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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o361.
Published online 2009 January 23. doi:  10.1107/S1600536809001834
PMCID: PMC2968175

Bis(2-bromo­benz­yl) tris­ulfide

Abstract

The title mol­ecule, C14H12Br2S3, lies on a crystallographic twofold rotation axis which bis­ects the S—S—S angle. The dihedral angle between the two symmetry-related benzene rings is 89.91 (9)°. In terms of hybridization principles, the S—C—C angle is slightly larger than expected.

Related literature

For related literature, see: Haoyun et al. (2006 [triangle]); De Sousa et al. (1990 [triangle]); Johnson et al. (1997 [triangle]); Rys et al. (2008 [triangle]). For a related synthesis see: Banerji & Kalena (1980 [triangle]); O’Donnell & Schwan (2003 [triangle]). For a related crystal structure, see: Abu-Yousef et al. (2006 [triangle]).

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Object name is e-65-0o361-scheme1.jpg

Experimental

Crystal data

  • C14H12Br2S3
  • M r = 436.24
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o361-efi1.jpg
  • a = 12.771 (3) Å
  • b = 13.030 (3) Å
  • c = 4.7635 (10) Å
  • V = 792.7 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 5.49 mm−1
  • T = 150 (1) K
  • 0.16 × 0.12 × 0.10 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SORTAV; Blessing, 1995 [triangle]) T min = 0.378, T max = 0.576
  • 5451 measured reflections
  • 1745 independent reflections
  • 1447 reflections with I > 2σ(I)
  • R int = 0.047

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.081
  • S = 1.06
  • 1745 reflections
  • 87 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.72 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 659 Friedel pairs
  • Flack parameter: −0.024 (13)

Data collection: COLLECT (Nonius, 2002 [triangle]); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected bond angles (°)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001834/pv2135sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001834/pv2135Isup2.hkl

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

Acknowledgments

Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research. AJL thanks NSERC Canada for funding.

supplementary crystallographic information

Comment

Organic sulfides are an attractive class of compounds because of their synthetic and pharmaceutical applications. Dibenzyl trisulfide was isolated from the sub-tropical shrub Petiveria alliacea L. (De Sousa et al., 1990; Johnson et al., 1997). Dibenzyl trisulfide dervatives have been synthesized in moderate yield via a diimidazolyl sulfide derivative (Banerji & Kalena, 1980). The immunomodulatory activitities, molecular mechanism, anti tumor activities and some other biological activities of dibenzyltrisulfide derivatives have been reported (Haoyun et al., 2006).

In the title molecule (Fig. 1), the bond lengths and bond angles are comparable to those observed in a similar compound (Abu-Yousef et al., 2006).

Experimental

The N-protected amino acid derivative (1) (Fig. 2) was synthesized by following the described procedure for its benzyl analog (O'Donnell & Schwan, 2003). Compound (1) was reacted with trifluoroacetic acid (20 equiv.) at 273 K for 2 hr to give amino acid derivative (2). The title compound (3) was prepared by stirring (2) in dichloromethane at room temperature in 20% yield and was crystallized by slow evaporation of a dichloromethane/methanol (9:1, v/v) solution. It should be noted that compound (2) in dichlorometane on standing at room temperature for several days also gave compound (3).

Refinement

H atoms bonded to C atoms were placed in calculated positions with C—H = 0.95 - 0.99Å and were included in a riding-model approximation with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of title compound. All non-H atoms are represented by 30% probability displacement ellipsoids. Atoms labeled with the suffix 'a' are related by the symmetry operator (-x + 1, -y, z).
Fig. 2.
The reaction scheme for the formation of the title compound.

Crystal data

C14H12Br2S3F(000) = 428
Mr = 436.24Dx = 1.828 Mg m3
Orthorhombic, P21212Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 5451 reflections
a = 12.771 (3) Åθ = 3.1–27.5°
b = 13.030 (3) ŵ = 5.49 mm1
c = 4.7635 (10) ÅT = 150 K
V = 792.7 (3) Å3Block, colourless
Z = 20.16 × 0.12 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer1745 independent reflections
Radiation source: fine-focus sealed tube1447 reflections with I > 2σ(I)
graphiteRint = 0.047
Detector resolution: 9 pixels mm-1θmax = 27.5°, θmin = 3.1°
[var phi] scans and ω scans with κ offsetsh = −16→16
Absorption correction: multi-scan (SORTAV; Blessing, 1995)k = −16→16
Tmin = 0.378, Tmax = 0.576l = −6→6
5451 measured 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)] = 0.034H-atom parameters constrained
wR(F2) = 0.081w = 1/[σ2(Fo2) + (0.0416P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
1745 reflectionsΔρmax = 0.32 e Å3
87 parametersΔρmin = −0.72 e Å3
0 restraintsAbsolute structure: Flack (1983), 659 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.024 (13)

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 (Å2)

xyzUiso*/Ueq
Br10.42247 (3)0.38038 (3)0.13013 (11)0.04922 (17)
S10.50000.00000.2536 (3)0.0305 (3)
S20.53734 (6)0.11976 (7)−0.0036 (2)0.0319 (2)
C10.4113 (3)0.1583 (3)−0.1526 (8)0.0311 (8)
H1A0.42210.2196−0.27180.037*
H1B0.38530.1024−0.27500.037*
C20.3293 (3)0.1822 (3)0.0620 (7)0.0271 (8)
C30.2529 (3)0.1057 (3)0.1324 (8)0.0356 (9)
H3A0.25440.04120.03950.043*
C40.1784 (3)0.1239 (3)0.3296 (8)0.0369 (9)
H4A0.12820.07240.37220.044*
C50.1750 (3)0.2175 (3)0.4693 (9)0.0433 (11)
H5A0.12320.22940.60860.052*
C60.2470 (3)0.2930 (3)0.4058 (8)0.0367 (10)
H6A0.24460.35720.50020.044*
C70.3222 (3)0.2750 (3)0.2054 (8)0.0283 (8)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0469 (2)0.0294 (2)0.0713 (3)−0.00040 (19)−0.0036 (2)0.0041 (2)
S10.0356 (7)0.0339 (7)0.0219 (6)0.0098 (6)0.0000.000
S20.0286 (4)0.0303 (4)0.0369 (5)0.0012 (4)0.0002 (4)−0.0007 (5)
C10.0356 (19)0.0353 (18)0.0224 (18)0.0040 (16)−0.0018 (16)0.0010 (15)
C20.0272 (18)0.0307 (19)0.023 (2)0.0053 (15)−0.0051 (13)0.0018 (15)
C30.043 (2)0.037 (2)0.027 (2)0.0185 (18)−0.015 (2)−0.007 (2)
C40.0286 (19)0.044 (2)0.038 (2)−0.0044 (18)−0.0051 (16)0.010 (2)
C50.033 (2)0.063 (3)0.033 (2)0.016 (2)0.0022 (18)0.004 (2)
C60.038 (2)0.041 (2)0.031 (2)0.0149 (19)−0.0079 (19)−0.0082 (18)
C70.0277 (19)0.0294 (18)0.028 (2)0.0042 (14)−0.0081 (15)0.0033 (15)

Geometric parameters (Å, °)

Br1—C71.911 (3)C3—C41.358 (5)
S1—S2i2.0403 (13)C3—H3A0.9500
S1—S22.0403 (13)C4—C51.389 (5)
S2—C11.829 (3)C4—H4A0.9500
C1—C21.496 (5)C5—C61.380 (6)
C1—H1A0.9900C5—H5A0.9500
C1—H1B0.9900C6—C71.374 (5)
C2—C71.392 (5)C6—H6A0.9500
C2—C31.435 (5)
S2i—S1—S2106.21 (9)C2—C3—H3A119.5
C1—S2—S1103.71 (12)C3—C4—C5120.5 (4)
C2—C1—S2114.0 (3)C3—C4—H4A119.8
C2—C1—H1A108.7C5—C4—H4A119.8
S2—C1—H1A108.7C6—C5—C4120.0 (4)
C2—C1—H1B108.7C6—C5—H5A120.0
S2—C1—H1B108.7C4—C5—H5A120.0
H1A—C1—H1B107.6C7—C6—C5119.8 (4)
C7—C2—C3116.4 (3)C7—C6—H6A120.1
C7—C2—C1124.2 (3)C5—C6—H6A120.1
C3—C2—C1119.4 (3)C6—C7—C2122.3 (3)
C4—C3—C2121.1 (4)C6—C7—Br1118.4 (3)
C4—C3—H3A119.5C2—C7—Br1119.2 (3)

Symmetry codes: (i) −x+1, −y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2135).

References

  • Abu-Yousef, I. A., Rys, A. Z. & Harpp, D. N. (2006). J. Sulfur Chem.27, 15–24.
  • Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst.27, 435.
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  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • De Sousa, J. R., Demuner, A. J., Pinheiro, J. A., Breitmaier, E. & Cassels, B. K. (1990). Phytochemistry, 29, 3653–3655.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Haoyun, A., Jenny, Z., Xiaobo, W. & Xiao, X. (2006). Bioorg. Med. Chem. Lett.16, 4826–4829. [PubMed]
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  • O’Donnell, J. S. & Schwan, A. L. (2003). Tetrahedron Lett.44, 6293–6296.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet pp. 307–326. New York: Academic Press.
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  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

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