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The title compound, C10H16O4S2, was formed in a reaction of allyl alcohol and thio­glycolic acid followed by acid-catalyzed esterification of the resulting hydroxy acid. The compound forms triclinic crystals and there is an inversion center in the middle of the mol­ecule The structure was determined to be a 14-membered dilide which in the solid state assumes a centrosymmetric conformation where the S-C-C-O-C-C-C-S chain is roughly gauche-gauche-anti-anti-gauche-anti-gauche. Molecular-mechanics calculations showed that the X-ray conformation is 10 kJ above the global minimum.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003038/cv6004sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003038/cv6004Isup2.hkl
Contains datablock I

CCDC reference: 159865

Key indicators

  • Single-crystal X-ray study
  • T = 193 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.048
  • wR factor = 0.129
  • Data-to-parameter ratio = 10.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.916 Tmax scaled 0.916 Tmin scaled 0.811

Comment top

In an attempt to prepare 1,4-oxathian-2-one (Koskimies, 1984), allyl alcohol and thioglycolic acid were reacted followed by acid-catalyzed esterification of the hydroxy acid formed. A crystalline product, believed to be 1,4-thiepan-2-one (Davies et al., 1977) on the basis of its NMR spectrum, was obtained. However, its mass spectrum showed a molecular ion peak of 264, suggesting the dimer. The structure of the dimer was confirmed by X-ray structure analysis as a 14-membered dilide. The formation of the 14-membered ring rather than seven-membered lactone is probably facilitated by the presence of sulfur with long C—S bonds in the hydroxy acid chain: the seven-membered lactone is more strained than the corresponding carbocyclic lactone or the 14-membered dilide. In the solid state, the compound assumes a centrosymmetric conformation where the S1—C2—C3—O4—C5—C6—C7—S1A chain is roughly gauche-gauche-anti-anti-gauche-anti-gauche. The conformation may be classified as [77] using Dale's nomenclature (Dale, 1973) with corner points at both S atoms. This unusual structure is made possible by two parallel planar ester groups: C2, C3, O8, O4 and C5 are practically in the plane. The corresponding carbon dilide 1,8-dioxacyclotetradecane-2,9-dione (Groth, 1985), as well as tridecanolactone (Wiberg et al., 1991), both crystallize in the [3434] conformation. The latter diamond-lattice conformation is also preferred by the parent hydrocarbon cyclotetradecane (Ounsworth & Weiler, 1987). Molecular-mechanics calculations (Mohamadi, 1990) showed that the X-ray conformation is 10 kJ above the global minimum. This minimum-energy conformer is also centrosymmetric and of the [3434] type, the corner points in 2, 6, 2' and 6'. The conformation is very similar to that of 1,8-dioxacyclotetradecane-2,9-dione (Groth, 1985). The main difference between X-ray structure and the minimum conformation is that the latter is square-shaped with carbonyl bonds axial with respect to the molecular plain while the X-ray conformation is oval-shaped with S atoms at the both ends and the carbonyl O atoms in the ring plane. Molecular-mechanics calculations suggest that the solid-state conformation is favored in more polar media. Analysis of vicinal coupling constants in the 1H NMR spectrum indicate that in solution no single conformation is dominating, a fact also predicted by molecular-mechanics calculations.

Experimental top

The title compound was prepared by mixing aqueous (80%) thioglycolic acid (10 ml, 0.15 mol) and allyl alcohol (13.5 ml, 0.15 mol). When the reaction has subsided, benzene (100 ml) and p-toluenesulfonic acid (0.2 g) were added and the reaction flask fitted with a Dean–Stark trap and condenser. The solution was refluxed until no water was collected in the trap. The solid obtained was recrystallized from benzene dried in vacuo, yield 2.1 g (11%), m.p. 403.5–404.0 K. NMR (250 MHz) (CDCl3): 4.30 (t, J = 5 Hz), 3.27 (s), 2.86 (t, J = 5 Hz), 2.0 (m). Mass spectrum: 264,133, 132, 114, 89, 88, 87, 61, 46, 45. IR (ATR): 2964 (m), 1722 (s), 1460 (w), 1419 (m), 1376 (w), 1273 (m) 1220 (m), 1178 (m), 1127 (s), 1058 (m), 1015 (m), 951 (w), 876 (w), 847 (w), 797 (w), 740 (w), 713 (w). A crystal suitable for X-ray work were obtained from acetonitrile and mounted on a glass fiber using the oil-drop method (Kottke & Stalke, 1993) and data were collected at 193 K.

Refinement top

The intensity data were corrected for Lorentz and polarization effects and for absorption. All non-H atoms were refined anisotropically. H atoms were located from difference Fourier maps and were refined isotropically.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a); cell refinement: TEXSAN (Molecular Structure Corporation, 1993b); data reduction: TEXSAN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. View of the title molecule. The displacement ellipsoids are drawn at the 30% probability level.
(I) top
Crystal data top
C10H16O4S2Z = 1
Mr = 264.35F(000) = 140
Triclinic, P1Dx = 1.450 Mg m3
a = 5.3920 (18) ÅMo Kα radiation, λ = 0.71073 Å
b = 6.858 (3) ÅCell parameters from 25 reflections
c = 8.960 (6) Åθ = 3.5–7.5°
α = 71.88 (4)°µ = 0.44 mm1
β = 74.04 (3)°T = 193 K
γ = 85.41 (4)°Plate, colorless
V = 302.8 (3) Å30.40 × 0.37 × 0.20 mm
Data collection top
Rigaku AFC-7S
diffractometer
1017 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.076
Graphite monochromatorθmax = 25.2°, θmin = 3.1°
ω/2θ scansh = 66
Absorption correction: ψ scan
(North et al., 1968)
k = 88
Tmin = 0.885, Tmax = 1.000l = 1010
2360 measured reflections3 standard reflections every 200 reflections
1082 independent reflections intensity decay: 0.1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129All H-atom parameters refined
S = 1.04 w = 1/[σ2(Fo2) + (0.0741P)2 + 0.1359P]
where P = (Fo2 + 2Fc2)/3
1082 reflections(Δ/σ)max < 0.001
105 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = 0.59 e Å3
Crystal data top
C10H16O4S2γ = 85.41 (4)°
Mr = 264.35V = 302.8 (3) Å3
Triclinic, P1Z = 1
a = 5.3920 (18) ÅMo Kα radiation
b = 6.858 (3) ŵ = 0.44 mm1
c = 8.960 (6) ÅT = 193 K
α = 71.88 (4)°0.40 × 0.37 × 0.20 mm
β = 74.04 (3)°
Data collection top
Rigaku AFC-7S
diffractometer
1017 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.076
Tmin = 0.885, Tmax = 1.0003 standard reflections every 200 reflections
2360 measured reflections intensity decay: 0.1%
1082 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.129All H-atom parameters refined
S = 1.04Δρmax = 0.42 e Å3
1082 reflectionsΔρmin = 0.59 e Å3
105 parameters
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 > 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) top
xyzUiso*/Ueq
S10.23774 (10)0.32376 (8)0.93150 (7)0.0339 (3)
C20.3355 (4)0.1144 (3)0.8452 (3)0.0300 (5)
H2A0.278 (5)0.008 (4)0.936 (4)0.031 (6)*
H2B0.522 (6)0.113 (4)0.805 (4)0.041 (7)*
C30.2011 (4)0.1243 (3)0.7160 (3)0.0271 (5)
O40.3425 (3)0.2284 (3)0.5675 (2)0.0346 (4)
C50.2336 (5)0.2514 (4)0.4309 (3)0.0342 (6)
H5A0.049 (6)0.254 (4)0.467 (4)0.045 (8)*
H5B0.287 (6)0.132 (5)0.393 (4)0.045 (8)*
C60.3355 (4)0.4494 (4)0.3022 (3)0.0330 (5)
H6A0.279 (5)0.561 (4)0.350 (4)0.040 (7)*
H6B0.252 (6)0.466 (5)0.215 (5)0.059 (9)*
C70.6307 (4)0.4529 (3)0.2375 (3)0.0319 (5)
H7A0.690 (6)0.338 (5)0.193 (4)0.048 (8)*
H7B0.708 (6)0.433 (4)0.325 (4)0.044 (8)*
O80.0088 (3)0.0500 (3)0.7408 (2)0.0435 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0345 (4)0.0308 (4)0.0321 (5)0.0044 (3)0.0001 (3)0.0103 (3)
C20.0264 (11)0.0253 (11)0.0351 (14)0.0001 (8)0.0058 (10)0.0066 (10)
C30.0249 (10)0.0207 (10)0.0336 (13)0.0013 (8)0.0049 (9)0.0082 (9)
O40.0284 (8)0.0408 (9)0.0310 (10)0.0117 (7)0.0054 (7)0.0052 (8)
C50.0317 (12)0.0387 (13)0.0337 (15)0.0072 (10)0.0085 (10)0.0112 (11)
C60.0295 (12)0.0326 (12)0.0352 (14)0.0016 (9)0.0067 (10)0.0090 (11)
C70.0307 (11)0.0266 (11)0.0350 (14)0.0004 (9)0.0032 (10)0.0094 (10)
O80.0323 (9)0.0510 (11)0.0417 (12)0.0162 (8)0.0061 (8)0.0055 (9)
Geometric parameters (Å, º) top
S1—C7i1.812 (3)C5—H5A0.96 (3)
S1—C21.812 (2)C5—H5B0.97 (3)
C2—C31.508 (3)C6—C71.536 (3)
C2—H2A0.97 (3)C6—H6A0.98 (3)
C2—H2B0.97 (3)C6—H6B0.97 (4)
C3—O81.214 (3)C7—S1i1.812 (3)
C3—O41.341 (3)C7—H7A0.99 (3)
O4—C51.459 (3)C7—H7B0.96 (3)
C5—C61.507 (4)
C7i—S1—C2102.91 (12)C6—C5—H5B112.4 (19)
C3—C2—S1111.21 (14)H5A—C5—H5B109 (2)
C3—C2—H2A108.8 (15)C5—C6—C7113.0 (2)
S1—C2—H2A104.2 (15)C5—C6—H6A107.6 (17)
C3—C2—H2B112.3 (18)C7—C6—H6A110.0 (16)
S1—C2—H2B110.3 (16)C5—C6—H6B106 (2)
H2A—C2—H2B110 (2)C7—C6—H6B111 (2)
O8—C3—O4123.5 (2)H6A—C6—H6B108 (2)
O8—C3—C2125.2 (2)C6—C7—S1i115.03 (17)
O4—C3—C2111.31 (18)C6—C7—H7A110.8 (17)
C3—O4—C5117.05 (18)S1i—C7—H7A103.3 (19)
O4—C5—C6107.84 (18)C6—C7—H7B109.6 (19)
O4—C5—H5A109.3 (19)S1i—C7—H7B111.8 (19)
C6—C5—H5A110.8 (18)H7A—C7—H7B106 (2)
O4—C5—H5B106.9 (18)
C7i—S1—C2—C366.99 (18)C3—O4—C5—C6150.67 (19)
S1—C2—C3—O886.9 (2)O4—C5—C6—C761.0 (3)
S1—C2—C3—O492.61 (19)C5—C6—C7—S1i174.15 (16)
O8—C3—O4—C50.1 (3)S1—C2—C3—O492.61 (19)
C2—C3—O4—C5179.42 (17)C3—O4—C5—C6150.67 (19)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC10H16O4S2
Mr264.35
Crystal system, space groupTriclinic, P1
Temperature (K)193
a, b, c (Å)5.3920 (18), 6.858 (3), 8.960 (6)
α, β, γ (°)71.88 (4), 74.04 (3), 85.41 (4)
V3)302.8 (3)
Z1
Radiation typeMo Kα
µ (mm1)0.44
Crystal size (mm)0.40 × 0.37 × 0.20
Data collection
DiffractometerRigaku AFC-7S
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.885, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
2360, 1082, 1017
Rint0.076
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.129, 1.04
No. of reflections1082
No. of parameters105
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.42, 0.59

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a), TEXSAN (Molecular Structure Corporation, 1993b), TEXSAN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1994), SHELXL97.

Selected torsion angles (º) top
C7i—S1—C2—C366.99 (18)C3—O4—C5—C6150.67 (19)
S1—C2—C3—O886.9 (2)O4—C5—C6—C761.0 (3)
S1—C2—C3—O492.61 (19)C5—C6—C7—S1i174.15 (16)
O8—C3—O4—C50.1 (3)S1—C2—C3—O492.61 (19)
C2—C3—O4—C5179.42 (17)C3—O4—C5—C6150.67 (19)
Symmetry code: (i) x+1, y+1, z+1.
 

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