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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o250.
Published online 2007 December 12. doi:  10.1107/S1600536807065488
PMCID: PMC2915307

Dibenzyl penta­thio­dicarbonate

Abstract

In the title compound, C16H14S5, the non-bonded intra­molecular distances between the non-terminal S atoms are 2.808 (16) and 2.784 (16) Å, shorter than the typical distance of 2.9 Å. One phenyl ring participates in an offset π-π inter­action with another phenyl ring related by a centre of inversion; the inter­planar distance is 3.41 (2) Å. The crystal structure also exhibits edge-to-face C—H(...)π stacking of the phenyl rings, thus forming a herring-bone packing motif.

Related literature

For related literature, see: Amin et al. (1979 [triangle]); Degani et al. (1986 [triangle]); McLeary & Klumperman (2006 [triangle]); Moad et al. (2005 [triangle]).

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Object name is e-64-0o250-scheme1.jpg

Experimental

Crystal data

  • C16H14S5
  • M r = 366.57
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o250-efi1.jpg
  • a = 8.4085 (18) Å
  • b = 19.670 (4) Å
  • c = 11.085 (3) Å
  • β = 111.953 (4)°
  • V = 1700.4 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.67 mm−1
  • T = 100 (2) K
  • 0.18 × 0.14 × 0.08 mm

Data collection

  • Bruker APEX CCD area-detector diffractometer
  • Absorption correction: none
  • 10376 measured reflections
  • 3872 independent reflections
  • 2278 reflections with I > 2σ(I)
  • R int = 0.080

Refinement

  • R[F 2 > 2σ(F 2)] = 0.061
  • wR(F 2) = 0.107
  • S = 0.92
  • 3872 reflections
  • 190 parameters
  • H-atom parameters constrained
  • Δρmax = 0.47 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2003 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]; Atwood & Barbour, 2003 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807065488/wn2221sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065488/wn2221Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Prof L. J. Barbour, Dr Martin Bredenkamp and Dr Catharine Esterhuysen for helpful discussions. Financial support for this work was provided by the National Research Foundation of South Africa. The data collection was undertaken on an instrument managed by the Central Analytical Facility at the University of Stellenbosch

supplementary crystallographic information

Comment

Di- and trithiocarbonate systems have recently found widespread application as mediators in free radical polymerization (Moad et al., 2005 and McLeary & Klumperman, 2006). As part of a further investigation of the interaction of these multi-thio compounds with radical species, extended polythiocarbonate systems have been examined. The preparation and characterization of pentathiodicarbonates is presented here. Two new dialkyl pentathiodicarbonates R–S–C(?S)–S–C(?S)–S–R with R = benzyl and tert-butyl were prepared by reaction of potassium benzyl- or tert-butyl-trithiocarbonate, respectively, with 2-chloro–N-methylpyridinium iodide (Scheme 2). The title compound is also formed by the reaction of potassium benzyltrithiocarbonate with benzyl dithiochloroformate (36% yield). The structure and details of the title compound are reported here.

The non-bonded intramolecular distance between S1 and S3 is 2.808 (16) Å and between S3 and S5 is 2.784 (16) Å. These are shorter than the 2.9 Å separation that is typically associated with distances of this type. The short contact is possible because of the out-of-plane twisting of the two thiono atoms, S2 and S4, and is likely brought about by steric hindrance between these two atoms. The intramolecular non-bonded distance between the two thiono atoms, S2 and S4, is 3.826 (16) Å.

The packing motif is mediated by the benzyl rings at either end of the molecule. For the purposes of this discussion we shall refer to the ring that is made up of C1, C2, C3, C4, C5 and C6 as Ring A and the ring consisting of C11, C12, C13, C14, C15 and C16 as Ring B. Ring A participates in an offset π-π interaction with another Ring A that is related by a centre of inversion. The linking methylene carbon atom (C7) also takes part in the interaction between these units. The interplanar spacing between the planes defined by the atoms of the two benzyl rings is 3.41 (2) Å. On its opposite side, Ring A interacts with a neighbouring Ring B, of a molecule related by 1 + x, y, 1 + z, in an edge-to-face manner where H12 is situated 3.009 (4) Å from the plane defined by the atoms of Ring A.

Packing in the solid state is further mediated by a number of close contacts with neighbouring molecules, although none of the classical H-bond variety. A short intermolecular distance of 2.949 (4) Å is found between S5 and H5 of a molecule related by the 2 - x, -y, 1 - z symmetry operation. S4 is separated from H14 (x, y, 1 + z) and S2 from H3 (x-1,y, z - 1) by 2.998 (4) Å and 3.048 (5) Å, respectively. S1 is at a distance of 3.011 Å (4) from H13 (1 + x, y, 1 + z).

Experimental

Potassium benzyltrithiocarbonate was prepared in situ by the reaction of benzyl mercaptan with carbon disulfide in aqueous potassium hydroxide (Degani,et al., 1986) and 2-chloro-N-methylpyridinium iodide from 2-chloropyridine and methyl iodide (Amin et al., 1979). Dibenzyl pentathiodicarbonate was prepared by adding 6.4 g (25 mmol) pyridinium salt within 5 min to a stirred and cooled aqueous solution of 50 mmol of potassium benzyl trithiocarbonate. Stirring continued for another 30 min and the red crystals formed were filtered off and washed several times with water. The crude product can be crystallized from acetonitrile with slow cooling to form larger red crystals. Yield = 7.6 g (83%). 1H NMR (300 MHz, CDCl3) δ (p.p.m.): 7.30–7.35 (m, 10H, Ar), 4.52 (s, 4H, CH2); 13C NMR (75 MHz, CDCl3) δ (p.p.m.): 214.30 (C?S), 133.88, 129.51, 128.95 and 128.20 (C-aromatic), 43.00 (CH2).

Refinement

H atoms were positioned geometrically and refined using a riding model [Csp3—H = 0.99 Å and Csp2—H = 0.95 Å; Uiso(H) = 1.2Ueq(C)].

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
The crystal packing of the title compound, viewed along [100], showing a herringbone packing motif.
Fig. 3.
The preparation of dibenzyl pentathiodicarbonate.

Crystal data

C16H14S5F000 = 760
Mr = 366.57Dx = 1.432 Mg m3
Monoclinic, P21/nMelting point = 318.15–319.15 K
Hall symbol: -P 2ynMo Kα radiation λ = 0.71073 Å
a = 8.4085 (18) ÅCell parameters from 2278 reflections
b = 19.670 (4) Åθ = 2.6–28.3º
c = 11.085 (3) ŵ = 0.67 mm1
β = 111.953 (4)ºT = 100 (2) K
V = 1700.4 (6) Å3Block, red
Z = 40.18 × 0.14 × 0.08 mm

Data collection

Bruker APEX CCD area-detector diffractometer2278 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.080
Monochromator: graphiteθmax = 28.3º
T = 100(2) Kθmin = 2.1º
ω scansh = −11→6
Absorption correction: nonek = −24→24
10376 measured reflectionsl = −14→14
3872 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.107  w = 1/[σ2(Fo2) + (0.0279P)2] where P = (Fo2 + 2Fc2)/3
S = 0.92(Δ/σ)max < 0.001
3872 reflectionsΔρmax = 0.47 e Å3
190 parametersΔρmin = −0.39 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 > 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)

xyzUiso*/Ueq
S50.77686 (14)0.15552 (5)0.17633 (10)0.0237 (3)
S11.03496 (15)0.09626 (6)0.69649 (11)0.0306 (3)
S40.66740 (14)0.21112 (5)0.38636 (11)0.0254 (3)
S30.96317 (13)0.11315 (5)0.42975 (11)0.0255 (3)
S20.72043 (14)0.02767 (5)0.51002 (11)0.0299 (3)
C110.6056 (5)0.20472 (19)−0.0574 (4)0.0204 (9)
C100.6221 (5)0.21790 (19)0.0801 (4)0.0224 (10)
H10A0.51050.21180.08950.027*
H10B0.66390.26470.10700.027*
C61.1089 (5)0.05569 (19)0.9414 (4)0.0202 (9)
C130.4729 (5)0.1434 (2)−0.2583 (4)0.0255 (10)
H130.38750.1128−0.31040.031*
C140.5886 (5)0.17070 (19)−0.3055 (4)0.0261 (10)
H140.58260.1594−0.39040.031*
C80.8884 (5)0.07591 (18)0.5457 (4)0.0231 (10)
C90.7847 (5)0.16372 (18)0.3323 (4)0.0190 (9)
C160.7212 (5)0.23211 (19)−0.1066 (4)0.0227 (10)
H160.80610.2632−0.05530.027*
C51.2588 (6)0.01676 (19)0.9908 (5)0.0278 (11)
H51.2793−0.01830.93950.033*
C120.4803 (5)0.1602 (2)−0.1365 (4)0.0243 (10)
H120.39910.1413−0.10520.029*
C150.7139 (5)0.2148 (2)−0.2283 (4)0.0265 (10)
H150.79540.2332−0.26000.032*
C11.0855 (5)0.1055 (2)1.0204 (4)0.0279 (11)
H10.98440.13240.98860.034*
C21.2013 (6)0.1176 (2)1.1416 (5)0.0347 (12)
H21.18120.15271.19290.042*
C41.3762 (5)0.0294 (2)1.1135 (5)0.0355 (12)
H41.47870.00341.14570.043*
C31.3486 (6)0.0789 (2)1.1907 (5)0.0378 (13)
H31.42930.08641.27640.045*
C70.9785 (6)0.0428 (2)0.8083 (4)0.0352 (12)
H7A0.86230.05440.80490.042*
H7B0.9796−0.00570.78480.042*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S50.0273 (7)0.0242 (6)0.0186 (6)0.0081 (5)0.0073 (5)0.0018 (5)
S10.0329 (7)0.0374 (7)0.0211 (7)−0.0161 (6)0.0097 (5)−0.0005 (5)
S40.0272 (7)0.0260 (6)0.0265 (7)0.0055 (5)0.0142 (5)0.0015 (5)
S30.0218 (6)0.0297 (6)0.0249 (6)0.0061 (5)0.0086 (5)0.0076 (5)
S20.0257 (7)0.0267 (6)0.0302 (7)−0.0055 (5)0.0021 (5)0.0040 (5)
C110.021 (2)0.019 (2)0.020 (2)0.0088 (19)0.0068 (19)0.0058 (19)
C100.019 (2)0.022 (2)0.023 (3)0.0065 (19)0.0032 (19)0.0024 (19)
C60.026 (3)0.017 (2)0.018 (2)−0.0084 (19)0.0096 (19)−0.0011 (18)
C130.023 (3)0.025 (2)0.024 (3)0.000 (2)0.005 (2)0.001 (2)
C140.035 (3)0.026 (2)0.018 (2)0.007 (2)0.010 (2)0.0065 (19)
C80.026 (3)0.019 (2)0.024 (3)0.0005 (19)0.010 (2)−0.0016 (19)
C90.016 (2)0.019 (2)0.021 (2)−0.0035 (18)0.0062 (18)0.0039 (18)
C160.018 (2)0.018 (2)0.028 (3)0.0034 (18)0.004 (2)0.0013 (19)
C50.040 (3)0.014 (2)0.043 (3)−0.008 (2)0.031 (3)−0.006 (2)
C120.021 (2)0.030 (3)0.023 (3)−0.002 (2)0.010 (2)0.002 (2)
C150.026 (3)0.026 (2)0.034 (3)0.000 (2)0.019 (2)0.010 (2)
C10.027 (3)0.021 (2)0.036 (3)0.006 (2)0.013 (2)0.002 (2)
C20.044 (3)0.022 (3)0.042 (3)−0.006 (2)0.020 (3)−0.012 (2)
C40.014 (3)0.036 (3)0.055 (4)0.006 (2)0.011 (2)0.024 (3)
C30.031 (3)0.051 (3)0.024 (3)−0.022 (3)0.002 (2)0.007 (2)
C70.038 (3)0.045 (3)0.022 (3)−0.019 (2)0.011 (2)0.002 (2)

Geometric parameters (Å, °)

S5—C91.713 (4)C13—H130.9500
S5—C101.816 (4)C14—C151.386 (5)
S1—C81.712 (4)C14—H140.9500
S1—C71.818 (4)C16—C151.371 (5)
S4—C91.626 (4)C16—H160.9500
S3—C81.786 (4)C5—C41.372 (6)
S3—C91.788 (4)C5—H50.9500
S2—C81.623 (4)C12—H120.9500
C11—C161.388 (5)C15—H150.9500
C11—C121.398 (5)C1—C21.353 (6)
C11—C101.500 (5)C1—H10.9500
C10—H10A0.9900C2—C31.380 (6)
C10—H10B0.9900C2—H20.9500
C6—C11.375 (5)C4—C31.371 (6)
C6—C51.400 (5)C4—H40.9500
C6—C71.495 (5)C3—H30.9500
C13—C121.368 (5)C7—H7A0.9900
C13—C141.374 (5)C7—H7B0.9900
C9—S5—C10106.15 (18)C11—C16—H16119.7
C8—S1—C7104.72 (19)C4—C5—C6119.8 (4)
C8—S3—C9102.81 (18)C4—C5—H5120.1
C16—C11—C12118.1 (4)C6—C5—H5120.1
C16—C11—C10121.3 (4)C13—C12—C11121.0 (4)
C12—C11—C10120.5 (4)C13—C12—H12119.5
C11—C10—S5104.7 (2)C11—C12—H12119.5
C11—C10—H10A110.8C16—C15—C14120.4 (4)
S5—C10—H10A110.8C16—C15—H15119.8
C11—C10—H10B110.8C14—C15—H15119.8
S5—C10—H10B110.8C2—C1—C6122.4 (4)
H10A—C10—H10B108.9C2—C1—H1118.8
C1—C6—C5117.6 (4)C6—C1—H1118.8
C1—C6—C7121.5 (4)C1—C2—C3120.1 (4)
C5—C6—C7121.0 (4)C1—C2—H2120.0
C12—C13—C14120.3 (4)C3—C2—H2120.0
C12—C13—H13119.9C3—C4—C5121.4 (4)
C14—C13—H13119.9C3—C4—H4119.3
C13—C14—C15119.5 (4)C5—C4—H4119.3
C13—C14—H14120.2C4—C3—C2118.7 (4)
C15—C14—H14120.2C4—C3—H3120.6
S2—C8—S1128.2 (2)C2—C3—H3120.6
S2—C8—S3124.9 (3)C6—C7—S1107.0 (3)
S1—C8—S3106.8 (2)C6—C7—H7A110.3
S4—C9—S5128.8 (2)S1—C7—H7A110.3
S4—C9—S3125.7 (2)C6—C7—H7B110.3
S5—C9—S3105.34 (19)S1—C7—H7B110.3
C15—C16—C11120.7 (4)H7A—C7—H7B108.6
C15—C16—H16119.7
C16—C11—C10—S5−83.6 (4)C7—C6—C5—C4−179.8 (3)
C12—C11—C10—S591.5 (4)C14—C13—C12—C11−0.5 (6)
C9—S5—C10—C11−174.6 (3)C16—C11—C12—C130.7 (6)
C12—C13—C14—C150.7 (6)C10—C11—C12—C13−174.6 (4)
C7—S1—C8—S27.5 (3)C11—C16—C15—C141.4 (6)
C7—S1—C8—S3−168.2 (2)C13—C14—C15—C16−1.1 (6)
C9—S3—C8—S259.4 (3)C5—C6—C1—C20.1 (6)
C9—S3—C8—S1−124.7 (2)C7—C6—C1—C2179.5 (4)
C10—S5—C9—S45.7 (3)C6—C1—C2—C3−0.6 (7)
C10—S5—C9—S3−170.05 (18)C6—C5—C4—C31.3 (6)
C8—S3—C9—S442.3 (3)C5—C4—C3—C2−1.7 (6)
C8—S3—C9—S5−141.73 (19)C1—C2—C3—C41.4 (6)
C12—C11—C16—C15−1.2 (6)C1—C6—C7—S190.3 (4)
C10—C11—C16—C15174.1 (3)C5—C6—C7—S1−90.4 (4)
C1—C6—C5—C4−0.4 (6)C8—S1—C7—C6176.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C12—H12···Cgi0.953.013.9056 (4)163

Symmetry codes: (i) x+1, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WN2221).

References

  • Amin, S. G., Glazer, R. D. & Manhas, M. S. (1979). Synthesis, pp. 210–213.
  • Atwood, J. L. & Barbour, L. J. (2003). Cryst. Growth Des.3, 3–8.
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2002). SMART Version 5.628. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2003). SAINT Version 6.45. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Degani, I., Fochi, R., Gatti, A. & Regondi, V. (1986). Synthesis, pp. 894–899.
  • McLeary, J. B. & Klumperman, B. (2006). Soft Matter, 2, 44–53.
  • Moad, G., Rizzardo, E. & Thang, S. H. (2005). Aust. J. Chem.58, 379–410.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Westrip, S. P. (2008). publCIF Version 1.9.0_c. In preparation.

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