)
C4—C1—C2107.7 (4)O2—C5—C3107.8 (2)
C4—C1—H1A110.2O1—C5—C3106.8 (2)
C2—C1—H1A110.2O2—C5—C4112.5 (2)
C4—C1—H1B110.2O1—C5—C4112.4 (2)
C2—C1—H1B110.2C3—C5—C4106.0 (3)
H1A—C1—H1B108.5O1—C6—C7111.4 (2)
C3—C2—C1108.8 (4)O1—C6—H6A109.4
C3—C2—H2A109.9C7—C6—H6A109.4
C1—C2—H2A109.9O1—C6—H6B109.4
C3—C2—H2B109.9C7—C6—H6B109.4
C1—C2—H2B109.9H6A—C6—H6B108.0
H2A—C2—H2B108.3C6—C7—C6i108.1 (3)
C2—C3—C5108.0 (3)C6—C7—C8107.99 (15)
C2—C3—H3A110.1C6i—C7—C8111.22 (14)
C5—C3—H3A110.1C6—C7—C8i111.22 (14)
C2—C3—H3B110.1C6i—C7—C8i107.99 (15)
C5—C3—H3B110.1C8—C7—C8i110.3 (3)
H3A—C3—H3B108.4O2—C8—C7109.86 (18)
C1—C4—C5107.1 (3)O2—C8—H8A109.7
C1—C4—H4A110.3C7—C8—H8A109.7
C5—C4—H4A110.3O2—C8—H8B109.7
C1—C4—H4B110.3C7—C8—H8B109.7
C5—C4—H4B110.3H8A—C8—H8B108.2

Symmetry codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6B···O2ii0.972.583.413 (4)143

Symmetry codes: (ii) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2414).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Enraf–Nonius (1989). CAD-4 Software Version 5. Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Jermy, B. R. & Pandurangan, A. (2005). Appl. Catal. A, 295, 185–192.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Sun, X., Wang, X.-F., Jin, T.-S. & Li, T.-S. (2001). J. Hebei Univ. (Nat. Sci. Ed.), 21, 49–52.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography