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Acta Cryst. (2007). E63, o4166    [ doi:10.1107/S160053680704679X ]

3-Oxapentane-1,5-diyl bis(allylsulfonate)

B. R. Srinivasan, V. S. Nadkarni, V. Mandrekar and P. Raghavaiah

Abstract top

The title compound, C10H18O7S2, was synthesized by reacting diethylene glycol with allyl chlorosulfonate in the presence of pyridine. The asymmetric unit consists of half a molecule, which is located on a twofold rotation axis. In the crystal structure, the molecules are involved in several weak C-H...O interactions.

Comment top

As part of an ongoing research programme, we are designing monomers and polymers for nuclear track detection purpose (Mascarenhas et al., 2006). During the course of this study we have synthesized two monomers namely diethylene glycol bis(allylsulfonate) (I) and the corresponding isomer allyl diglycol sulphite (ADS) having the same molecular formula [C10H18O7S2] but different functional groups. Interestingly compound (I) is a solid while the functional isomer (ADS) is a liquid at room temperature. The structure of (I) is described in this report.

In the crystal structure of the title compound the molecules are located with the ether oxygen atom (O1) on a 2-fold axis with one half of the molecule constituting the asymmetric unit (Fig. 1). An analysis of the structure reveals that each molecule of (I) is hydrogen bonded to four symmetry related molecules with the aid of C—H···O interactions (Fig. 2). All these O···H contacts are shorter than the sum of their van der Waals radii (Bondi, 1964) (Table 1).

Related literature top

For related work on monomers and polymers for nuclear track detection purposes, see: Mascarenhas et al. (2006). For related literature, see: Bondi (1964).

Experimental top

Diethylene glycol (10 g, 0.094 mol) was condended with allyl chlorosulphonate (26.695 g, 0.19 mol) in the presence of pyridine (16.53 g, 0.209 mol). The product obtained was purified by column chromatography. Yield: 25.61 g (86%) of a colourless solid (m.p. 43–45°C). Crystals suitable for structure determination were prepared by recrystallizing from a mixture of 1:1 ethyl acetate and petroleum ether.

Refinement top

The H atoms were positioned with idealized geometry (C—H = 0.93 and 0.97 Å and were refined isotropic (Uiso(H) = 1.2Ueq(C)) using a riding model.

Computing details top

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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2001).

Figures top
[Figure 1] Fig. 1. Crystal structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at 30% probability level. The O1 atom is situated on a twofold axis. Symmetry code: i) −x + 1, y, −z + 3/2.
[Figure 2] Fig. 2. A view of the surroundings of (I) showing its linking to four symmetry related molecules. (C—H···O bonds are shown as dashed lines). Symmetry codes: i) −x + 1, y, −z + 3/2; ii) −x + 1/2, −y + 1/2, −z + 1; iii) −x + 1, −y, −z + 1; iv) −x + 1/2, −y − 1/2, −z + 1; v) −x + 1/2, y − 1/2, −z + 3/2.
3-Oxapentane-1,5-diyl bis(allylsulfonate) top
Crystal data top
C10H18O7S2F000 = 664
Mr = 314.38Dx = 1.424 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2760 reflections
a = 12.022 (3) Åθ = 2.8–26.0º
b = 8.3484 (18) ŵ = 0.39 mm−1
c = 14.894 (3) ÅT = 298 (2) K
β = 101.096 (3)ºBlock, colourless
V = 1466.8 (5) Å30.38 × 0.38 × 0.22 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		1437 independent reflections
Radiation source: fine-focus sealed tube1233 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 298(2) Kθmax = 26.0º
φ and ω scansθmin = 2.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −14→13
Tmin = 0.867, Tmax = 0.920k = −10→9
4456 measured reflectionsl = −18→18
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039  w = 1/[σ2(Fo2) + (0.0668P)2 + 0.3626P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.111(Δ/σ)max < 0.001
S = 1.06Δρmax = 0.23 e Å−3
1437 reflectionsΔρmin = −0.26 e Å−3
88 parametersExtinction correction: SHELXTL (Sheldrick, 2001), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0102 (14)
Secondary atom site location: difference Fourier map
Crystal data top
C10H18O7S2V = 1466.8 (5) Å3
Mr = 314.38Z = 4
Monoclinic, C2/cMo Kα
a = 12.022 (3) ŵ = 0.39 mm−1
b = 8.3484 (18) ÅT = 298 (2) K
c = 14.894 (3) Å0.38 × 0.38 × 0.22 mm
β = 101.096 (3)º
Data collection top
Bruker SMART APEX CCD
diffractometer		1437 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1233 reflections with I > 2σ(I)
Tmin = 0.867, Tmax = 0.920Rint = 0.019
4456 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03988 parameters
wR(F2) = 0.111H-atom parameters constrained
S = 1.06Δρmax = 0.23 e Å−3
1437 reflectionsΔρmin = −0.26 e Å−3
Special details top

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 > 2sigma(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) top
xyzUiso*/Ueq
C10.47766 (16)0.3496 (2)0.66959 (12)0.0598 (5)
H1A0.54330.41470.66540.072*
H1B0.41400.42030.67110.072*
C20.45113 (15)0.2405 (2)0.58925 (12)0.0583 (5)
H2A0.44860.30020.53300.070*
H2B0.50900.15840.59310.070*
C30.38595 (16)−0.1408 (2)0.60957 (12)0.0575 (5)
H3A0.3680−0.24590.58300.069*
H3B0.4666−0.12300.61420.069*
C40.35810 (16)−0.1363 (2)0.70316 (12)0.0633 (5)
H40.3820−0.04810.74000.076*
C50.3028 (2)−0.2478 (3)0.73597 (16)0.0864 (7)
H5A0.2778−0.33740.70080.104*
H5B0.2880−0.23830.79480.104*
O10.50000.25490 (19)0.75000.0588 (5)
O20.34023 (10)0.16683 (15)0.59020 (8)0.0564 (4)
O30.19171 (12)−0.01518 (16)0.53390 (11)0.0709 (4)
O40.34969 (13)0.01089 (16)0.45264 (9)0.0689 (4)
S10.30943 (4)0.00679 (5)0.53678 (3)0.0551 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0652 (12)0.0545 (11)0.0604 (10)0.0051 (8)0.0139 (8)0.0084 (8)
C20.0543 (10)0.0676 (12)0.0549 (10)0.0098 (8)0.0153 (7)0.0064 (8)
C30.0533 (10)0.0643 (11)0.0548 (9)0.0123 (8)0.0098 (7)0.0046 (8)
C40.0588 (11)0.0730 (13)0.0572 (10)0.0088 (9)0.0091 (8)0.0067 (9)
C50.0861 (17)0.0939 (17)0.0859 (15)0.0038 (13)0.0334 (12)0.0152 (12)
O10.0705 (12)0.0506 (10)0.0527 (9)0.0000.0054 (8)0.000
O20.0527 (7)0.0643 (8)0.0539 (7)0.0107 (6)0.0147 (5)−0.0047 (5)
O30.0506 (8)0.0839 (10)0.0737 (9)0.0082 (6)0.0008 (6)0.0005 (7)
O40.0794 (11)0.0815 (10)0.0454 (7)0.0187 (7)0.0109 (6)−0.0017 (5)
S10.0523 (3)0.0662 (4)0.0451 (3)0.01240 (18)0.0054 (2)−0.00064 (17)
Geometric parameters (Å, °) top
C1—O11.4170 (19)C3—H3B0.9700
C1—C21.489 (3)C4—C51.293 (3)
C1—H1A0.9700C4—H40.9300
C1—H1B0.9700C5—H5A0.9300
C2—O21.471 (2)C5—H5B0.9300
C2—H2A0.9700O1—C1i1.4169 (19)
C2—H2B0.9700O2—S11.5626 (13)
C3—C41.495 (2)O3—S11.4196 (15)
C3—S11.7764 (18)O4—S11.4279 (15)
C3—H3A0.9700
O1—C1—C2108.31 (14)S1—C3—H3B109.3
O1—C1—H1A110.0H3A—C3—H3B107.9
C2—C1—H1A110.0C5—C4—C3123.9 (2)
O1—C1—H1B110.0C5—C4—H4118.0
C2—C1—H1B110.0C3—C4—H4118.0
H1A—C1—H1B108.4C4—C5—H5A120.0
O2—C2—C1107.61 (13)C4—C5—H5B120.0
O2—C2—H2A110.2H5A—C5—H5B120.0
C1—C2—H2A110.2C1i—O1—C1112.15 (19)
O2—C2—H2B110.2C2—O2—S1118.61 (10)
C1—C2—H2B110.2O3—S1—O4118.74 (10)
H2A—C2—H2B108.5O3—S1—O2105.25 (7)
C4—C3—S1111.66 (13)O4—S1—O2109.83 (8)
C4—C3—H3A109.3O3—S1—C3108.96 (9)
S1—C3—H3A109.3O4—S1—C3109.21 (8)
C4—C3—H3B109.3O2—S1—C3103.77 (8)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O3ii0.972.533.219 (2)128
C2—H2B···O4iii0.972.413.332 (2)159
C3—H3A···O3iv0.972.653.594 (2)163
C5—H5B···O2v0.932.643.447 (2)146
Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1, −y, −z+1; (iv) −x+1/2, −y−1/2, −z+1; (v) −x+1/2, y−1/2, −z+3/2.
Selected geometric parameters (Å, °) top
C1—O11.4170 (19)C4—C51.293 (3)
C1—C21.489 (3)O1—C1i1.4169 (19)
C2—O21.471 (2)O2—S11.5626 (13)
C3—C41.495 (2)O3—S11.4196 (15)
C3—S11.7764 (18)O4—S11.4279 (15)
O1—C1—C2108.31 (14)O3—S1—O4118.74 (10)
O2—C2—C1107.61 (13)O3—S1—O2105.25 (7)
C4—C3—S1111.66 (13)O4—S1—O2109.83 (8)
C5—C4—C3123.9 (2)O3—S1—C3108.96 (9)
C1i—O1—C1112.15 (19)O4—S1—C3109.21 (8)
C2—O2—S1118.61 (10)O2—S1—C3103.77 (8)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O3ii0.972.533.219 (2)128
C2—H2B···O4iii0.972.413.332 (2)159
C3—H3A···O3iv0.972.653.594 (2)163
C5—H5B···O2v0.932.643.447 (2)146
Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1; (iii) −x+1, −y, −z+1; (iv) −x+1/2, −y−1/2, −z+1; (v) −x+1/2, y−1/2, −z+3/2.
Acknowledgements top

VSN thanks Dr Samar K. Das, School of Chemistry, University of Hyderabad, for the X-ray intensity data collection, and the Atomic Energy Regulatory Board (AERB), Government of India, for financial support.

references
References top

Bondi, A. (1964). J. Phys. Chem. 68, 441–451.B

Brandenburg, K. (1999). DIAMOND. Release 2.1c. Crystal Impact GbR, Bonn, Germany.

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Mascarenhas, A. A. A., Kolekar, R. V., Kalsi, P. C., Ramaswami, A., Joshi, V. B., Tilve, S. G. & Nadkarni, V. S. (2006). Radiat. Meas. 41, 23–30.

Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.