organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Butane-1,4-diyl bis­­(benzene­carbodi­thio­ate)

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 7 October 2013; accepted 8 October 2013; online 12 October 2013)

The title compound, C18H18S4, which lies on an inversion center, adopts a transgauche+transgauchetrans (tg+tgt) conformation of the S—CH2—CH2—CH2—CH2—S bond sequence. In the crystal, a ππ inter­action with a centroid–centroid distance of 3.8797 (16) Å is observed.

Related literature

For crystal structures and conformations of C6H5C(=S)S(CH2)2SC(=S)C6H5 and C6H5C(=O)S(CH2)4SC(=O)C6H5, see: Abe et al. (2011[Abe, D., Sasanuma, Y. & Sato, H. (2011). Acta Cryst. E67, o961.], 2013[Abe, D. & Sasanuma, Y. (2013). Acta Cryst. E69, o1612.]). For related compounds, see: Sawanobori et al. (2001[Sawanobori, M., Sasanuma, Y. & Kaito, A. (2001). Macromolecules, 34, 8321-8329.]); Sasanuma et al. (2002[Sasanuma, Y., Ohta, H., Touma, I., Matoba, H., Hayashi, Y. & Kaito, A. (2001). Macromolecules, 35, 3748-3761.]). For the synthesis of piperidinium di­thio­benzoate, see: Kato et al. (1973[Kato, S., Mitani, T. & Mizuta, M. (1973). Int. J. Sulfur Chem. 8, 359-366.]).

[Scheme 1]

Experimental

Crystal data
  • C18H18S4

  • Mr = 362.56

  • Monoclinic, P 21 /n

  • a = 11.0205 (6) Å

  • b = 7.2535 (5) Å

  • c = 11.3090 (7) Å

  • β = 110.805 (2)°

  • V = 845.06 (9) Å3

  • Z = 2

  • Cu Kα radiation

  • μ = 5.09 mm−1

  • T = 173 K

  • 0.40 × 0.20 × 0.01 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.235, Tmax = 0.951

  • 4872 measured reflections

  • 1480 independent reflections

  • 1468 reflections with I > 2σ(I)

  • Rint = 0.028

Refinement
  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.100

  • S = 1.13

  • 1480 reflections

  • 100 parameters

  • H-atom parameters constrained

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and Mercury (Macrae et al., 2006[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.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The aromatic polyesters, [–O(CH2)nO(C=O)C6H4(C=O)-]x (n = 2– 4), have been mass-produced and used as fibers, films, bottles, and engineering plastics. In a series of our studies, we have investigated conformational characteristics and configurational properties of their analogs, [–X(CH2)nX(C=Y)C6H4(C=Y)-]x, that is, polythioesters (X = S, Y = O, abbreviated herein as PnTS2) and polydithioesters (X = Y = S, PnTS4). As model compounds of PnTS2 and PnTS4, we have adopted oligomethylenedithiobenzoate (nDBS2) and oligomethylenetetrathiobenzoate (nDBS4), respectively. This paper describes synthesis and X-ray diffraction analysis of one of them, 4DBS4.

Figure 1 shows the molecular structure of 4DBS4. The S—CH2—CH2—CH2—CH2—S bonds lie in the transgauche+transgauche-trans (tg+tg-t) conformation. On the other hand, 4DBS2, a model of P4TS2, crystallizes to form the g+tttg- conformation (Abe & Sasanuma, 2013). In general, the S—CH2 single bond prefers the gauche state (Sawanobori et al., 2001; Sasanuma et al., 2002). For instance, the crystalline 2DBS4 molecule adopts the g+tg- conformation in the S—CH2–CH2—S linkage (Abe et al., 2011). By contraries, the two S—CH2 bonds of 4DBS4 were found here to be in the trans conformation. Our molecular orbital calculations at the MP2/6–311+G(2 d,p)//B3LYP/6–311+G(2 d,p) level for gaseous 4DBS4 yielded free energies (relative to the all-trans state) of the two conformers: 0.49 kcal mol-1 (tg+tg-t) and -0.86 kcal mol-1 (g+tttg-). Therefore, 4DBS4 is not allowed to crystallize in the most stable conformation.

In differential scanning calorimetric measurements, a 4DBS4 sample, which was recrystallized from methanol, exhibited only one endothermic peak at 68 °C on heating, whereas its melt-crystallized sample showed two endothermic peaks at 48 and 68 °C. The former and latter samples yielded powder X-ray diffraction patterns different from each other.

Interestingly, nDBS4's (n = 2, 3, 4, and 5) show odd-even effects in melting; 2DBS4 and 4DBS4, respectively, melt at 109 and 68 °C, whereas 3DBS4 and 5DBS4 are liquid at room temperature but exhibit grass transitions at -51 °C (n = 3) and -54 °C (n = 5).

Related literature top

For crystal structures and conformations of C6H5C(=S)S(CH2)2SC(=S)C6H5 and C6H5C(=O)S(CH2)4SC(=O)C6H5, see: Abe et al. (2011, 2013); For related compounds, see: Sawanobori et al. (2001); Sasanuma et al. (2002). For the synthesis of piperidinium dithiobenzoate, see: Kato et al. (1973).

Experimental top

Piperidinium dithiobenzoate (1.26 g, 5.3 mmol) was prepared according to the literature (Kato et al., 1973). Dibromobutane (0.54 g, 2.5 mmol) was added dropwise into piperidinium dithiobenzoate dissolved in dimethylformamide (DMF, 15 ml) and then stirred for 8 h under nitrogen atmosphere. The reaction mixture was diluted with a mixture of ethyl acetate and n-hexane (1:4 in volume) and washed thrice with water, and the organic layer was dried overnight over anhydrous magnesium sulfate. The solution was condensed, dissolved in a toluene/n-hexane mixture (1:2 in volume), and fractionated by silica-gel chromatograph (Rf = 0.3–0.5). The collected fractions were condensed and recrystallized from a methanol/n-hexane mixture (1:1 in volume) to yield 4DBS4 (0.37 g, 41%).

The product was dissolved in chloroform in an open vessel. The vessel was placed in a larger one containing n-hexane, a poor solvent for 4DBS4, to facilitate precipitation of crystals by vapor diffusion of n-hexane into the chloroform solution.

Refinement top

All C—H hydrogen atoms were geometrically positioned with C—H = 0.95 and 0.99 Å for the aromatic and methylene groups, respectively, and refined as riding by Uiso(H) = 1.2 Ueq(C).

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).

Figures top
[Figure 1] Fig. 1. Molecular structure of S,S'-butane-1,4-diyl bis(benzenecarbodithioate) (4DBS4). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Packing diagrams of 4DBS4, viewed down the a (a), b (b), and c (c) axes.
Butane-1,4-diyl bis(benzenecarbodithioate) top
Crystal data top
C18H18S4F(000) = 380
Mr = 362.56Dx = 1.425 Mg m3
Monoclinic, P21/nMelting point: 341 K
Hall symbol: -P 2ynCu Kα radiation, λ = 1.54178 Å
a = 11.0205 (6) ÅCell parameters from 5003 reflections
b = 7.2535 (5) Åθ = 4.8–67.8°
c = 11.3090 (7) ŵ = 5.09 mm1
β = 110.805 (2)°T = 173 K
V = 845.06 (9) Å3Plate, pink
Z = 20.40 × 0.20 × 0.01 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1480 independent reflections
Radiation source: Bruker TXS fine-focus rotating anode1468 reflections with I > 2σ(I)
Bruker Helios multilayer confocal mirror monochromatorRint = 0.028
Detector resolution: 8.333 pixels mm-1θmax = 68.1°, θmin = 4.8°
ϕ and ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
k = 87
Tmin = 0.235, Tmax = 0.951l = 1313
4872 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0393P)2 + 1.0478P]
where P = (Fo2 + 2Fc2)/3
1480 reflections(Δ/σ)max < 0.001
100 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
C18H18S4V = 845.06 (9) Å3
Mr = 362.56Z = 2
Monoclinic, P21/nCu Kα radiation
a = 11.0205 (6) ŵ = 5.09 mm1
b = 7.2535 (5) ÅT = 173 K
c = 11.3090 (7) Å0.40 × 0.20 × 0.01 mm
β = 110.805 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1480 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1468 reflections with I > 2σ(I)
Tmin = 0.235, Tmax = 0.951Rint = 0.028
4872 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.13Δρmax = 0.35 e Å3
1480 reflectionsΔρmin = 0.31 e Å3
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
xyzUiso*/Ueq
C10.0082 (2)0.2157 (3)0.3798 (2)0.0226 (5)
C20.0225 (2)0.2350 (4)0.5097 (2)0.0271 (5)
H20.10680.20290.56580.033*
C30.0686 (2)0.3004 (4)0.5579 (2)0.0309 (5)
H30.04630.31380.64670.037*
C40.1921 (2)0.3461 (4)0.4770 (3)0.0314 (6)
H40.25470.39040.51000.038*
C50.2237 (2)0.3270 (4)0.3480 (3)0.0347 (6)
H50.30850.35810.29230.042*
C60.1329 (2)0.2628 (4)0.2992 (2)0.0300 (5)
H60.15560.25080.21030.036*
C70.0885 (2)0.1450 (3)0.3270 (2)0.0222 (5)
C80.3424 (2)0.0498 (4)0.3534 (2)0.0288 (5)
H8A0.31230.07960.33750.035*
H8B0.33130.10800.27100.035*
C90.4854 (2)0.0543 (4)0.4385 (2)0.0270 (5)
H9A0.51210.18410.45940.032*
H9B0.53810.00310.39130.032*
S10.04887 (5)0.05242 (9)0.18505 (5)0.0286 (2)
S20.24732 (5)0.17228 (9)0.42927 (5)0.0278 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0177 (10)0.0217 (12)0.0276 (11)0.0011 (9)0.0072 (9)0.0005 (9)
C20.0197 (11)0.0330 (13)0.0271 (11)0.0003 (10)0.0064 (9)0.0023 (10)
C30.0304 (12)0.0364 (14)0.0286 (12)0.0004 (11)0.0136 (10)0.0013 (11)
C40.0255 (12)0.0310 (14)0.0429 (14)0.0014 (10)0.0186 (11)0.0034 (11)
C50.0189 (11)0.0430 (16)0.0389 (14)0.0067 (11)0.0063 (10)0.0015 (12)
C60.0210 (11)0.0391 (15)0.0269 (11)0.0026 (10)0.0047 (9)0.0026 (10)
C70.0169 (10)0.0228 (12)0.0255 (11)0.0010 (8)0.0058 (8)0.0044 (9)
C80.0178 (11)0.0406 (15)0.0283 (11)0.0071 (10)0.0087 (9)0.0003 (10)
C90.0172 (11)0.0335 (14)0.0312 (12)0.0040 (9)0.0097 (9)0.0022 (10)
S10.0211 (3)0.0387 (4)0.0246 (3)0.0006 (2)0.0062 (2)0.0052 (2)
S20.0143 (3)0.0394 (4)0.0271 (3)0.0035 (2)0.0040 (2)0.0065 (2)
Geometric parameters (Å, º) top
C1—C21.392 (3)C6—H60.9500
C1—C61.395 (3)C7—S11.649 (2)
C1—C71.487 (3)C7—S21.732 (2)
C2—C31.386 (4)C8—C91.527 (3)
C2—H20.9500C8—S21.807 (2)
C3—C41.383 (4)C8—H8A0.9900
C3—H30.9500C8—H8B0.9900
C4—C51.381 (4)C9—C9i1.530 (5)
C4—H40.9500C9—H9A0.9900
C5—C61.384 (3)C9—H9B0.9900
C5—H50.9500
C2—C1—C6118.6 (2)C1—C6—H6119.8
C2—C1—C7121.2 (2)C1—C7—S1123.48 (16)
C6—C1—C7120.2 (2)C1—C7—S2113.01 (16)
C3—C2—C1120.7 (2)S1—C7—S2123.51 (13)
C3—C2—H2119.6C9—C8—S2109.43 (16)
C1—C2—H2119.6C9—C8—H8A109.8
C4—C3—C2120.1 (2)S2—C8—H8A109.8
C4—C3—H3120.0C9—C8—H8B109.8
C2—C3—H3120.0S2—C8—H8B109.8
C5—C4—C3119.6 (2)H8A—C8—H8B108.2
C5—C4—H4120.2C8—C9—C9i113.5 (2)
C3—C4—H4120.2C8—C9—H9A108.9
C4—C5—C6120.5 (2)C9i—C9—H9A108.9
C4—C5—H5119.7C8—C9—H9B108.9
C6—C5—H5119.7C9i—C9—H9B108.9
C5—C6—C1120.4 (2)H9A—C9—H9B107.7
C5—C6—H6119.8C7—S2—C8104.20 (11)
C6—C1—C2—C30.3 (4)C2—C1—C7—S1158.30 (19)
C7—C1—C2—C3179.8 (2)C6—C1—C7—S121.2 (3)
C1—C2—C3—C40.5 (4)C2—C1—C7—S222.3 (3)
C2—C3—C4—C50.3 (4)C6—C1—C7—S2158.2 (2)
C3—C4—C5—C60.1 (4)S2—C8—C9—C9i66.7 (3)
C4—C5—C6—C10.3 (4)C1—C7—S2—C8172.54 (17)
C2—C1—C6—C50.1 (4)S1—C7—S2—C88.11 (19)
C7—C1—C6—C5179.4 (2)C9—C8—S2—C7176.88 (17)
Symmetry code: (i) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC18H18S4
Mr362.56
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)11.0205 (6), 7.2535 (5), 11.3090 (7)
β (°) 110.805 (2)
V3)845.06 (9)
Z2
Radiation typeCu Kα
µ (mm1)5.09
Crystal size (mm)0.40 × 0.20 × 0.01
Data collection
DiffractometerBruker APEXII CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.235, 0.951
No. of measured, independent and
observed [I > 2σ(I)] reflections
4872, 1480, 1468
Rint0.028
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.100, 1.13
No. of reflections1480
No. of parameters100
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.35, 0.31

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

We thank Dr Masu and Dr Yagishita of the Center for Analytical Instrumentation, Chiba University, for helpful advice about the 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

First citationAbe, D., Sasanuma, Y. & Sato, H. (2011). Acta Cryst. E67, o961.  Web of Science CSD CrossRef IUCr Journals
First citationAbe, D. & Sasanuma, Y. (2013). Acta Cryst. E69, o1612.  CSD CrossRef IUCr Journals
First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationBruker (2007). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationKato, S., Mitani, T. & Mizuta, M. (1973). Int. J. Sulfur Chem. 8, 359–366.  CAS
First citationMacrae, 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
First citationSasanuma, Y., Ohta, H., Touma, I., Matoba, H., Hayashi, Y. & Kaito, A. (2001). Macromolecules, 35, 3748–3761.  Web of Science CrossRef
First citationSawanobori, M., Sasanuma, Y. & Kaito, A. (2001). Macromolecules, 34, 8321–8329.  Web of Science CrossRef CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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