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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.111
• Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3A    ..  O3      ..       2.65 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5B    ..  O2      ..       2.64 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	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.
	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)

Crystal data

C10H18O7S2	F(000) = 664
Mr = 314.38	Dx = 1.424 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2760 reflections
a = 12.022 (3) Å	θ = 2.8–26.0°
b = 8.3484 (18) Å	µ = 0.39 mm^−1
c = 14.894 (3) Å	T = 298 K
β = 101.096 (3)°	Block, colourless
V = 1466.8 (5) Å^3	0.38 × 0.38 × 0.22 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	1437 independent reflections
Radiation source: fine-focus sealed tube	1233 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 26.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −14→13
Tmin = 0.867, Tmax = 0.920	k = −10→9
4456 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0668P)^2 + 0.3626P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1437 reflections	Δρmax = 0.23 e Å^−3
88 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2001), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0102 (14)

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.47766 (16)	0.3496 (2)	0.66959 (12)	0.0598 (5)
H1A	0.5433	0.4147	0.6654	0.072*
H1B	0.4140	0.4203	0.6711	0.072*
C2	0.45113 (15)	0.2405 (2)	0.58925 (12)	0.0583 (5)
H2A	0.4486	0.3002	0.5330	0.070*
H2B	0.5090	0.1584	0.5931	0.070*
C3	0.38595 (16)	−0.1408 (2)	0.60957 (12)	0.0575 (5)
H3A	0.3680	−0.2459	0.5830	0.069*
H3B	0.4666	−0.1230	0.6142	0.069*
C4	0.35810 (16)	−0.1363 (2)	0.70316 (12)	0.0633 (5)
H4	0.3820	−0.0481	0.7400	0.076*
C5	0.3028 (2)	−0.2478 (3)	0.73597 (16)	0.0864 (7)
H5A	0.2778	−0.3374	0.7008	0.104*
H5B	0.2880	−0.2383	0.7948	0.104*
O1	0.5000	0.25490 (19)	0.7500	0.0588 (5)
O2	0.34023 (10)	0.16683 (15)	0.59020 (8)	0.0564 (4)
O3	0.19171 (12)	−0.01518 (16)	0.53390 (11)	0.0709 (4)
O4	0.34969 (13)	0.01089 (16)	0.45264 (9)	0.0689 (4)
S1	0.30943 (4)	0.00679 (5)	0.53678 (3)	0.0551 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0652 (12)	0.0545 (11)	0.0604 (10)	0.0051 (8)	0.0139 (8)	0.0084 (8)
C2	0.0543 (10)	0.0676 (12)	0.0549 (10)	0.0098 (8)	0.0153 (7)	0.0064 (8)
C3	0.0533 (10)	0.0643 (11)	0.0548 (9)	0.0123 (8)	0.0098 (7)	0.0046 (8)
C4	0.0588 (11)	0.0730 (13)	0.0572 (10)	0.0088 (9)	0.0091 (8)	0.0067 (9)
C5	0.0861 (17)	0.0939 (17)	0.0859 (15)	0.0038 (13)	0.0334 (12)	0.0152 (12)
O1	0.0705 (12)	0.0506 (10)	0.0527 (9)	0.000	0.0054 (8)	0.000
O2	0.0527 (7)	0.0643 (8)	0.0539 (7)	0.0107 (6)	0.0147 (5)	−0.0047 (5)
O3	0.0506 (8)	0.0839 (10)	0.0737 (9)	0.0082 (6)	0.0008 (6)	0.0005 (7)
O4	0.0794 (11)	0.0815 (10)	0.0454 (7)	0.0187 (7)	0.0109 (6)	−0.0017 (5)
S1	0.0523 (3)	0.0662 (4)	0.0451 (3)	0.01240 (18)	0.0054 (2)	−0.00064 (17)

Geometric parameters (Å, º)

C1—O1	1.4170 (19)	C3—H3B	0.9700
C1—C2	1.489 (3)	C4—C5	1.293 (3)
C1—H1A	0.9700	C4—H4	0.9300
C1—H1B	0.9700	C5—H5A	0.9300
C2—O2	1.471 (2)	C5—H5B	0.9300
C2—H2A	0.9700	O1—C1^i	1.4169 (19)
C2—H2B	0.9700	O2—S1	1.5626 (13)
C3—C4	1.495 (2)	O3—S1	1.4196 (15)
C3—S1	1.7764 (18)	O4—S1	1.4279 (15)
C3—H3A	0.9700
O1—C1—C2	108.31 (14)	S1—C3—H3B	109.3
O1—C1—H1A	110.0	H3A—C3—H3B	107.9
C2—C1—H1A	110.0	C5—C4—C3	123.9 (2)
O1—C1—H1B	110.0	C5—C4—H4	118.0
C2—C1—H1B	110.0	C3—C4—H4	118.0
H1A—C1—H1B	108.4	C4—C5—H5A	120.0
O2—C2—C1	107.61 (13)	C4—C5—H5B	120.0
O2—C2—H2A	110.2	H5A—C5—H5B	120.0
C1—C2—H2A	110.2	C1^i—O1—C1	112.15 (19)
O2—C2—H2B	110.2	C2—O2—S1	118.61 (10)
C1—C2—H2B	110.2	O3—S1—O4	118.74 (10)
H2A—C2—H2B	108.5	O3—S1—O2	105.25 (7)
C4—C3—S1	111.66 (13)	O4—S1—O2	109.83 (8)
C4—C3—H3A	109.3	O3—S1—C3	108.96 (9)
S1—C3—H3A	109.3	O4—S1—C3	109.21 (8)
C4—C3—H3B	109.3	O2—S1—C3	103.77 (8)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O3^ii	0.97	2.53	3.219 (2)	128
C2—H2B···O4^iii	0.97	2.41	3.332 (2)	159
C3—H3A···O3^iv	0.97	2.65	3.594 (2)	163
C5—H5B···O2^v	0.93	2.64	3.447 (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.