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Bis[(methyl­sulfan­yl)carbon­yl]disulfane

aDepartment of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA
*Correspondence e-mail: barany@umn.edu

(Received 2 April 2012; accepted 30 May 2012; online 13 June 2012)

The title compound, C4H6O2S4, was prepared by repeating, with subtle improvements, a multi-step route originally described by Mott & Barany [J. Chem. Soc. Perkin Trans. 1 (1984)[Mott, A. W. & Barany, G. (1984). J. Chem. Soc. Perkin Trans. 1, pp. 2615-2621.], pp. 2615–2621]. The title compound was obtained for the first time as a crystalline material. The two [(methyl­sulfan­yl)carbon­yl]sulfenyl moieties are essentially perpendic­ular to each other, each approximately planar (r.m.s. deviations of 0.02 and 0.01 Å) and with a C—S—S—C torsion angle = 90.99 (6)°, which compares well with the theoretical value of 90°.

Related literature

For the preparation of the title compound and for the preparation and structures of the corresponding trisulfane and tetrasulfane compounds, see: Mott & Barany (1984[Mott, A. W. & Barany, G. (1984). J. Chem. Soc. Perkin Trans. 1, pp. 2615-2621.]). For other related structures, see: Bereman et al. (1983[Bereman, R. D., Baird, D. N., Bordner, J. & Dorfman, J. R. (1983). Polyhedron, 2, 25-30.]); Rout et al. (1983[Rout, G. C., Seshasayee, M., Subrahmanyan, T. & Aravamudan, G. (1983). Acta Cryst. C39, 1387-1389.]); Paul & Srikrishnan (2004[Paul, C. & Srikrishnan, T. (2004). J. Chem. Crystallogr. 34, 211-217.]); Li et al. (2006[Li, F., Yin, H.-D., Hong, M., Zhai, J. & Wang, D.-Q. (2006). Acta Cryst. E62, m1417-m1418.]); Schroll et al. (2012[Schroll, A. L., Pink, M. & Barany, G. (2012). Acta Cryst. E68, o1550.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]). For optimum dihedral angles, see: Pauling (1960[Pauling, L. (1960). The Nature of the Chemical Bond, pp. 134-135. Ithaca, New York: Cornell University Press.]). For background to isomeric bis­(alk­oxy­thio­carbon­yl)­poly­sulfanes, see: Reid (1962[Reid, E. E. (1962). Organic Chemistry of Bivalent Sulfur, Vol. 4, pp. 150-153. New York: Chemical Publishing.]).

[Scheme 1]

Experimental

Crystal data
  • C4H6O2S4

  • Mr = 214.33

  • Triclinic, [P \overline 1]

  • a = 5.3300 (7) Å

  • b = 8.6935 (12) Å

  • c = 9.9166 (13) Å

  • α = 109.875 (2)°

  • β = 92.154 (2)°

  • γ = 101.481 (2)°

  • V = 420.71 (10) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 1.07 mm−1

  • T = 123 K

  • 0.35 × 0.30 × 0.25 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008a[Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany. ]) Tmin = 0.707, Tmax = 0.776

  • 5024 measured reflections

  • 1894 independent reflections

  • 1774 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.021

  • wR(F2) = 0.054

  • S = 1.07

  • 1894 reflections

  • 93 parameters

  • H-atom parameters constrained

  • Δρmax = 0.36 e Å−3

  • Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 1998[Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SMART; data reduction: SAINT (Bruker, 1998[Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b[Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

While bis(alkoxysulfanylcarbonyl)polysulfanes, [RO(CS)]2Sn (n = 1, 2, 3, 4) have been known for a long time due to their derivation from readily formed xanthate salts (Reid, 1962), much less information is available about the isomeric bis[alkyl(sulfanylcarbonyl)]polysulfanes, [RS(CO)]2Sn (Mott & Barany, 1984). In 1984, we reported methodology for the preparation of reasonably pure (>95%) exemplars in the latter family for R = Me; the trisulfane and tetrasulfane of the series were obtained as crystals and their structures were solved by X-ray diffraction (Mott & Barany, 1984). Beyond the successful synthetic routes reported therein, a number of alternative methods were tested, which seemed rather straightforward and were well precedented for analogous compounds, but failed for the series under investigation. For the present studies, we carried out more careful experimental work aimed at the disulfane (Fig. 3), and obtained it in crystalline form for the first time. The structure of the disulfane was solved by X-ray crystallography, and compared to the structures determined earlier.

All bond distances and angles are within expected ranges. Because the disulfane is adjacent to carbonyl groups, the S—S bond length of 2.03 Å is slightly shorter than the 2.07 Å reported for the S—S bond length in S8. This phenomenon is quite general and has been observed for related compounds. In all, a search of the Cambridge Database for compounds of the formula R(CO)SS(CO)R provided four different compounds for comparison [CSD refcodes: BOWGAV (Bereman et al., 1983), DBZOSS01&03 (Rout et al., 1983; Paul & Srikrishnan, 2004), UDALER (Li et al., 2006), and 880326 (Schroll et al., 2012)]. The most noteworthy feature of our newly reported structure is that the torsion angle about the disulfane was 90.99°, which comes closer to the theoretical optimum of 90° (Pauling, 1960) than any other of the comparison compounds with the exception of bis(N,N-dicyclohexylsulfanylcarbamoyl)disulfane, where this angle is 89.7° (Li et al., 2006).

Note regarding nomenclature: The title compound is named in a manner that is consistent with our prior publications and modern conventions. The related compound studied by Li et al. (2006) was named bis(N,N-dicyclohexylsulfanylcarbamoyl)disulfide by those authors.

Related literature top

For background to analogous bis(alkoxysulfanylcarbonyl)polysulfanes, see: Reid (1962). For the preparation of the title compound and of closely related structures, see: Mott & Barany (1984). For other related structures, see: Bereman et al. (1983); Rout et al. (1983); Paul & Srikrishnan (2004); Li et al. (2006); Schroll et al. (2012). For the Cambridge Structural Database, see: Allen (2002). For optimum dihedral angles, see: Pauling (1960).

Experimental top

S-Methyl O-t-butyl disulfanylcarbonate (1). First, potassium t-butyl xanthate was prepared by adding carbon disulfide (37.0 ml, 0.61 mol) over 15 min to a well stirred suspension of potassium t-butoxide (69.7 g, 0.62 mol) in p-xylene (450 ml) at 80°C. The reaction mixture was allowed to cool to 25°C, and the orange-yellow precipitate which had formed was collected on a Buchner funnel, and washed with ethyl ether (1.7 l total, gravity filtration) over a 1 h period. After the final ether wash, the solid was air-dried by suction applied to the filtration apparatus from a water aspirator, and then dried further in a desiccator (20 mm) for 72 h (time required to achieve constant mass). Yield of xanthate salt: 80.3 g (70%). A portion of the xanthate salt (23.9 g, 127 mmol) was suspended in ether (200 ml), and neat iodomethane (12.0 ml, 193 mmol) was added, under magnetic stirring, at 25°C over a 2 min period. After 24 h, the reaction mixture was filtered and concentrated in vacuo to provide an unstable yellow oil (10.0 g, 48%) that was stored at -20°C and was usable for about 4 months. 1H NMR (CDCl3, 300 MHz) δ 2.46 [s, 3H, SMe], 1.70 [s, 9H, tBuO].

Bis[(methylsulfanyl)carbonyl]disulfane (2). Neat sulfuryl chloride (1.3 ml, 16.2 mmol) was added, with stirring at 4°C, over 1 min, to a solution of compound 1 (5.0 g, 30.4 mmol) in CHCl3 (20 ml). After completion of addition, stirring continued for a further 5 min, following which the homogeneous reaction mixture was concentrated in vacuo to provide the crude title product as a yellow oil [3.4 g, nominally quantitative, but comprising primarily desired 2 and starting 1 in a molar ratio of 7:4, along with smaller amounts of other impurities that were not identified further]. A portion (2.0 g) of the crude oil was purified by silica gel chromatography, eluted with hexanes–ethyl acetate (6:1). The purest fractions were placed under petroleum ether at -20°C, whereupon white crystals (0.27 g, >99% pure, 14% yield), m.p. 31–32°C, formed within 24 h. 1H NMR (CDCl3, 300 MHz) δ 2.48 [s, 6H, SCH3].

Refinement top

All of the H atoms were positioned geometrically (C—H = 0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXTL (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top
Crystallographic structure of bis[(methylsulfanyl)carbonyl]disulfane with all non-hydrogen atoms labeled and numbered.

Packing diagram for bis[(methylsulfanyl)carbonyl]disulfane.

Chemistry used to prepare bis[(methylsulfanyl)carbonyl]disulfane (experimental procedures are provided herein).
Bis[(methylsulfanyl)carbonyl]disulfane top
Crystal data top
C4H6O2S4Z = 2
Mr = 214.33F(000) = 220
Triclinic, P1Dx = 1.692 Mg m3
a = 5.3300 (7) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.6935 (12) ÅCell parameters from 2965 reflections
c = 9.9166 (13) Åθ = 2.2–27.5°
α = 109.875 (2)°µ = 1.07 mm1
β = 92.154 (2)°T = 123 K
γ = 101.481 (2)°Block, colourless
V = 420.71 (10) Å30.35 × 0.30 × 0.25 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1894 independent reflections
Radiation source: sealed tube1774 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ϕ and ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
h = 66
Tmin = 0.707, Tmax = 0.776k = 1110
5024 measured reflectionsl = 012
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)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0267P)2 + 0.1517P]
where P = (Fo2 + 2Fc2)/3
1894 reflections(Δ/σ)max = 0.001
93 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C4H6O2S4γ = 101.481 (2)°
Mr = 214.33V = 420.71 (10) Å3
Triclinic, P1Z = 2
a = 5.3300 (7) ÅMo Kα radiation
b = 8.6935 (12) ŵ = 1.07 mm1
c = 9.9166 (13) ÅT = 123 K
α = 109.875 (2)°0.35 × 0.30 × 0.25 mm
β = 92.154 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1894 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
1774 reflections with I > 2σ(I)
Tmin = 0.707, Tmax = 0.776Rint = 0.022
5024 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0210 restraints
wR(F2) = 0.054H-atom parameters constrained
S = 1.07Δρmax = 0.36 e Å3
1894 reflectionsΔρmin = 0.24 e Å3
93 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 > 2σ(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
S10.14601 (6)0.32879 (4)0.88175 (3)0.01738 (9)
S20.29712 (6)0.29567 (4)0.58244 (3)0.01738 (9)
S30.59396 (6)0.46586 (4)0.72293 (4)0.01720 (9)
S40.23910 (6)0.67401 (4)0.66158 (4)0.01664 (9)
O10.13318 (18)0.13895 (12)0.63241 (11)0.0206 (2)
O20.68271 (19)0.78866 (12)0.83115 (12)0.0242 (2)
C10.1386 (3)0.22275 (18)0.93481 (15)0.0203 (3)
H1A0.12280.25641.04020.030*
H1B0.15670.10110.89140.030*
H1C0.29060.25330.90160.030*
C20.0631 (2)0.23846 (16)0.69410 (14)0.0151 (3)
C30.5248 (2)0.66889 (17)0.75182 (14)0.0162 (3)
C40.2779 (3)0.89933 (17)0.72402 (17)0.0224 (3)
H4A0.12400.92640.68890.034*
H4B0.42910.94900.68720.034*
H4C0.30160.94470.82980.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.01675 (17)0.01802 (17)0.01540 (17)0.00122 (12)0.00094 (12)0.00507 (13)
S20.01809 (17)0.01627 (17)0.01596 (17)0.00210 (12)0.00280 (12)0.00433 (13)
S30.01357 (16)0.01617 (17)0.02213 (18)0.00337 (12)0.00094 (13)0.00725 (13)
S40.01479 (16)0.01637 (17)0.01887 (17)0.00321 (12)0.00024 (12)0.00678 (13)
O10.0178 (5)0.0190 (5)0.0212 (5)0.0005 (4)0.0005 (4)0.0048 (4)
O20.0210 (5)0.0181 (5)0.0297 (6)0.0003 (4)0.0060 (4)0.0070 (4)
C10.0189 (7)0.0214 (7)0.0213 (7)0.0026 (5)0.0049 (5)0.0094 (6)
C20.0164 (6)0.0130 (6)0.0169 (6)0.0058 (5)0.0021 (5)0.0050 (5)
C30.0151 (6)0.0169 (6)0.0184 (6)0.0037 (5)0.0031 (5)0.0083 (5)
C40.0231 (7)0.0162 (7)0.0288 (8)0.0053 (5)0.0006 (6)0.0090 (6)
Geometric parameters (Å, º) top
S1—C21.7553 (14)O2—C31.2067 (17)
S1—C11.8057 (14)C1—H1A0.9800
S2—C21.8057 (13)C1—H1B0.9800
S2—S32.0332 (5)C1—H1C0.9800
S3—C31.8047 (14)C4—H4A0.9800
S4—C31.7528 (14)C4—H4B0.9800
S4—C41.8077 (14)C4—H4C0.9800
O1—C21.2037 (16)
C2—S1—C198.04 (6)O1—C2—S2116.70 (10)
C2—S2—S3105.23 (5)S1—C2—S2117.13 (7)
C3—S3—S2105.85 (5)O2—C3—S4126.34 (11)
C3—S4—C497.96 (7)O2—C3—S3116.20 (10)
S1—C1—H1A109.5S4—C3—S3117.46 (7)
S1—C1—H1B109.5S4—C4—H4A109.5
H1A—C1—H1B109.5S4—C4—H4B109.5
S1—C1—H1C109.5H4A—C4—H4B109.5
H1A—C1—H1C109.5S4—C4—H4C109.5
H1B—C1—H1C109.5H4A—C4—H4C109.5
O1—C2—S1126.15 (10)H4B—C4—H4C109.5
C2—S2—S3—C390.99 (6)C4—S4—C3—O21.13 (14)
C1—S1—C2—O11.09 (13)C4—S4—C3—S3178.16 (8)
C1—S1—C2—S2177.21 (8)S2—S3—C3—O2178.71 (10)
S3—S2—C2—O1179.07 (9)S2—S3—C3—S40.65 (8)
S3—S2—C2—S12.46 (8)

Experimental details

Crystal data
Chemical formulaC4H6O2S4
Mr214.33
Crystal system, space groupTriclinic, P1
Temperature (K)123
a, b, c (Å)5.3300 (7), 8.6935 (12), 9.9166 (13)
α, β, γ (°)109.875 (2), 92.154 (2), 101.481 (2)
V3)420.71 (10)
Z2
Radiation typeMo Kα
µ (mm1)1.07
Crystal size (mm)0.35 × 0.30 × 0.25
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008a)
Tmin, Tmax0.707, 0.776
No. of measured, independent and
observed [I > 2σ(I)] reflections
5024, 1894, 1774
Rint0.022
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.054, 1.07
No. of reflections1894
No. of parameters93
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.36, 0.24

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008b).

 

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals
First citationBereman, R. D., Baird, D. N., Bordner, J. & Dorfman, J. R. (1983). Polyhedron, 2, 25–30.  CSD CrossRef CAS Web of Science
First citationBruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationLi, F., Yin, H.-D., Hong, M., Zhai, J. & Wang, D.-Q. (2006). Acta Cryst. E62, m1417–m1418.  Web of Science CSD CrossRef IUCr Journals
First citationMott, A. W. & Barany, G. (1984). J. Chem. Soc. Perkin Trans. 1, pp. 2615–2621.  CSD CrossRef Web of Science
First citationPaul, C. & Srikrishnan, T. (2004). J. Chem. Crystallogr. 34, 211–217.  Web of Science CSD CrossRef CAS
First citationPauling, L. (1960). The Nature of the Chemical Bond, pp. 134–135. Ithaca, New York: Cornell University Press.
First citationReid, E. E. (1962). Organic Chemistry of Bivalent Sulfur, Vol. 4, pp. 150–153. New York: Chemical Publishing.
First citationRout, G. C., Seshasayee, M., Subrahmanyan, T. & Aravamudan, G. (1983). Acta Cryst. C39, 1387–1389.  CSD CrossRef CAS Web of Science IUCr Journals
First citationSchroll, A. L., Pink, M. & Barany, G. (2012). Acta Cryst. E68, o1550.  CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008b). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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