Ethane-1,2-diyl bis­(benzene­dithio­ate)

Abe, D.; Sasanuma, Y.; Sato, H.

doi:10.1107/S1600536811010245

organic compounds

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Volume 67| Part 4| April 2011| Page o961

doi:10.1107/S1600536811010245

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Ethane-1,2-diyl bis(benzenedithioate)

Daisuke Abe,^a Yuji Sasanuma ^a ^* and Hiroyasu Sato ^b

^aDepartment of Applied Chemistry and Biotechnology, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan, and ^bApplication Laboratory, Rigaku Corporation, 3-9-12 Matsubara-cho, Akishima-shi, Tokyo 196-8666, Japan
^*Correspondence e-mail: sasanuma@faculty.chiba-u.jp

(Received 8 March 2011; accepted 18 March 2011; online 26 March 2011)

In the crystal structure, the title compound, C₁₆H₁₄S₄, is located on an inversion center and exhibits a gauche⁺–trans–gauche⁻ conformation in the S—CH₂—CH₂—S bond sequence. The S—C=S plane makes a dihedral angle of 30.63 (17)° with the phenyl ring. An intermolecular C—H⋯π interaction is observed.

Related literature

For crystal structures and conformations of related compounds with S—CH₂—CH₂—S bond sequences, see: for example, Takahashi et al. (1968 ); Deguire & Brisse (1988 ); Sasanuma & Watanabe (2006 ).

Experimental

Crystal data

C₁₆H₁₄S₄
M_r = 334.53
Monoclinic, P 2₁ /c
a = 11.5431 (7) Å
b = 8.74071 (16) Å
c = 8.93720 (16) Å
β = 122.3772 (7)°
V = 761.54 (5) Å³
Z = 2
Cu Kα radiation
μ = 5.60 mm⁻¹
T = 93 K
0.32 × 0.27 × 0.08 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.195, T_max = 0.639
8415 measured reflections
1389 independent reflections
1292 reflections with F² > 2σ(F²)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.079
S = 1.14
1389 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.39 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
C8—H8A⋯Cg1ⁱ	0.99	2.65	3.451 (1)	138
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku Americas & Rigaku, 2007 ); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010245/is2686sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010245/is2686Isup2.hkl

checkCIF report

Comment top

The S—CH₂—CH₂—S part of crystallized poly(ethylene sulfide) (PES, [–CH₂CH₂S–]_x) lies in the gauche⁺ – trans – gauche^- (g⁺tg^-) conformation (Takahashi et al., 1968); the two S—C bonds are in opposite gauche states, and dipole moments are formed along bisectors of the C—S—C angles. The dipole–dipole interaction was suggested to be the source of its high melting point (215–220 °C) in comparison with that (66–69 °C) of poly(ethylene oxide), [–CH₂CH₂O–]_x (Sasanuma & Watanabe, 2006). Therefore, poly(thioethylenethioterephthaloyl) ([–SCH₂CH₂SCOC₆H₄CO–]_x) and poly(thioethylenethiodithioterephthaloyl) ([–SCH₂CH₂SCSC₆H₄CS–]_x), having the same S—CH₂—CH₂—S bond sequence as PES, are expected to be superior in some physical properties to their homologous polyester, poly(ethylene terephthalate) ([–OCH₂CH₂OCOC₆H₄CO–]_x). Crystal conformations of polymers are requisite to derive their configurational properties and thermodynamic quantities. Because a polymer tends to have a crystal conformation similar to that of its small model compounds, the models provide the physicochemical information on the polymer. The crystal structure of 1,2-bis(benzoylthio)ethane (BBTE, C₆H₅C(=O)SCH₂CH₂SC(=O)C₆H₅), a model compound of poly(thioethylenethioterephthaloyl), was determined already (Deguire & Brisse, 1988); its S—CH₂—CH₂—S part also lies in the g⁺tg^- state. We have investigated structure-property relationships of the above-mentioned polyester, polythioester, and polydithioester. As part of the work, this study has dealt with 1,2-bis(dithiobenzoyl)ethane (BDTBE, C₆H₅C(=S)SCH₂CH₂SC(=S)C₆H₅), a model compounds of poly(thioethylenethiodithioterephthaloyl); the crystal structure has been determined and compared with those of BBTE and PES.

Figure 1 shows the molecular structure of BDTBE. Its S—CH₂—CH₂—S bond sequence adopts the g⁺tg^- conformation, as found for PES and BBTE. The g⁺tg^- conformation renders the two phenyl rings parallel to each other; however, this is partly because the BDTBE molecule is located on the center of symmetry. The C₆H₅—C(=O)—S part of BBTE is essentially coplanar, whereas the C=S bond of BDTBE is out of the phenyl plane; the S–C═S plane makes a dihedral angle of 30.63 (17)° with the phenyl ring. This is probably due to the van der Waals radius (1.80 Å) of sulfur larger than that (1.52 Å) of oxygen.

The BBTE crystal seems to include intermolecular π–π interactions of a near vertical type (Deguire & Brisse, 1988). In addition, dipole moments, formed close to the O=C bonds, are either parallel or antiparallel to one another. The dipole-dipole interactions are known to stabilize the crystal structure (Sasanuma & Watanabe, 2006). On the other hand, Figure 2 shows that the C=S bonds of BDTBE do not have such clear orientations, because the small difference in electronegativity between C and S little polarizes the C=S bond. In the BDTBE crystal, instead, C—H···π interactions appear to exist between C8—H8A bond and its neighboring phenyl (Ph) ring, and the H···Ph spacing can be estimated to be 2.65 Å.

Related literature top

For crystal structures and conformations of related compounds with S—CH₂—CH₂—S bond sequences, see: for example, Takahashi et al. (1968); Deguire & Brisse (1988); Sasanuma & Watanabe (2006).

Experimental top

Benzoyl chloride (19.5 g) was added dropwise into 1,2-ethanedithiol (6.2 g) and pyridine (11 ml) in a four-neck flask equipped with a mechanical stirrer and a reflux condenser, and the mixture was stirred at 0 °C for 30 m and, furthermore, at room temperature overnight. The reaction mixture was subjected to extraction with water and ether. The organic layer was washed three times with 8% sodium hydrogen carbonate solution, dried overnight over anhydrous magnesium sulfate, filtrated, and condensed on a rotary evaporator. The residue was recrystallized twice from ethanol and dried under reduced pressure. 1,2-Bis(benzoylthio)ethane (1.5 g) thus prepared, Lawesson's reagent (2.5 g), and toluene (10 ml) were mixed and refluxed for 5 h. The reaction mixture was condensed, dissolved in a mixed solvent (15 ml) of toluene and n-hexane (volume ratio 1:3), and fractionated by a silica-gel column chromatograph. The reddish fraction was collected, condensed, recrystallized twice from ethanol, and dried in vacuo.

Crystals for X-ray diffraction were prepared by slow evaporation of a dimethyl sulfoxide solution. Then, the solution was kept in an open vessel so that water vapor, a poor solvent, would be immixed and hasten the crystallization.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku Americas & Rigaku, 2007); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure (Rigaku Americas & Rigaku, 2007).

Figures top

	Fig. 1. Molecular structure of 1,2-bis(dithiobenzoyl)ethane (BDTBE). Displacement ellipsoids are drawn at the 50% probability level. The asterisk corresponds to symmetry code -x, -y + 1, -z.
	Fig. 2. Packing diagram of BDTBE, viewed down (a) the b axis and (b) the c axis. Displacement ellipsoids are drawn at the 50% probability level. The dotted lines represent C–H···π interactions.

Ethane-1,2-diyl bis(benzenedithioate) top

Crystal data top

C₁₆H₁₄S₄	F(000) = 348.00
M_r = 334.53	D_x = 1.459 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybc	Cell parameters from 7723 reflections
a = 11.5431 (7) Å	θ = 4.5–68.2°
b = 8.74071 (16) Å	µ = 5.60 mm⁻¹
c = 8.93720 (16) Å	T = 93 K
β = 122.3772 (7)°	Prism, orange
V = 761.54 (5) Å³	0.32 × 0.27 × 0.08 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1292 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.054
ω scans	θ_max = 68.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
T_min = 0.195, T_max = 0.639	k = −10→10
8415 measured reflections	l = −10→10
1389 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0329P)² + 0.4332P] where P = (F_o² + 2F_c²)/3
1389 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₆H₁₄S₄	V = 761.54 (5) Å³
M_r = 334.53	Z = 2
Monoclinic, P2₁/c	Cu Kα radiation
a = 11.5431 (7) Å	µ = 5.60 mm⁻¹
b = 8.74071 (16) Å	T = 93 K
c = 8.93720 (16) Å	0.32 × 0.27 × 0.08 mm
β = 122.3772 (7)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1389 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1292 reflections with F² > 2σ(F²)
T_min = 0.195, T_max = 0.639	R_int = 0.054
8415 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.14	Δρ_max = 0.31 e Å⁻³
1389 reflections	Δρ_min = −0.39 e Å⁻³
91 parameters

Special details top

Geometry. All e.s.d.'s (except that 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 was performed with all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F², while the R-factor on F. The threshold expression of F² > 2.0 σ(F²) was used only for calculating R-factor.

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

	x	y	z	U_iso*/U_eq
S1	0.27738 (4)	0.43962 (5)	0.38957 (6)	0.01677 (15)
S2	0.03137 (4)	0.26716 (5)	0.11103 (6)	0.01529 (15)
C1	0.26047 (17)	0.1259 (2)	0.3631 (2)	0.0107 (3)
C2	0.35523 (17)	0.1069 (2)	0.5448 (2)	0.0132 (4)
C3	0.41019 (18)	−0.0366 (2)	0.6127 (2)	0.0154 (4)
C4	0.37290 (18)	−0.1615 (2)	0.4996 (2)	0.0174 (4)
C5	0.28006 (18)	−0.1431 (2)	0.3188 (2)	0.0157 (4)
C6	0.22359 (18)	−0.0005 (2)	0.2505 (2)	0.0134 (3)
C7	0.19836 (18)	0.2793 (2)	0.2954 (2)	0.0116 (3)
C8	−0.02347 (18)	0.4635 (2)	0.0565 (2)	0.0143 (4)
H2	0.3821	0.1924	0.6221	0.016*
H3	0.4733	−0.0493	0.7363	0.019*
H4	0.4109	−0.2594	0.5460	0.021*
H5	0.2552	−0.2285	0.2417	0.019*
H6	0.1596	0.0112	0.1269	0.016*
H8A	−0.1248	0.4677	−0.0080	0.017*
H8B	0.0137	0.5229	0.1674	0.017*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0199 (2)	0.0102 (2)	0.0133 (2)	−0.00211 (16)	0.0043 (2)	−0.00110 (17)
S2	0.0121 (2)	0.0111 (2)	0.0152 (3)	0.00043 (15)	0.0024 (2)	0.00257 (17)
C1	0.0106 (7)	0.0115 (8)	0.0113 (9)	0.0003 (6)	0.0068 (7)	0.0013 (7)
C2	0.0112 (7)	0.0137 (9)	0.0129 (10)	−0.0019 (6)	0.0053 (7)	0.0001 (7)
C3	0.0113 (8)	0.0176 (9)	0.0123 (10)	−0.0007 (6)	0.0029 (7)	0.0027 (7)
C4	0.0150 (8)	0.0120 (9)	0.0236 (11)	0.0024 (6)	0.0092 (8)	0.0045 (8)
C5	0.0162 (8)	0.0118 (8)	0.0168 (10)	−0.0003 (6)	0.0072 (8)	−0.0021 (7)
C6	0.0127 (8)	0.0156 (9)	0.0098 (9)	−0.0005 (6)	0.0045 (7)	0.0005 (7)
C7	0.0134 (8)	0.0137 (9)	0.0089 (9)	0.0001 (6)	0.0067 (7)	0.0002 (7)
C8	0.0143 (8)	0.0119 (8)	0.0153 (10)	0.0050 (6)	0.0070 (8)	0.0039 (7)

Geometric parameters (Å, º) top

S1—C7	1.6376 (17)	C5—C6	1.387 (2)
S2—C7	1.7436 (15)	C8—C8ⁱ	1.519 (3)
S2—C8	1.8033 (17)	C2—H2	0.950
C1—C2	1.400 (2)	C3—H3	0.950
C1—C6	1.399 (2)	C4—H4	0.950
C1—C7	1.488 (2)	C5—H5	0.950
C2—C3	1.390 (2)	C6—H6	0.950
C3—C4	1.389 (2)	C8—H8A	0.990
C4—C5	1.390 (2)	C8—H8B	0.990

S1···H4ⁱⁱ	2.990	H4···S1^vi	2.990
C1···H8Aⁱⁱⁱ	2.866	H4···H2^v	2.664
C2···H8Aⁱⁱⁱ	2.779	H5···H8A^vii	2.763
C3···H8Aⁱⁱⁱ	2.903	H8A···C1^viii	2.866
H2···H3^iv	2.687	H8A···C2^viii	2.779
H2···H4^iv	2.664	H8A···C3^viii	2.903
H3···H2^v	2.687	H8A···H5^vii	2.763

C7—S2—C8	104.35 (7)	C3—C2—H2	119.9
C2—C1—C6	119.24 (15)	C2—C3—H3	120.0
C2—C1—C7	119.06 (16)	C4—C3—H3	120.0
C6—C1—C7	121.67 (14)	C3—C4—H4	120.0
C1—C2—C3	120.25 (17)	C5—C4—H4	120.0
C2—C3—C4	120.03 (16)	C4—C5—H5	119.9
C3—C4—C5	120.03 (16)	C6—C5—H5	119.9
C4—C5—C6	120.22 (17)	C1—C6—H6	119.9
C1—C6—C5	120.22 (16)	C5—C6—H6	119.9
S1—C7—S2	124.57 (10)	S2—C8—H8A	109.1
S1—C7—C1	123.21 (11)	S2—C8—H8B	109.1
S2—C7—C1	112.18 (11)	C8ⁱ—C8—H8A	109.1
S2—C8—C8ⁱ	112.39 (16)	C8ⁱ—C8—H8B	109.1
C1—C2—H2	119.9	H8A—C8—H8B	107.9

C7—S2—C8—C8ⁱ	83.65 (14)	C6—C1—C7—S1	−152.1 (2)
C8—S2—C7—S1	0.8 (2)	C6—C1—C7—S2	30.0 (3)
C8—S2—C7—C1	178.65 (18)	C7—C1—C6—C5	−177.9 (2)
C2—C1—C6—C5	0.3 (3)	C1—C2—C3—C4	1.1 (3)
C6—C1—C2—C3	−1.0 (3)	C2—C3—C4—C5	−0.3 (3)
C2—C1—C7—S1	29.7 (3)	C3—C4—C5—C6	−0.4 (3)
C2—C1—C7—S2	−148.13 (18)	C4—C5—C6—C1	0.5 (3)
C7—C1—C2—C3	177.1 (2)

Symmetry codes: (i) −x, −y+1, −z; (ii) x, y+1, z; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, y+1/2, −z+3/2; (v) −x+1, y−1/2, −z+3/2; (vi) x, y−1, z; (vii) −x, −y, −z; (viii) −x, 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
C8—H8A···Cg1^viii	0.99	2.65	3.451 (1)	138

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄S₄
M_r	334.53
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	93
a, b, c (Å)	11.5431 (7), 8.74071 (16), 8.93720 (16)
β (°)	122.3772 (7)
V (Å³)	761.54 (5)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	5.60
Crystal size (mm)	0.32 × 0.27 × 0.08

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.195, 0.639
No. of measured, independent and observed [F² > 2σ(F²)] reflections	8415, 1389, 1292
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.14
No. of reflections	1389
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.39

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku Americas & Rigaku, 2007), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

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
C8—H8A···Cg1ⁱ	0.99	2.65	3.451 (1)	138

Symmetry code: (i) −x, y+1/2, −z+1/2.

Acknowledgements

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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o961

doi:10.1107/S1600536811010245

Open

access