S,S′-Butane-1,4-diyl bis­(benzene­carbo­thio­ate)

Abe, D.; Sasanuma, Y.

doi:10.1107/S1600536813026822

organic compounds

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S,S′-Butane-1,4-diyl bis(benzenecarbothioate)

Daisuke Abe ^a and Yuji Sasanuma ^a ^*

^aDepartment of Applied Chemistry and Biotechnology, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
^*Correspondence e-mail: sasanuma@faculty.chiba-u.jp

(Received 20 September 2013; accepted 30 September 2013; online 5 October 2013)

The title compound, C₁₈H₁₈O₂S₂, which lies on an inversion center, adopts a gauche⁺–trans–trans–trans–gauche⁻ (g⁺tttg⁻) conformation in the S—CH₂—CH₂—CH₂—CH₂—S bond sequence. In the crystal, molecules are packed in a herringbone arrangement through intermolecular C—H⋯π interactions.

CCDC reference: 963649

Related literature

For crystal structures and conformations of C₆H₅C(=O)S(CH₂)_nSC(=O)C₆H₅ (n = 2, 3, 5, 7, 9), see: for example, Deguire & Brisse (1988 ); Leblanc & Brisse (1992 ); Abe & Sasanuma (2012 ).

Experimental

Crystal data

C₁₈H₁₈O₂S₂
M_r = 330.44
Monoclinic, P 2₁ /c
a = 13.2230 (14) Å
b = 4.8903 (5) Å
c = 13.2638 (15) Å
β = 106.897 (1)°
V = 820.67 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 173 K
0.30 × 0.30 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.908, T_max = 0.984
4326 measured reflections
1845 independent reflections
1626 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.083
S = 1.05
1845 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Cg1ⁱ	0.95	3.09	3.8810 (15)	141
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 963649

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813026822/is5305sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026822/is5305Isup2.hkl

checkCIF report

Comment top

In expectation of superior properties such as chemical and thermal resistance, we have investigated structures and properties of polythioesters ([–S(CH₂)_nSCOC₆H₄CO–]_x, abbreviated as PnTS₂), where n denotes the number of methylene units. Instead of the polymer itself, a small model compound corresponding to the repeating unit is often employed to elucidate conformational characteristics of the polymer; therefore, we have adopted oligomethylenedithiobenzoate (nDBS₂). This paper describes synthesis and X-ray diffraction analysis of 4DBS₂, a model compound of P4TS₂.

The crystal structure of 2DBS₂ was determined previously (Deguire & Brisse, 1988). In the 2DBS₂ crystal, the S—CH₂—CH₂—S bonds lie in the gauche⁺ - trans - gauche^- (g⁺tg^-) conformation. Our molecular orbital calculations and NMR experiments (Abe & Sasanuma, 2012) showed that this conformation is significantly stable even in isolated and liquid states owing to the anti-parallel arrangement of S—C═O dipole moments (the intramolecular dipole-dipole interaction).

Figure 1 shows the molecular structure of 4DBS₂. The S—CH₂—CH₂—CH₂—CH₂—S part adopts the g⁺tttg^- conformation, and the intramolecular dipole-dipole interaction similar to that of 2DBS₂ may be formed; however, 2DBS₂ and 4DBS₂ have markedly different melting points and densities: 94 °C and 1.41 g cm^-3 (2DBS₂); 49 °C and 1.34 g cm^-3 (4DBS₂). These differences may be partly due to strengths of intermolecular interactions. In the 2DBS₂ crystal, a number of intermolecular interactions such as C═O···H—C, C—H···S, and C—H···π can be found. In contrast, the 4DBS₂ crystal has only a few C—H···π interactions (Fig. 2).

Crystal structures of nDBS₂ (n = 3, 5, 7, 9) were also reported (Leblanc & Brisse, 1992). The nDBS₂ molecules adopt (t)_n g⁺ conformations in the S—(CH₂)_n—S part. Interestingly, the nDBS₂ molecules show clear odd-even effects in the alkyl conformation: g⁺(t)_n_-1 g^- (n = even); (t)_n g⁺ (n = odd).

Related literature top

For crystal structures and conformations of C₆H₅C(═ O)S(CH₂)_nSC(═O)C₆H₅ (n = 2, 3, 5, 7, 9), see: for example, Deguire & Brisse (1988); Leblanc & Brisse (1992); Abe & Sasanuma (2012).

Experimental top

Benzoyl chloride (15.5 g, 0.11 mol) was added dropwise into 1,4-butanedithiol (6.1 g, 0.05 mol) and pyridine (8.7 g, 0.11 mol) kept at 0 °C, and then the mixture was stirred for 2 h. The crude product was diluted with diethyl ether (50 ml) and washed with water, 8% sodium hydrogen carbonate solution, and water. The organic layer was condensed, and white solid remained. The solid was recrystallized from ethanol to yield 4DBS₂ (8.7 g, 53%).

The product was dissolved in chloroform in an open vessel. The vessel was placed in a larger one containing methanol, a poor solvent for 4DBS₂, to facilitate precipitation of crystals by vapor diffusion of methanol into the chloroform solution.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of S,S'-butane-1,4-diyl dibenzothioate (4DBS₂). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of 4DBS₂, viewed down the (a) a, (b) b, and (c) c axes. The dotted lines represent C—H···π interactions.

S,S'-Butane-1,4-diyl bis(benzenecarbothioate) top

Crystal data top

C₁₈H₁₈O₂S₂	F(000) = 348
M_r = 330.44	D_x = 1.337 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 323 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.2230 (14) Å	Cell parameters from 2016 reflections
b = 4.8903 (5) Å	θ = 3.2–26.8°
c = 13.2638 (15) Å	µ = 0.33 mm⁻¹
β = 106.897 (1)°	T = 173 K
V = 820.67 (15) Å³	Plate, colourless
Z = 2	0.30 × 0.30 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1845 independent reflections
Radiation source: fine-focus sealed tube	1626 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
Detector resolution: 8.333 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −15→17
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −6→6
T_min = 0.908, T_max = 0.984	l = −13→17
4326 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0413P)² + 0.1965P] where P = (F_o² + 2F_c²)/3
1845 reflections	(Δ/σ)_max = 0.001
100 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₈H₁₈O₂S₂	V = 820.67 (15) Å³
M_r = 330.44	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2230 (14) Å	µ = 0.33 mm⁻¹
b = 4.8903 (5) Å	T = 173 K
c = 13.2638 (15) Å	0.30 × 0.30 × 0.05 mm
β = 106.897 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1845 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1626 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.984	R_int = 0.015
4326 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.05	Δρ_max = 0.21 e Å⁻³
1845 reflections	Δρ_min = −0.24 e Å⁻³
100 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 > 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
C1	0.70285 (9)	0.4894 (3)	0.15671 (9)	0.0292 (3)
C2	0.62320 (10)	0.6555 (3)	0.09507 (10)	0.0350 (3)
H2	0.6032	0.6402	0.0205	0.042*
C3	0.57314 (11)	0.8429 (3)	0.14248 (12)	0.0422 (3)
H3	0.5188	0.9562	0.1003	0.051*
C4	0.60192 (12)	0.8656 (3)	0.25099 (12)	0.0414 (3)
H4	0.5688	0.9982	0.2832	0.050*
C5	0.67851 (12)	0.6964 (3)	0.31244 (11)	0.0427 (3)
H5	0.6968	0.7092	0.3870	0.051*
C6	0.72895 (11)	0.5077 (3)	0.26594 (10)	0.0376 (3)
H6	0.7814	0.3905	0.3087	0.045*
C7	0.75788 (10)	0.2993 (3)	0.10215 (10)	0.0311 (3)
C8	0.91038 (11)	−0.0700 (3)	0.08957 (11)	0.0377 (3)
H8A	0.9495	−0.2334	0.1244	0.045*
H8B	0.8470	−0.1342	0.0344	0.045*
C9	0.98021 (10)	0.0896 (3)	0.03740 (11)	0.0382 (3)
H9A	1.0415	0.1647	0.0924	0.046*
H9B	0.9397	0.2452	−0.0023	0.046*
O1	0.73074 (8)	0.2677 (2)	0.00745 (7)	0.0429 (3)
S1	0.86863 (3)	0.12549 (8)	0.18584 (3)	0.03886 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0297 (6)	0.0284 (6)	0.0294 (6)	−0.0041 (5)	0.0084 (5)	0.0010 (5)
C2	0.0353 (7)	0.0401 (7)	0.0308 (6)	0.0017 (5)	0.0115 (5)	0.0074 (5)
C3	0.0405 (7)	0.0437 (8)	0.0455 (8)	0.0097 (6)	0.0174 (6)	0.0129 (6)
C4	0.0428 (8)	0.0397 (7)	0.0477 (8)	0.0029 (6)	0.0224 (6)	−0.0016 (6)
C5	0.0469 (8)	0.0496 (9)	0.0322 (7)	0.0018 (7)	0.0123 (6)	−0.0050 (6)
C6	0.0392 (7)	0.0415 (8)	0.0294 (6)	0.0040 (6)	0.0057 (5)	0.0006 (6)
C7	0.0315 (6)	0.0308 (6)	0.0295 (6)	−0.0024 (5)	0.0063 (5)	0.0014 (5)
C8	0.0353 (7)	0.0341 (7)	0.0414 (7)	0.0042 (5)	0.0076 (6)	−0.0029 (6)
C9	0.0319 (7)	0.0347 (7)	0.0471 (8)	0.0018 (5)	0.0099 (6)	−0.0062 (6)
O1	0.0479 (6)	0.0495 (6)	0.0282 (5)	0.0103 (5)	0.0060 (4)	−0.0027 (4)
S1	0.0346 (2)	0.0456 (2)	0.0328 (2)	0.00686 (14)	0.00426 (14)	−0.00058 (14)

Geometric parameters (Å, º) top

C1—C6	1.3913 (17)	C6—H6	0.9500
C1—C2	1.3916 (17)	C7—O1	1.2117 (15)
C1—C7	1.4912 (17)	C7—S1	1.7761 (13)
C2—C3	1.3841 (19)	C8—C9	1.5204 (19)
C2—H2	0.9500	C8—S1	1.8053 (14)
C3—C4	1.382 (2)	C8—H8A	0.9900
C3—H3	0.9500	C8—H8B	0.9900
C4—C5	1.377 (2)	C9—C9ⁱ	1.526 (3)
C4—H4	0.9500	C9—H9A	0.9900
C5—C6	1.384 (2)	C9—H9B	0.9900
C5—H5	0.9500

C6—C1—C2	119.39 (12)	C1—C6—H6	120.0
C6—C1—C7	122.48 (11)	O1—C7—C1	122.90 (12)
C2—C1—C7	118.13 (11)	O1—C7—S1	121.94 (10)
C3—C2—C1	119.98 (12)	C1—C7—S1	115.15 (9)
C3—C2—H2	120.0	C9—C8—S1	113.65 (10)
C1—C2—H2	120.0	C9—C8—H8A	108.8
C4—C3—C2	120.21 (13)	S1—C8—H8A	108.8
C4—C3—H3	119.9	C9—C8—H8B	108.8
C2—C3—H3	119.9	S1—C8—H8B	108.8
C5—C4—C3	120.04 (13)	H8A—C8—H8B	107.7
C5—C4—H4	120.0	C8—C9—C9ⁱ	111.70 (14)
C3—C4—H4	120.0	C8—C9—H9A	109.3
C4—C5—C6	120.26 (13)	C9ⁱ—C9—H9A	109.3
C4—C5—H5	119.9	C8—C9—H9B	109.3
C6—C5—H5	119.9	C9ⁱ—C9—H9B	109.3
C5—C6—C1	120.06 (13)	H9A—C9—H9B	107.9
C5—C6—H6	120.0	C7—S1—C8	100.22 (6)

C6—C1—C2—C3	2.1 (2)	C6—C1—C7—O1	174.55 (14)
C7—C1—C2—C3	−177.31 (13)	C2—C1—C7—O1	−6.1 (2)
C1—C2—C3—C4	−0.1 (2)	C6—C1—C7—S1	−6.66 (18)
C2—C3—C4—C5	−1.8 (2)	C2—C1—C7—S1	172.72 (11)
C3—C4—C5—C6	1.7 (2)	S1—C8—C9—C9ⁱ	175.95 (10)
C4—C5—C6—C1	0.4 (2)	O1—C7—S1—C8	−0.26 (14)
C2—C1—C6—C5	−2.3 (2)	C1—C7—S1—C8	−179.07 (11)
C7—C1—C6—C5	177.12 (14)	C9—C8—S1—C7	83.52 (11)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cg1ⁱⁱ	0.95	3.09	3.8810 (15)	141

Symmetry code: (ii) −x+1, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cg1ⁱ	0.95	3.09	3.8810 (15)	141

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Acknowledgements

We thank Dr Masu and Dr Yagishita of the Center for Analytical Instrumentation, Chiba University, for helpful advice on X-ray diffraction measurements. This study was partly supported by a Grant-in-Aid for Scientific Research (C) (22550190) from the Japan Society for the Promotion of Science.

References

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Leblanc, C. & Brisse, F. (1992). Can. J. Chem. 70, 900–909. CrossRef CAS Web of Science Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1612

doi:10.1107/S1600536813026822

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