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Acta Crystallogr Sect E Struct Rep Online. 2009 January 1; 65(Pt 1): o36.
Published online 2008 December 6. doi:  10.1107/S1600536808036891
PMCID: PMC2967953

2,4,8,10-Tetra­oxa-3,9-dithia­spiro­[5.5]undecane 3,9-dioxide

Abstract

The asymmetric unit of the title compound, C5H8O6S2, consists of two spiro­[5.5]undecane mol­ecules. The nonplanar six-membered rings adopt chair conformations. In the crystal structure, weak inter­molecular C—H(...)O inter­actions, together with close O(...)S contacts in the range 3.308 (3)–3.315 (3) Å, stabilize the packing.

Related literature

For background to the use of the title compound in the synthesis of pesticides, see: Jermy & Pandurangan (2005 [triangle]). For ring conformation puckering parameters, see: Cremer & Pople (1975 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-00o36-scheme1.jpg

Experimental

Crystal data

  • C5H8O6S2
  • M r = 228.25
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-00o36-efi1.jpg
  • a = 6.0489 (5) Å
  • b = 12.8431 (11) Å
  • c = 21.5830 (18) Å
  • V = 1676.7 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.63 mm−1
  • T = 293 (2) K
  • 0.25 × 0.23 × 0.19 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.858, T max = 0.890
  • 8878 measured reflections
  • 1604 independent reflections
  • 1531 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.078
  • S = 1.07
  • 1604 reflections
  • 235 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.41 e Å−3
  • Absolute structure: Flack (1983 [triangle]), with 1497 Friedel pairs
  • Flack parameter: 0.09 (9)

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [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: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036891/at2669sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036891/at2669Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge the Natural Science Foundation of China (grant No. 20767001), the International Collaborative Project of Guizhou Province, the Governor Foundation of Guizhou Province and the Natural Science Youth Foundation of Guizhou University (grant No. 2007-005) for financial support.

supplementary crystallographic information

Comment

As part of our ongoing investigation into pentaerythritol compounds, we present 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 crystal structure of the title compound, (I), consists of two spiro[5,5]undecane molecules (Fig. 1), in which the bond lengths are within normal ranges (Allen et al., 1987). The four six-membered rings are not planar and adopt chair conformations, with a total puckering amplitude, QT, of 0.607 (2) Å.

In the crystal structure, weak intermolecular C—H···O interactions, Table 1, together with close O5···S2 [dO···S = 3.315 (3)] and O6···S3 [dO···S = 3.308 (3)] contacts stabilize the packing.

Experimental

A solution of thionyl chloride 30 ml (13.6 g 0.1 mol) in CH2Cl2 (30 ml) was added to a stirred solution of pentaerythritol (13.6 g 0.1 mol) in CH2Cl2 (50 ml) at room temperature for 24 h, and was then heated to reflux for 5 h. The resulting solution was evaporated to dryness under reduced pressure and the white product washed with warm water, the mixture filtered and the residue dissolved in 80 ml boiling distilled water then cooled. Single crystals of (I) were obtained after several days.

Refinement

Water H atoms were located in a difference Fourier map and refined as riding in their as-found positions relative to O atoms with Uiso(H) = 1.2Ueq(O). All other H atoms were placed in calculated positions and refined as riding, with C—H = 0.93–0.97 Å, N—H = 0.86 Å, and Uiso(H) = 1.2–1.5Ueq(C,N).

Figures

Fig. 1.
The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C5H8O6S2F(000) = 944
Mr = 228.25Dx = 1.808 Mg m3
Orthorhombic, Pbn21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2abCell parameters from 1606 reflections
a = 6.0489 (5) Åθ = 1.9–25.5°
b = 12.8431 (11) ŵ = 0.63 mm1
c = 21.5830 (18) ÅT = 293 K
V = 1676.7 (2) Å3Prism, colourless
Z = 80.25 × 0.23 × 0.19 mm

Data collection

Bruker SMART CCD area-detector diffractometer1604 independent reflections
Radiation source: fine-focus sealed tube1531 reflections with I > 2σ(I)
graphiteRint = 0.028
[var phi] and ω scansθmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −7→7
Tmin = 0.858, Tmax = 0.890k = −15→15
8878 measured reflectionsl = −25→25

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.078w = 1/[σ2(Fo2) + (0.0528P)2 + 0.284P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1604 reflectionsΔρmax = 0.29 e Å3
235 parametersΔρmin = −0.41 e Å3
1 restraintAbsolute structure: Flack (1983), with 1497 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.09 (9)

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
C10.5760 (5)0.8962 (2)−0.21898 (13)0.0267 (6)
C20.3243 (5)0.8908 (2)−0.21098 (16)0.0320 (7)
H2A0.28030.9325−0.17560.038*
H2B0.25250.9189−0.24750.038*
C30.6435 (5)0.8264 (3)−0.27315 (14)0.0336 (7)
H3A0.58370.8547−0.31130.040*
H3B0.80330.8258−0.27670.040*
C40.6446 (5)1.0070 (2)−0.23563 (14)0.0331 (7)
H4A0.80111.0084−0.24530.040*
H4B0.56411.0296−0.27210.040*
C50.6937 (6)0.8619 (3)−0.15935 (16)0.0332 (7)
H5A0.64170.7934−0.14720.040*
H5B0.85160.8576−0.16670.040*
C60.0841 (5)0.8707 (2)0.04429 (13)0.0282 (6)
C70.1496 (6)0.7587 (3)0.06034 (15)0.0380 (7)
H7A0.30620.75610.06990.046*
H7B0.06890.73630.09680.046*
C80.2024 (6)0.9046 (3)−0.01531 (15)0.0317 (7)
H8A0.15250.9734−0.02730.038*
H8B0.36050.9077−0.00810.038*
C90.1562 (5)0.9395 (3)0.09843 (15)0.0366 (7)
H9A0.09910.91070.13680.044*
H9B0.31630.93970.10100.044*
C10−0.1658 (5)0.8766 (2)0.03668 (16)0.0344 (7)
H10A−0.21050.83580.00100.041*
H10B−0.23720.84770.07310.041*
O10.2555 (4)0.7835 (2)−0.20175 (13)0.0391 (6)
O20.5638 (4)0.72017 (16)−0.26492 (13)0.0393 (6)
O30.1990 (5)0.7482 (2)−0.31274 (14)0.0511 (7)
O40.6503 (4)0.93608 (18)−0.10970 (10)0.0384 (5)
O50.6001 (4)1.07751 (17)−0.18509 (11)0.0383 (5)
O60.9676 (4)1.0477 (2)−0.13830 (14)0.0483 (7)
O70.1022 (4)0.68874 (18)0.00930 (12)0.0414 (6)
O80.1555 (4)0.83071 (19)−0.06494 (10)0.0380 (5)
O90.4707 (4)0.7194 (2)−0.03627 (15)0.0532 (7)
O100.0777 (4)1.04518 (17)0.09141 (13)0.0430 (6)
O11−0.2349 (4)0.9845 (2)0.02836 (13)0.0424 (6)
O12−0.2837 (5)1.0115 (2)0.13974 (14)0.0618 (9)
S10.73630 (15)1.05361 (7)−0.12165 (4)0.0379 (2)
S20.29956 (16)0.70421 (6)−0.25830 (4)0.0384 (2)
S30.24084 (16)0.71310 (7)−0.05390 (5)0.0399 (2)
S4−0.18731 (16)1.06085 (7)0.08585 (5)0.0446 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0256 (15)0.0307 (15)0.0239 (14)0.0010 (11)0.0020 (11)−0.0003 (11)
C20.0286 (17)0.0333 (17)0.0340 (17)0.0035 (12)0.0030 (13)−0.0055 (13)
C30.0327 (16)0.0354 (17)0.0325 (17)0.0003 (13)0.0040 (12)−0.0063 (12)
C40.0368 (17)0.0334 (17)0.0292 (14)−0.0013 (13)0.0011 (14)0.0015 (12)
C50.0360 (17)0.0324 (15)0.0311 (16)0.0027 (13)−0.0013 (14)0.0006 (14)
C60.0305 (16)0.0303 (16)0.0240 (14)−0.0022 (12)0.0025 (12)−0.0006 (11)
C70.0466 (19)0.0381 (18)0.0295 (15)−0.0005 (15)0.0001 (15)0.0056 (14)
C80.0369 (18)0.0316 (16)0.0265 (15)−0.0014 (13)0.0059 (12)−0.0014 (12)
C90.0383 (18)0.0416 (17)0.0298 (16)−0.0040 (14)−0.0015 (14)−0.0038 (14)
C100.0281 (17)0.0380 (18)0.0370 (17)−0.0043 (13)0.0031 (14)−0.0091 (14)
O10.0367 (14)0.0426 (14)0.0380 (14)−0.0083 (9)0.0122 (9)−0.0059 (11)
O20.0417 (14)0.0312 (12)0.0451 (13)0.0043 (9)0.0050 (11)−0.0058 (10)
O30.0535 (16)0.0548 (17)0.0450 (15)−0.0016 (13)−0.0126 (12)−0.0107 (12)
O40.0460 (14)0.0413 (12)0.0278 (11)−0.0029 (11)0.0013 (10)−0.0014 (10)
O50.0423 (13)0.0308 (12)0.0418 (12)0.0034 (9)−0.0036 (11)−0.0016 (10)
O60.0351 (13)0.0505 (14)0.0594 (17)−0.0048 (11)−0.0049 (12)−0.0102 (12)
O70.0505 (15)0.0306 (12)0.0432 (13)−0.0041 (10)0.0035 (12)−0.0017 (10)
O80.0489 (14)0.0418 (13)0.0232 (10)0.0043 (10)0.0018 (10)−0.0021 (9)
O90.0399 (15)0.0535 (16)0.0663 (19)0.0066 (12)0.0044 (14)−0.0147 (13)
O100.0471 (14)0.0375 (12)0.0445 (14)−0.0105 (10)0.0045 (13)−0.0094 (10)
O110.0392 (15)0.0431 (14)0.0450 (15)0.0095 (10)−0.0050 (10)−0.0082 (12)
O120.071 (2)0.0582 (19)0.056 (2)−0.0121 (15)0.0297 (15)−0.0165 (15)
S10.0379 (5)0.0403 (4)0.0355 (5)0.0005 (4)−0.0027 (3)−0.0106 (4)
S20.0431 (4)0.0326 (4)0.0397 (5)−0.0040 (3)0.0036 (4)−0.0059 (4)
S30.0417 (5)0.0397 (5)0.0382 (5)0.0028 (3)0.0022 (3)−0.0106 (4)
S40.0476 (5)0.0371 (5)0.0492 (6)0.0018 (4)0.0103 (5)−0.0122 (4)

Geometric parameters (Å, °)

C1—C41.526 (4)C7—H7B0.9700
C1—C31.528 (4)C8—O81.458 (4)
C1—C21.534 (4)C8—H8A0.9700
C1—C51.535 (4)C8—H8B0.9700
C2—O11.454 (4)C9—O101.446 (4)
C2—H2A0.9700C9—H9A0.9700
C2—H2B0.9700C9—H9B0.9700
C3—O21.458 (4)C10—O111.458 (4)
C3—H3A0.9700C10—H10A0.9700
C3—H3B0.9700C10—H10B0.9700
C4—O51.443 (4)O1—S21.612 (3)
C4—H4A0.9700O2—S21.618 (3)
C4—H4B0.9700O3—S21.439 (3)
C5—O41.458 (4)O4—S11.617 (2)
C5—H5A0.9700O5—S11.627 (3)
C5—H5B0.9700O6—S11.446 (3)
C6—C101.522 (4)O7—S31.632 (3)
C6—C91.528 (4)O8—S31.614 (3)
C6—C71.532 (4)O9—S31.444 (3)
C6—C81.535 (4)O10—S41.620 (3)
C7—O71.450 (4)O11—S41.608 (3)
C7—H7A0.9700O12—S41.447 (3)
C4—C1—C3107.1 (2)C6—C7—H7B109.4
C4—C1—C2109.8 (2)H7A—C7—H7B108.0
C3—C1—C2108.9 (2)O8—C8—C6109.9 (2)
C4—C1—C5109.8 (2)O8—C8—H8A109.7
C3—C1—C5110.5 (2)C6—C8—H8A109.7
C2—C1—C5110.7 (3)O8—C8—H8B109.7
O1—C2—C1110.0 (2)C6—C8—H8B109.7
O1—C2—H2A109.7H8A—C8—H8B108.2
C1—C2—H2A109.7O10—C9—C6111.6 (3)
O1—C2—H2B109.7O10—C9—H9A109.3
C1—C2—H2B109.7C6—C9—H9A109.3
H2A—C2—H2B108.2O10—C9—H9B109.3
O2—C3—C1111.5 (2)C6—C9—H9B109.3
O2—C3—H3A109.3H9A—C9—H9B108.0
C1—C3—H3A109.3O11—C10—C6110.2 (2)
O2—C3—H3B109.3O11—C10—H10A109.6
C1—C3—H3B109.3C6—C10—H10A109.6
H3A—C3—H3B108.0O11—C10—H10B109.6
O5—C4—C1110.9 (2)C6—C10—H10B109.6
O5—C4—H4A109.5H10A—C10—H10B108.1
C1—C4—H4A109.5C2—O1—S2116.6 (2)
O5—C4—H4B109.5C3—O2—S2117.12 (19)
C1—C4—H4B109.5C5—O4—S1115.8 (2)
H4A—C4—H4B108.0C4—O5—S1115.05 (18)
O4—C5—C1110.2 (2)C7—O7—S3114.5 (2)
O4—C5—H5A109.6C8—O8—S3116.0 (2)
C1—C5—H5A109.6C9—O10—S4116.69 (19)
O4—C5—H5B109.6C10—O11—S4115.7 (2)
C1—C5—H5B109.6O6—S1—O4107.55 (15)
H5A—C5—H5B108.1O6—S1—O5106.90 (16)
C10—C6—C9109.7 (3)O4—S1—O598.48 (12)
C10—C6—C7109.1 (3)O3—S2—O1107.47 (16)
C9—C6—C7107.2 (3)O3—S2—O2107.21 (16)
C10—C6—C8111.0 (3)O1—S2—O298.65 (12)
C9—C6—C8110.1 (2)O9—S3—O8107.12 (14)
C7—C6—C8109.6 (3)O9—S3—O7106.59 (18)
O7—C7—C6111.0 (3)O8—S3—O797.95 (13)
O7—C7—H7A109.4O12—S4—O11106.32 (16)
C6—C7—H7A109.4O12—S4—O10106.55 (18)
O7—C7—H7B109.4O11—S4—O1099.11 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2A···O6i0.972.533.343 (4)141
C10—H10A···O9i0.972.573.375 (4)141
C3—H3B···O3ii0.972.713.610 (4)155
C9—H9A···O2iii0.972.723.635 (4)159

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) x−1/2, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2669).

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.
  • Bruker (2002). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Jermy, B. R. & Pandurangan, A. (2005). Appl. Catal. A, 295, 185–192.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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