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Ethane-1,2-diyl S,S′-bis­(thio­acetate), H3CC(O)SCH2CH2SC(O)CH3 or C6H10O2S2, forms centrosymmetric mol­ecules in the solid state and the molecular structure determined by X-ray crystallography is in good agreement with that obtained by density functional geometry optimization. The planarity of the O=C—S—C fragment, which is also found in structures of other thio­acetates, is attributed to a strong np(S)–π*(C—O) orbital interaction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004408/na6061sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004408/na6061Isup2.hkl
Contains datablock I

CCDC reference: 162819

Key indicators

  • Single-crystal X-ray study
  • T = 183 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.040
  • wR factor = 0.118
  • Data-to-parameter ratio = 20.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
CRYSS_02 Alert B The value of _exptl_crystal_size_max is > 1.0 Maximum crystal size given = 1.260
Yellow Alert Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.101
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

Thioesters are very important acetylating agents in biochemical processes as well as in many chemical transformations (Nicolaou, 1977; Hirama et al., 1979; Zheng et al., 1999). We obtained ethanedithiol diacetate, H3CC(O)SCH2CH2SC(O)CH3, (I), as a by-product in the synthesis of ethanedithiol monoacetate, HSCH2CH2SC(O)CH3, (II), according to literature procedure (Wiesler et al., 1996). Crystals of (I) precipitated at 278 K from its solution in (II). They were washed with cold petroleum ether and identified and checked for purity by 1H NMR (Bauer et al., 1965). One of them was selected for single-crystal X-ray diffraction.

The molecular structure of (I) as found in the solid state is depicted in Fig. 1. Table 1 shows selected structural parameters from the XRD experiment in comparison with those obtained by a density functional (DF) geometry optimization. Apart from the two S—C and the C2—C3 distances, the DF structural parameters agree quite well with the experimental ones, regardless that the former refer to an isolated molecule and the latter do not (see Table 1). We attribute the differences in the bond distances mentioned to the chosen level of theory and the agreement among most of the above values to the absence of significant intermolecular interactions in the crystal. The structural parameters of (I) agree well with those found for other compounds exhibiting an S-acetyl moiety (Evans et al., 1999; Divjakovic et al., 1992; Huber et al., 1984; Kiel et al., 1974; Mackay et al., 1992; Mattes et al., 1977, 1983; Shefter et al., 1969). This implies the S-acetyl fragment to be a relatively rigid structural unit. An analysis of the bonding situation in terms of natural bond orbitals (Reed at al., 1988) reveals a strong delocalization of electron density within the OC—S fragment. The p-type lone pair of the S atom interacts strongly with the π*(C—O) orbital (see Fig. 2a) and the p-type lone pair of the O-atom interacts strongly with the σ*(S—C) orbital (see Fig. 2 b). The np(S)–π*(C—O) interaction explains very well the nearly planar conformation of the C1—S1—C2—O1 moiety.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare, 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976).

Figures top
[Figure 1] Fig. 1. ORTEPII (Johnson, 1976) view of the centrosymmetric molecule of (I). Displacement ellipsoids are shown at the 50% probability level. H atoms are shown as spheres of fixed radius. The methyl group is disordered (0.45/0.55).
[Figure 2] Fig. 2. Scheme of orbital interaction within the –C(O)—S moiety of (I). See text for details.
Ethanedithiol Diacetate top
Crystal data top
C6H10O2S2F(000) = 188
Mr = 178.26Dx = 1.385 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
a = 5.1677 (6) ÅCell parameters from 2083 reflections
b = 7.1944 (9) Åθ = 3.3–28.3°
c = 11.6869 (15) ŵ = 0.56 mm1
β = 100.449 (2)°T = 183 K
V = 427.30 (9) Å3Block, colourless
Z = 21.26 × 0.37 × 0.30 mm
Data collection top
Smart CCD
diffractometer
968 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.101
Graphite monochromatorθmax = 28.3°, θmin = 3.3°
θ and ϕ scansh = 66
2629 measured reflectionsk = 95
1042 independent reflectionsl = 1515
Refinement top
Refinement on F2Secondary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.118 w = 1/[σ2(Fo2) + (0.0565P)2 + 0.0812P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
1042 reflectionsΔρmax = 0.45 e Å3
50 parametersΔρmin = 0.25 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.19 (2)
Crystal data top
C6H10O2S2V = 427.30 (9) Å3
Mr = 178.26Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.1677 (6) ŵ = 0.56 mm1
b = 7.1944 (9) ÅT = 183 K
c = 11.6869 (15) Å1.26 × 0.37 × 0.30 mm
β = 100.449 (2)°
Data collection top
Smart CCD
diffractometer
968 reflections with I > 2σ(I)
2629 measured reflectionsRint = 0.101
1042 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 1.10Δρmax = 0.45 e Å3
1042 reflectionsΔρmin = 0.25 e Å3
50 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*/UeqOcc. (<1)
S10.27383 (8)0.23911 (5)0.49337 (3)0.0326 (2)
O10.4897 (3)0.22872 (17)0.30668 (12)0.0403 (4)
C10.5368 (3)0.4064 (2)0.52802 (11)0.0287 (4)
H1A0.68630.36040.49910.034 (3)*
H1B0.57430.41220.61130.034 (3)*
C20.3155 (3)0.1687 (2)0.35255 (11)0.0274 (3)
C30.1178 (3)0.0283 (2)0.29814 (13)0.0362 (4)
H3A0.00340.00080.35140.060 (8)*0.45
H3B0.20850.08590.28230.060 (8)*0.45
H3C0.01870.07790.22510.060 (8)*0.45
H3D0.15270.00560.22110.061 (7)*0.55
H3E0.05930.08110.29020.061 (7)*0.55
H3F0.13050.08270.34750.061 (7)*0.55
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0404 (3)0.0322 (3)0.0286 (3)0.00492 (14)0.01547 (18)0.00315 (12)
O10.0504 (8)0.0418 (7)0.0338 (7)0.0111 (5)0.0212 (5)0.0088 (4)
C10.0341 (7)0.0296 (8)0.0221 (6)0.0020 (6)0.0046 (5)0.0001 (5)
C20.0344 (7)0.0238 (7)0.0250 (6)0.0035 (6)0.0080 (5)0.0004 (5)
C30.0405 (8)0.0284 (8)0.0394 (8)0.0021 (6)0.0065 (6)0.0061 (6)
Geometric parameters (Å, º) top
S1—C21.7720 (13)C1—C1i1.516 (3)
S1—C11.8056 (15)C2—C31.494 (2)
O1—C21.2080 (18)
C2—S1—C1100.69 (7)O1—C2—S1122.40 (12)
C1i—C1—S1112.06 (12)C3—C2—S1113.56 (10)
O1—C2—C3124.04 (13)
C2—S1—C1—C1i80.29 (14)C1—S1—C2—C3179.10 (11)
C1—S1—C2—O11.53 (15)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC6H10O2S2
Mr178.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)183
a, b, c (Å)5.1677 (6), 7.1944 (9), 11.6869 (15)
β (°) 100.449 (2)
V3)427.30 (9)
Z2
Radiation typeMo Kα
µ (mm1)0.56
Crystal size (mm)1.26 × 0.37 × 0.30
Data collection
DiffractometerSmart CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2629, 1042, 968
Rint0.101
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.118, 1.10
No. of reflections1042
No. of parameters50
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.25

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SIR92 (Altomare, 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).

Comparison of selected structural parameters (Å, °) from the molecular structures of (I) in the solid state (XRD) and from density functional (DF) geometry optimization [B3LYP/6-311+G(2d,p)] (Frisch et al., 1995) top
XRDDF
S1—C11.806 (2)1.833
S1—C21.772 (1)1.798
C1—C1a1.516 (3)1.522
C2—C31.494 (2)1.511
O1—C21.208 (2)1.206
C2—S1—-C1100.7 (1)100.2
C1a—C1–S1112.1 (1)112.3
O1—C2—C3124.0 (1)123.5
O1—C2—S1122.4 (1)123.1
C3—C2—S1113.6 (1)113.5
C2—S1—C1—C1a80.3 (1)82.0
C1—S1—C2—O11.5 (2)0.2
C1—S1—C2—C3-179.1 (1)-179.7
 

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