Diethyl 2,2′-(tris­ulfane-1,3-di­yl)dibenzoate

Boukebbous, K.; Laifa, E.A.; De Mallmann, A.; Taoufik, M.

doi:10.1107/S2414314616017089

organic compounds

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ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161708

https://doi.org/10.1107/S2414314616017089

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Diethyl 2,2′-(trisulfane-1,3-diyl)dibenzoate

Khaled Boukebbous,^a ^* El Adoui Laifa,^a Aimery De Mallmann ^b and Mostafa Taoufik ^b

^aDepartment of Chemistry, University of Constantine, BP, 325 Route de Ain El Bey, Constantine 25017, Algeria, and ^bC2P2 (CNRS–UMR 5265), COMS group, Lyon 1 University, ESCPE Lyon, 43 Boulevard du 11 Novembre 1918, Villeurbanne 69626, France
^*Correspondence e-mail: boukebbous.khaled@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 October 2016; accepted 24 October 2016; online 4 November 2016)

The title compound, C₁₈H₁₈O₄S₃, was synthesized in the presence of chloridoauric acid from 3H-1,2-benzodithiole-3-thione as starting material. The asymmetric unit comprises one half of the molecule, the complete molecule being generated by the application of twofold rotation symmetry. The two benzene rings are inclined by 81.0 (2)°. In the crystal, slipped π–π stacking interactions are observed between the benzene rings of neighbouring molecules.

Keywords: crystal structure; dithiolethione derivatives; sulfur organic compounds; 1,2-dithiole-3-thiones; reactivity; benzoate compounds.

CCDC reference: 1511354

Structure description

3H-1,2-Benzodithiole-3-thione is a representative of 1,2-dithiole-3-thiones that define a bioactive family of compounds (Li et al., 2016 ; Russell et al., 2015 ). A bimolecular condensation reaction of 3H-1,2-benzodithiole-3-thione produced the title compound. The half-molecule present in the asymmetric unit is almost planar, with the maximum deviation being 0.114 (4) Å involving the carbonyl O atom of the ester group. The two equivalent S—S bond lengths of 2.0434 (17) Å and the S—S—S angle of 106.91 (11)° are typical for trisulfanyl groups (Fig. 1). The bent molecules are stacked along the b axis and interact through slightly displaced π–π stacking interactions [plane-to-plane separation between parallel benzene rings = 3.371 (7) Å] (Fig. 2).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius. Unlabelled atoms are related to the labelled atoms by symmetry code (−x + 1, y, −z + $[{3\over 2}]$ ).

Figure 2
The packing of the molecules in the title structure in a view along the a axis, showing π–π stacking interactions as dashed blue lines.

Synthesis and crystallization

The title compound was prepared by a condensation reaction of two 3H-1,2-benzodithiole-3-thione molecules in the presence of HAuCl₄·3H₂O in ethanol. 3H-1,2-Benzodithiole-3-thione (90 mg) dissolved in 10 ml of absolute ethanol was added to 200 mg of HAuCl₄·3H₂O dissolved in 10 ml of THF. The mixture was stirred for 1 h under reflux, cooled to room temperature and left undisturbed for several hours. After filtration, the remaining solution was evaporated and the product dissolved in diethyl ether from which crystals of the title compound were harvested after 5 d.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₈H₁₈O₄S₃
M_r	394.54
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	15.071 (3), 4.4304 (11), 27.422 (9)
β (°)	106.59 (3)
V (Å³)	1754.8 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.44
Crystal size (mm)	0.44 × 0.19 × 0.10

Data collection
Diffractometer	Rigaku OF Xcalibur Atlas Gemini ultra
Absorption correction	Analytical (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.872, 0.963
No. of measured, independent and observed [I > 2.0σ(I)] reflections	6690, 2177, 1653
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.166, 1.00
No. of reflections	2175
No. of parameters	142
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.89, −1.00
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ), SUPERFLIP (Palatinus & Chapuis, 2007 ), CRYSTALS (Betteridge et al., 2003 ) and Mercury (Macrae et al., 2006 ).

Structural data

CCDC reference: 1511354

Crystal structure: contains datablocks global, New_Global_Publ_Block, I. DOI: https://doi.org/10.1107/S2414314616017089/wm4032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017089/wm4032Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

(I) top

Crystal data top

C₁₈H₁₈O₄S₃	F(000) = 824
M_r = 394.54	D_x = 1.493 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1198 reflections
a = 15.071 (3) Å	θ = 4.9–27.5°
b = 4.4304 (11) Å	µ = 0.44 mm⁻¹
c = 27.422 (9) Å	T = 150 K
β = 106.59 (3)°	Lath, light yellow
V = 1754.8 (8) Å³	0.44 × 0.19 × 0.10 mm
Z = 4

Data collection top

Rigaku OF Xcalibur Atlas Gemini ultra diffractometer	2177 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1653 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 10.4685 pixels mm^-1	θ_max = 30.0°, θ_min = 3.6°
ω scans	h = −19→20
Absorption correction: analytical (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	k = −6→6
T_min = 0.872, T_max = 0.963	l = −37→37
6690 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.079	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 0.372E + 04 0.520E + 04 0.373E + 04 0.166E + 04 752.
wR(F²) = 0.166	(Δ/σ)_max = 0.0002161
S = 1.00	Δρ_max = 0.89 e Å⁻³
2175 reflections	Δρ_min = −1.00 e Å⁻³
142 parameters	Extinction correction: Larson (1970), Equation 22
0 restraints	Extinction coefficient: 29 (8)
Primary atom site location: other

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98 and N—H in the range 0.86–0.89 Å) and U_iso(H) (in the range 1.2-1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints (Cooper et al., 2010).

Cooper, R. I., Thompson, A. L. & Watkin, D. J. (2010). J. Appl. Cryst. 43, 1100–1107.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3715 (3)	1.0334 (11)	0.67128 (17)	0.0268
C2	0.3092 (3)	1.1298 (12)	0.69705 (18)	0.0321
C3	0.2187 (3)	1.0225 (12)	0.6825 (2)	0.0339
C4	0.1900 (3)	0.8208 (14)	0.6436 (2)	0.0386
C5	0.2512 (3)	0.7263 (12)	0.61804 (19)	0.0336
C6	0.3420 (3)	0.8314 (11)	0.63087 (16)	0.0279
C7	0.4044 (3)	0.7398 (10)	0.60108 (17)	0.0263
C8	0.4233 (3)	0.4435 (13)	0.5337 (2)	0.0342
C9	0.3649 (4)	0.2518 (13)	0.4921 (2)	0.0364
S1	0.5000	1.4389 (4)	0.7500	0.0320
S2	0.48814 (8)	1.1643 (3)	0.68860 (4)	0.0297
O2	0.3662 (2)	0.5346 (8)	0.56525 (12)	0.0319
O1	0.4814 (2)	0.8383 (9)	0.60692 (12)	0.0349
H21	0.330 (4)	1.268 (13)	0.726 (2)	0.0389*
H31	0.181 (4)	1.099 (13)	0.702 (2)	0.0410*
H41	0.127 (4)	0.736 (14)	0.632 (2)	0.0459*
H51	0.229 (4)	0.568 (13)	0.589 (2)	0.0403*
H81	0.473 (4)	0.340 (13)	0.554 (2)	0.0408*
H82	0.444 (4)	0.637 (14)	0.520 (2)	0.0408*
H91	0.402 (4)	0.177 (15)	0.468 (2)	0.0548*
H92	0.341 (4)	0.065 (16)	0.504 (2)	0.0551*
H93	0.314 (4)	0.370 (15)	0.471 (2)	0.0548*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0220 (19)	0.027 (2)	0.033 (2)	0.0025 (18)	0.0097 (17)	0.0072 (19)
C2	0.030 (2)	0.035 (3)	0.033 (2)	0.001 (2)	0.0129 (19)	0.002 (2)
C3	0.028 (2)	0.036 (3)	0.043 (3)	0.003 (2)	0.019 (2)	0.006 (2)
C4	0.025 (2)	0.051 (3)	0.041 (3)	−0.005 (2)	0.0115 (19)	0.002 (3)
C5	0.027 (2)	0.038 (3)	0.036 (2)	−0.003 (2)	0.0108 (19)	0.002 (2)
C6	0.025 (2)	0.029 (2)	0.030 (2)	−0.003 (2)	0.0088 (17)	0.002 (2)
C7	0.0258 (19)	0.023 (2)	0.029 (2)	−0.0018 (17)	0.0071 (17)	0.0015 (17)
C8	0.029 (2)	0.037 (3)	0.041 (3)	−0.004 (2)	0.017 (2)	−0.003 (2)
C9	0.033 (2)	0.035 (3)	0.041 (3)	−0.005 (2)	0.012 (2)	−0.009 (2)
S1	0.0334 (8)	0.0258 (9)	0.0365 (9)	0.0000	0.0094 (7)	0.0000
S2	0.0251 (5)	0.0321 (7)	0.0327 (6)	−0.0028 (5)	0.0098 (4)	0.0001 (5)
O2	0.0285 (15)	0.0348 (19)	0.0346 (17)	−0.0071 (15)	0.0127 (13)	−0.0075 (15)
O1	0.0261 (15)	0.042 (2)	0.0384 (17)	−0.0040 (15)	0.0120 (13)	−0.0035 (17)

Geometric parameters (Å, º) top

C1—C2	1.394 (6)	C7—O2	1.342 (5)
C1—C6	1.395 (6)	C7—O1	1.208 (5)
C1—S2	1.782 (4)	C8—C9	1.490 (7)
C2—C3	1.390 (6)	C8—O2	1.442 (5)
C2—H21	0.98 (5)	C8—H81	0.92 (6)
C3—C4	1.364 (8)	C8—H82	1.02 (6)
C3—H31	0.95 (5)	C9—H91	1.02 (6)
C4—C5	1.373 (7)	C9—H92	0.99 (7)
C4—H41	0.99 (6)	C9—H93	0.97 (6)
C5—C6	1.393 (6)	S1—S2ⁱ	2.0434 (17)
C5—H51	1.05 (6)	S1—S2	2.0434 (17)
C6—C7	1.467 (6)

C2—C1—C6	119.4 (4)	C6—C7—O2	112.7 (4)
C2—C1—S2	121.4 (4)	C6—C7—O1	124.8 (4)
C6—C1—S2	119.1 (3)	O2—C7—O1	122.5 (4)
C1—C2—C3	119.8 (5)	C9—C8—O2	107.2 (4)
C1—C2—H21	120 (3)	C9—C8—H81	112 (4)
C3—C2—H21	120 (3)	O2—C8—H81	108 (3)
C2—C3—C4	121.0 (4)	C9—C8—H82	112 (3)
C2—C3—H31	115 (3)	O2—C8—H82	107 (3)
C4—C3—H31	124 (3)	H81—C8—H82	111 (4)
C3—C4—C5	119.3 (5)	C8—C9—H91	111 (3)
C3—C4—H41	124 (3)	C8—C9—H92	115 (4)
C5—C4—H41	117 (3)	H91—C9—H92	104 (5)
C4—C5—C6	121.6 (5)	C8—C9—H93	110 (4)
C4—C5—H51	119 (3)	H91—C9—H93	106 (5)
C6—C5—H51	120 (3)	H92—C9—H93	110 (5)
C1—C6—C5	118.8 (4)	S2ⁱ—S1—S2	106.91 (11)
C1—C6—C7	120.7 (4)	C1—S2—S1	105.12 (16)
C5—C6—C7	120.4 (4)	C8—O2—C7	115.1 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Acknowledgements

We acknowledge The French National Center for Scientific Research (CNRS) for financial support.

References

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