Bis(2-bromo­benz­yl) tris­ulfide

Singh, S.P.; Lough, A.J.; Schwan, A.L.

doi:10.1107/S1600536809001834

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o361

doi:10.1107/S1600536809001834

Open

access

Bis(2-bromobenzyl) trisulfide

Suneel. P. Singh,^a Alan. J. Lough ^b ^* and Adrian. L. Schwan ^a

^aDepartment of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario, Canada N1G 2W1, and ^bDepartment of Chemistry, University of Toronto, 80 St., George Street, Toronto, Ontario, Canada M5S 3H6
^*Correspondence e-mail: alough@chem.utoronto.ca

(Received 14 January 2009; accepted 14 January 2009; online 23 January 2009)

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

Experimental

Crystal data

C₁₄H₁₂Br₂S₃
M_r = 436.24
Orthorhombic, P 2₁ 2₁ 2
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 ) 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[F² > 2σ(F²)] = 0.034
wR(F²) = 0.081
S = 1.06
1745 reflections
87 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.72 e Å⁻³
Absolute structure: Flack (1983 ), 659 Friedel pairs
Flack parameter: −0.024 (13)

Table 1
Selected bond angles (°)

S2ⁱ—S1—S2	106.21 (9)
C2—C1—S2	114.0 (3)
Symmetry code: (i) -x+1, -y, z.

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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).

Computing details top

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

Figures top

	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.

Bis(2-bromobenzyl) trisulfide top

Crystal data top

C₁₄H₁₂Br₂S₃	F(000) = 428
M_r = 436.24	D_x = 1.828 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 5451 reflections
a = 12.771 (3) Å	θ = 3.1–27.5°
b = 13.030 (3) Å	µ = 5.49 mm⁻¹
c = 4.7635 (10) Å	T = 150 K
V = 792.7 (3) Å³	Block, colourless
Z = 2	0.16 × 0.12 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1745 independent reflections
Radiation source: fine-focus sealed tube	1447 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 9 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ϕ scans and ω scans with κ offsets	h = −16→16
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −16→16
T_min = 0.378, T_max = 0.576	l = −6→6
5451 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0416P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1745 reflections	Δρ_max = 0.32 e Å⁻³
87 parameters	Δρ_min = −0.72 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 659 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.024 (13)

Crystal data top

C₁₄H₁₂Br₂S₃	V = 792.7 (3) Å³
M_r = 436.24	Z = 2
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 12.771 (3) Å	µ = 5.49 mm⁻¹
b = 13.030 (3) Å	T = 150 K
c = 4.7635 (10) Å	0.16 × 0.12 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	1745 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	1447 reflections with I > 2σ(I)
T_min = 0.378, T_max = 0.576	R_int = 0.047
5451 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.081	Δρ_max = 0.32 e Å⁻³
S = 1.06	Δρ_min = −0.72 e Å⁻³
1745 reflections	Absolute structure: Flack (1983), 659 Friedel pairs
87 parameters	Absolute structure parameter: −0.024 (13)
0 restraints

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

	x	y	z	U_iso*/U_eq
Br1	0.42247 (3)	0.38038 (3)	0.13013 (11)	0.04922 (17)
S1	0.5000	0.0000	0.2536 (3)	0.0305 (3)
S2	0.53734 (6)	0.11976 (7)	−0.0036 (2)	0.0319 (2)
C1	0.4113 (3)	0.1583 (3)	−0.1526 (8)	0.0311 (8)
H1A	0.4221	0.2196	−0.2718	0.037*
H1B	0.3853	0.1024	−0.2750	0.037*
C2	0.3293 (3)	0.1822 (3)	0.0620 (7)	0.0271 (8)
C3	0.2529 (3)	0.1057 (3)	0.1324 (8)	0.0356 (9)
H3A	0.2544	0.0412	0.0395	0.043*
C4	0.1784 (3)	0.1239 (3)	0.3296 (8)	0.0369 (9)
H4A	0.1282	0.0724	0.3722	0.044*
C5	0.1750 (3)	0.2175 (3)	0.4693 (9)	0.0433 (11)
H5A	0.1232	0.2294	0.6086	0.052*
C6	0.2470 (3)	0.2930 (3)	0.4058 (8)	0.0367 (10)
H6A	0.2446	0.3572	0.5002	0.044*
C7	0.3222 (3)	0.2750 (3)	0.2054 (8)	0.0283 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0469 (2)	0.0294 (2)	0.0713 (3)	−0.00040 (19)	−0.0036 (2)	0.0041 (2)
S1	0.0356 (7)	0.0339 (7)	0.0219 (6)	0.0098 (6)	0.000	0.000
S2	0.0286 (4)	0.0303 (4)	0.0369 (5)	0.0012 (4)	0.0002 (4)	−0.0007 (5)
C1	0.0356 (19)	0.0353 (18)	0.0224 (18)	0.0040 (16)	−0.0018 (16)	0.0010 (15)
C2	0.0272 (18)	0.0307 (19)	0.023 (2)	0.0053 (15)	−0.0051 (13)	0.0018 (15)
C3	0.043 (2)	0.037 (2)	0.027 (2)	0.0185 (18)	−0.015 (2)	−0.007 (2)
C4	0.0286 (19)	0.044 (2)	0.038 (2)	−0.0044 (18)	−0.0051 (16)	0.010 (2)
C5	0.033 (2)	0.063 (3)	0.033 (2)	0.016 (2)	0.0022 (18)	0.004 (2)
C6	0.038 (2)	0.041 (2)	0.031 (2)	0.0149 (19)	−0.0079 (19)	−0.0082 (18)
C7	0.0277 (19)	0.0294 (18)	0.028 (2)	0.0042 (14)	−0.0081 (15)	0.0033 (15)

Geometric parameters (Å, º) top

Br1—C7	1.911 (3)	C3—C4	1.358 (5)
S1—S2ⁱ	2.0403 (13)	C3—H3A	0.9500
S1—S2	2.0403 (13)	C4—C5	1.389 (5)
S2—C1	1.829 (3)	C4—H4A	0.9500
C1—C2	1.496 (5)	C5—C6	1.380 (6)
C1—H1A	0.9900	C5—H5A	0.9500
C1—H1B	0.9900	C6—C7	1.374 (5)
C2—C7	1.392 (5)	C6—H6A	0.9500
C2—C3	1.435 (5)

S2ⁱ—S1—S2	106.21 (9)	C2—C3—H3A	119.5
C1—S2—S1	103.71 (12)	C3—C4—C5	120.5 (4)
C2—C1—S2	114.0 (3)	C3—C4—H4A	119.8
C2—C1—H1A	108.7	C5—C4—H4A	119.8
S2—C1—H1A	108.7	C6—C5—C4	120.0 (4)
C2—C1—H1B	108.7	C6—C5—H5A	120.0
S2—C1—H1B	108.7	C4—C5—H5A	120.0
H1A—C1—H1B	107.6	C7—C6—C5	119.8 (4)
C7—C2—C3	116.4 (3)	C7—C6—H6A	120.1
C7—C2—C1	124.2 (3)	C5—C6—H6A	120.1
C3—C2—C1	119.4 (3)	C6—C7—C2	122.3 (3)
C4—C3—C2	121.1 (4)	C6—C7—Br1	118.4 (3)
C4—C3—H3A	119.5	C2—C7—Br1	119.2 (3)

Symmetry code: (i) −x+1, −y, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂Br₂S₃
M_r	436.24
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	150
a, b, c (Å)	12.771 (3), 13.030 (3), 4.7635 (10)
V (Å³)	792.7 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.49
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.378, 0.576
No. of measured, independent and observed [I > 2σ(I)] reflections	5451, 1745, 1447
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.081, 1.06
No. of reflections	1745
No. of parameters	87
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.72
Absolute structure	Flack (1983), 659 Friedel pairs
Absolute structure parameter	−0.024 (13)

Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2003).

Selected bond angles (º) top

S2ⁱ—S1—S2

106.21 (9)

C2—C1—S2

114.0 (3)

Symmetry code: (i) −x+1, −y, z.

Acknowledgements

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.

References

Abu-Yousef, I. A., Rys, A. Z. & Harpp, D. N. (2006). J. Sulfur Chem. 27, 15–24. CSD CrossRef CAS Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Banerji, A. & Kalena, G. P. (1980). Tetrahedron Lett. 21, 3003–3004. CrossRef CAS Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
De Sousa, J. R., Demuner, A. J., Pinheiro, J. A., Breitmaier, E. & Cassels, B. K. (1990). Phytochemistry, 29, 3653–3655. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Haoyun, A., Jenny, Z., Xiaobo, W. & Xiao, X. (2006). Bioorg. Med. Chem. Lett. 16, 4826–4829. Web of Science PubMed Google Scholar
Johnson, L., Williams, L. A. D. & Roberst, E. V. (1997). Pestic. Sci. 50, 228–232. CrossRef CAS Google Scholar
Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
O'Donnell, J. S. & Schwan, A. L. (2003). Tetrahedron Lett. 44, 6293–6296. Web of Science CrossRef CAS Google Scholar
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. Google Scholar
Rys, A. Z., Abu-Yousef, I. A. & Harpp, D. N. (2008). Tetrahedron Lett. 49, 6670–6673. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar