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

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 1| January 2016| x160082
doi:10.1107/S2414314616000821

syn-6,15-Dihy­dr­oxy-2,11-di­thia­[3.3]meta­cyclo­phane ethyl acetate monosolvate

Tetsuji Moriguchi,a* Daisuke Miyamoto,a Ventakaprasad Jalli,a Kenji Yozab and Akihiko Tsugea

aDepartment of Applied Chemistry, Graduate School of Engineering, Kyushu Institute of Technology, 1-1 Sensui-cho, Tobata-ku, Kitakyushu 804-8550, Japan, and bJapan Bruker AXS, K.K.3-9, Moriya-cho Kanagawaku, Yokohama 221-0022, Japan
*Correspondence e-mail: moriguch@che.kyutech.ac.jp

Edited by S. Bernès, UANL, México (Received 2 January 2016; accepted 15 January 2016; online 20 January 2016)

The title compound, C16H16O2S2·C4H8O2, is a cyclo­phane derivative, which was crystallized from an ethyl­acetate/methanol solvent system. The meta­cyclo­phane moiety exists with the benzene rings in the syn orientation, and with a pseudo chair–chair conformation for the di­thia 12-membered ring. Both hy­droxy groups are positioned on same side of this ring. In the crystal, the cyclo­phane and the lattice solvent are linked by O—H⋯O hydrogen bonds.

CCDC reference: 1447490

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The synthesis and mol­ecular structure analysis of short-bridged cyclo­phanes continues to attract inter­est in supra­molecular chemistry. The understanding of the preferred conformations of cyclo­phane is of importance in the design of various supra­molecular systems. Small-sized cyclo­phane mol­ecules act as a model to explore the flexibility of such cyclo­phanes, due to the presence of a variety of conformational processes including ring-flipping, ring-tilting and syn--anti isomerization. Small-sized cyclo­phane units have been used as a platform to build cofacial bis­porphyrins (Tsuge et al., 2012[Tsuge, A., Ikeda, Y., Moriguchi, T. & Araki, K. (2012). J. Porphyrins Phthalocyanines, 16, 250-254.]). The [3.3]di­thia­meta­cyclo­phane skeleton has also been used to provide an appropriate platform to arrange two oligomer chains side by side in a stacked arrangement, because this kind of cyclo­phane assumes a syn structure (Tsuge et al., 2008[Tsuge, A., Hara, T., Moriguchi, T. & Yamaji, M. (2008). Chem. Lett. 37, 870-871.]).

We have compared the conformation of the title compound (Fig. 1[link]) with other cyclo­phanes having different substitutions at C5/C13 in the benzene rings. The title compound has OH groups at the C5/C13 positions and exists in a syn, pseudo chair-chair conformation, with both hy­droxy groups positioned on the same side of the core 12-membered di­thia ring. When methyl groups substitute the C5/C13 positions, the anti, pseudo boat-chair conformation is stabilized (Chan et al., 1977[Chan, T.-L., Chan, C.-K., Ho, K.-W., Tse, J. S. & Mak, T. C. W. (1977). J. Cryst. Mol. Struct. 7, 199-205.]). Unsubstituted cyclo­phane exists in a syn, pseudo chair–chair conformation (Anker et al., 1979[Anker, W., Bushnell, G. W. & Mitchell, R. H. (1979). Can. J. Chem. 57, 3080-3087.]), and when cyano group are bonded at C5/C13 positions the syn, pseudo boat-boat conformation is obtained (Bodwell et al., 1997[Bodwell, G. J., Bridson, J. N., Houghton, T. J. & Yarlagadda, B. (1997). Tetrahedron Lett. 38, 7475-7478.]).

[Figure 1]
Figure 1
Mol­ecular configuration and atom-numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are omitted for clarity.

The crystal structure (Fig. 2[link]) features O—H⋯O hydrogen bonds (Table 1[link]) involving the hy­droxy groups belonging to the cyclo­phane, and the carbonyl functionality of the ethyl acetate solvent.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1O⋯O2i 0.82 1.91 2.732 (3) 176
O2—H2O⋯O3ii 0.82 1.84 2.656 (3) 172
Symmetry codes: (i) -x+2, -y, -z; (ii) x, y-1, z.
[Figure 2]
Figure 2
Crystal packing diagram of the title compound, viewed along the a axis, with H atoms omitted for clarity.

Synthesis and crystallization

The synthesis of the title compound is shown in Fig. 3[link]. An ethanol solution (100 ml) of 3,5-bis­(bromo­meth­yl)phenol (2 mmol) and 3,5-bis­(mercaptometh­yl)phenol (2 mmol) was added dropwise to a solution of CsOH (5 mmol) as an alkaline catalyst in ethanol (250 ml). The reaction mixture was refluxed for 10 h. After completion of the reaction, the resulting mixture was cooled to room temperature, poured into ice-cold water, and extracted with di­chloro­methane. The organic layer was washed with water. The resulting organic layer was dried over MgSO4 and the solvent was removed under reduced pressure. The resulting residue was purified on column chromatography (silica gel), and the title cyclo­phane was obtained as a white powder. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate–methanol solution at room temperature.

[Figure 3]
Figure 3
Reaction scheme for the synthesis of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C16H16O2S2·C4H8O2
Mr 392.51
Crystal system, space group Monoclinic, P21/n
Temperature (K) 120
a, b, c (Å) 12.1691 (9), 13.1263 (10), 12.2750 (9)
β (°) 99.818 (1)
V (Å3) 1932.0 (2)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.30
Crystal size (mm) 0.40 × 0.40 × 0.40
 
Data collection
Diffractometer Bruker APEXII CCD diffractometer
Absorption correction Multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.770, 0.886
No. of measured, independent and observed [I > 2σ(I)] reflections 18213, 3400, 2628
Rint 0.055
(sin θ/λ)max (Å−1) 0.594
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.100, 1.00
No. of reflections 3400
No. of parameters 239
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 1.04, −0.21
Computer programs: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Structural data

CCDC reference: 1447490

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2414314616000821/bh4001sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616000821/bh4001Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616000821/bh4001Isup3.cml

checkCIF report


Structural commentary top

The synthesis and molecular structure analysis of short-bridged cyclo­phanes continue to attract inter­est in supra­molecular chemistry. The understanding of preferred conformations in cyclo­phane is of importance in the design of various supra­molecular systems. Small-sized cyclo­phane molecules act as a model to explore the flexibility of such cyclo­phanes, due to the presence of a variety of conformational processes including ring-flipping, ring-tilting and syn-anti isomerization. Small-sized cyclo­phane units have been used as a platform to build cofacial bis­porphyrins (Tsuge et al., 2012). The [3.3]di­thia­meta­cyclo­phane skeleton has also been used to provide an appropriate platform to arrange two oligomer chains side by side in a stacked arrangement, because this kind of cyclo­phane assumes a syn structure (Tsuge et al., 2008).

We have compared the conformation of the title compound (Fig. 1) with other cyclo­phanes having different substitutions at C5/C13 in the benzene rings. From the X-ray data analysis, the title compound having OH groups at C5/C13 positions exists in syn, pseudo chair-chair conformation, with both hy­droxy groups positioned on same side with respect to the core 12-membered di­thia ring. When methyl groups substitute C5/C13 positions, the anti, pseudo boat-chair conformation is stabilized (Chan et al., 1977). Unsubstituted cyclo­phane exists in syn, pseudo chair-chair conformation (Anker et al., 1979), and when cyano group are bonded at C5/C13 positions the syn, pseudo boat-boat conformation is obtained (Bodwell et al., 1997).

The crystal structure (Fig. 2) features O—H···O inter­molecular hydrogen bonds, involving the hy­droxy groups belonging to the cyclo­phane, and the carbonyl functionality of the ethyl acetate solvent.

Synthesis and crystallization top

The title compound was synthesized as follows (Fig. 3). Ethanol solution (100 ml) of 3,5-bis­(bromo­methyl)-phenol (2 mmol) and 3,5-bis­(mercapto­methyl)-phenol (2 mmol) was added dropwise to a solution of CsOH (5 mmol) as an alkaline catalyst in ethanol (250 ml). The reaction mixture was refluxed for 10 h. After completion of the reaction, the resulting mixture was cooled to room temperature, poured into ice-cold water, and extracted with di­chloro­methane. The organic layer was washed with water. The resulting organic layer was dried over MgSO4 and the solvent was removed under reduced pressure. The resulting residue was purified on column chromatography (silica gel), and the title cyclo­phane was obtained as a white powder. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate-methanol solution, at room temperature.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. A l l C-bonded H atoms were placed in calculated positions and refined as riding on their carrier C atom, with C—H bond lengths fixed to 0.93 (aromatic CH), 0.97 (methyl­ene CH2) or 0.96 Å (methyl CH3). Hydroxyl H atoms H1O and H2O were found in a difference map, but their positions were fixed in the final model, with O—H bond lengths constrained to 0.82 Å. Isotropic displacement parameters for H atoms were calculated as Uiso(H) = 1.5Ueq(C, O) for methyl and OH groups, and Uiso(H) = 1.2Ueq(C) for other H atoms.

Experimental top

The synthesis of the title compound is shown in Fig. 3. An ethanol solution (100 ml) of 3,5-bis(bromomethyl)phenol (2 mmol) and 3,5-bis(mercaptomethyl)phenol (2 mmol) was added dropwise to a solution of CsOH (5 mmol) as an alkaline catalyst in ethanol (250 ml). The reaction mixture was refluxed for 10 h. After completion of the reaction, the resulting mixture was cooled to room temperature, poured into ice-cold water, and extracted with dichloromethane. The organic layer was washed with water. The resulting organic layer was dried over MgSO4 and the solvent was removed under reduced pressure. The resulting residue was purified on column chromatography (silica gel), and the title cyclophane was obtained as a white powder. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate–methanol solution at room temperature.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2.

Structure description top

The synthesis and molecular structure analysis of short-bridged cyclophanes continues to attract interest in supramolecular chemistry. The understanding of the preferred conformations of cyclophane is of importance in the design of various supramolecular systems. Small-sized cyclophane molecules act as a model to explore the flexibility of such cyclophanes, due to the presence of a variety of conformational processes including ring-flipping, ring-tilting and syn--anti isomerization. Small-sized cyclophane units have been used as a platform to build cofacial bisporphyrins (Tsuge et al., 2012). The [3.3]dithiametacyclophane skeleton has also been used to provide an appropriate platform to arrange two oligomer chains side by side in a stacked arrangement, because this kind of cyclophane assumes a syn structure (Tsuge et al., 2008).

We have compared the conformation of the title compound (Fig. 1) with other cyclophanes having different substitutions at C5/C13 in the benzene rings. The title compound has OH groups at the C5/C13 positions and exists in a syn, pseudo chair-chair conformation, with both hydroxy groups positioned on the same side of the core 12-membered dithia ring. When methyl groups substitute the C5/C13 positions, the anti, pseudo boat-chair conformation is stabilized (Chan et al., 1977). Unsubstituted cyclophane exists in a syn, pseudo chair–chair conformation (Anker et al., 1979), and when cyano group are bonded at C5/C13 positions the syn, pseudo boat-boat conformation is obtained (Bodwell et al., 1997).

The crystal structure (Fig. 2) features O—H···O hydrogen bonds (Table 1) involving the hydroxy groups belonging to the cyclophane, and the carbonyl functionality of the ethyl acetate solvent.

Computing details top

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

Figures top
[Figure 1] Fig. 1. Molecular configuration and atom-numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are omitted for clarity.
[Figure 2] Fig. 2. Crystal packing diagram of the title compound, viewed along the a axis, with H atoms omitted for clarity.
[Figure 3] Fig. 3. Reaction scheme for the synthesis of the title compound.
syn-6,15-Dihydroxy-2,11-dithia[3.3]metacyclophane ethyl acetate monosolvate top
Crystal data top
C16H16O2S2·C4H8O2F(000) = 832
Mr = 392.51Dx = 1.349 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 12.1691 (9) ÅCell parameters from 3174 reflections
b = 13.1263 (10) Åθ = 2.2–24.1°
c = 12.2750 (9) ŵ = 0.30 mm−1
β = 99.818 (1)°T = 120 K
V = 1932.0 (2) Å3Prism, colorless
Z = 40.40 × 0.40 × 0.40 mm
Data collection top
Bruker APEXII CCD
diffractometer		3400 independent reflections
Radiation source: fine focus sealed tube2628 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
Detector resolution: 16.6666 pixels mm-1θmax = 25.0°, θmin = 2.2°
ω scansh = −14→14
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		k = −15→15
Tmin = 0.770, Tmax = 0.886l = −14→14
18213 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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.0368P)2 + 1.921P]
where P = (Fo2 + 2Fc2)/3
3400 reflections(Δ/σ)max = 0.001
239 parametersΔρmax = 1.04 e Å−3
0 restraintsΔρmin = −0.21 e Å−3
Crystal data top
C16H16O2S2·C4H8O2V = 1932.0 (2) Å3
Mr = 392.51Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.1691 (9) ŵ = 0.30 mm−1
b = 13.1263 (10) ÅT = 120 K
c = 12.2750 (9) Å0.40 × 0.40 × 0.40 mm
β = 99.818 (1)°
Data collection top
Bruker APEXII CCD
diffractometer		3400 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		2628 reflections with I > 2σ(I)
Tmin = 0.770, Tmax = 0.886Rint = 0.055
18213 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.00Δρmax = 1.04 e Å−3
3400 reflectionsΔρmin = −0.21 e Å−3
239 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8223 (2)0.2151 (2)0.3808 (2)0.0318 (6)
H1A0.74780.20520.39710.038*
H1B0.84560.28350.40430.038*
C21.0536 (2)0.1794 (2)0.4633 (2)0.0316 (6)
H2A1.05280.24970.48750.038*
H2B1.1070.14290.51710.038*
C31.0928 (2)0.1765 (2)0.35338 (19)0.0251 (6)
C41.1255 (2)0.0850 (2)0.3124 (2)0.0251 (6)
H41.12770.02590.35440.03*
C51.1548 (2)0.0824 (2)0.2078 (2)0.0235 (6)
C61.1500 (2)0.1698 (2)0.1439 (2)0.0251 (6)
H61.16670.16660.07290.03*
C71.1204 (2)0.2618 (2)0.1855 (2)0.0239 (6)
C81.0939 (2)0.2643 (2)0.2912 (2)0.0264 (6)
H81.07660.32630.32080.032*
C91.1167 (2)0.3573 (2)0.1168 (2)0.0293 (6)
H9A1.19160.37190.10390.035*
H9B1.09390.41350.15910.035*
C100.8876 (2)0.3704 (2)0.0228 (2)0.0319 (6)
H10A0.88990.43120.06790.038*
H10B0.83350.382−0.04380.038*
C110.8478 (2)0.2830 (2)0.0851 (2)0.0262 (6)
C120.8177 (2)0.1917 (2)0.0317 (2)0.0258 (6)
H120.8190.1855−0.04350.031*
C130.7856 (2)0.1099 (2)0.0899 (2)0.0245 (6)
C140.7863 (2)0.1176 (2)0.2029 (2)0.0259 (6)
H140.76630.06190.24190.031*
C150.8169 (2)0.2080 (2)0.2573 (2)0.0262 (6)
C160.8450 (2)0.2915 (2)0.1975 (2)0.0285 (6)
H160.8620.35350.2330.034*
C170.9315 (2)0.8870 (2)0.2122 (3)0.0384 (7)
H17A0.94190.94520.26020.058*
H17B0.86020.85680.21480.058*
H17C0.93470.9080.13790.058*
C181.0211 (2)0.8112 (2)0.2489 (2)0.0253 (6)
C191.0648 (2)0.6477 (2)0.3228 (2)0.0288 (6)
H19A1.11630.67160.38680.035*
H19B1.10690.63150.26470.035*
C201.0040 (2)0.5557 (2)0.3521 (3)0.0409 (7)
H20A0.96010.57340.40730.061*
H20B1.05680.50390.38050.061*
H20C0.9560.53080.28730.061*
O10.75162 (15)0.01893 (14)0.04032 (14)0.0315 (5)
H1O0.76680.0177−0.02220.047*
O21.19101 (16)−0.00557 (14)0.16493 (15)0.0322 (5)
H2O1.1684−0.05490.19560.048*
O31.11964 (14)0.82409 (13)0.24655 (14)0.0285 (4)
O40.98224 (14)0.72552 (13)0.28542 (14)0.0260 (4)
S10.91552 (6)0.12469 (6)0.46261 (5)0.03039 (19)
S21.02408 (6)0.35251 (5)−0.01616 (5)0.02919 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0282 (15)0.0450 (18)0.0238 (14)0.0036 (13)0.0087 (11)−0.0031 (12)
C20.0305 (15)0.0429 (17)0.0212 (14)−0.0031 (13)0.0037 (11)−0.0043 (12)
C30.0176 (13)0.0401 (16)0.0165 (12)−0.0027 (11)−0.0004 (10)−0.0038 (11)
C40.0219 (13)0.0339 (15)0.0188 (13)−0.0039 (11)0.0012 (10)0.0039 (11)
C50.0198 (13)0.0307 (15)0.0199 (13)−0.0011 (11)0.0028 (10)−0.0039 (11)
C60.0204 (13)0.0370 (16)0.0181 (13)−0.0025 (11)0.0036 (10)0.0007 (11)
C70.0172 (13)0.0322 (15)0.0213 (13)−0.0027 (11)0.0003 (10)0.0000 (11)
C80.0208 (13)0.0337 (16)0.0240 (14)−0.0013 (11)0.0012 (11)−0.0060 (12)
C90.0261 (14)0.0338 (16)0.0270 (14)−0.0055 (12)0.0017 (11)0.0007 (12)
C100.0282 (15)0.0358 (16)0.0304 (15)0.0029 (12)0.0012 (12)0.0031 (13)
C110.0185 (13)0.0353 (16)0.0243 (14)0.0041 (11)0.0020 (10)0.0031 (12)
C120.0204 (13)0.0380 (16)0.0186 (13)0.0038 (12)0.0023 (10)0.0032 (12)
C130.0180 (13)0.0333 (15)0.0214 (13)0.0012 (11)0.0014 (10)−0.0029 (11)
C140.0182 (13)0.0372 (16)0.0232 (13)0.0009 (11)0.0061 (10)0.0039 (12)
C150.0189 (13)0.0377 (16)0.0224 (13)0.0048 (11)0.0050 (10)0.0007 (12)
C160.0222 (14)0.0347 (16)0.0275 (14)0.0020 (12)0.0016 (11)−0.0053 (12)
C170.0296 (16)0.0331 (16)0.0498 (18)0.0004 (13)−0.0007 (14)0.0057 (14)
C180.0267 (15)0.0304 (15)0.0184 (13)0.0008 (12)0.0029 (11)−0.0015 (11)
C190.0260 (14)0.0341 (16)0.0259 (14)0.0055 (12)0.0033 (11)0.0042 (12)
C200.0348 (17)0.0374 (18)0.0510 (19)0.0059 (14)0.0090 (14)0.0095 (15)
O10.0362 (11)0.0373 (11)0.0218 (10)−0.0073 (9)0.0074 (8)−0.0031 (8)
O20.0430 (12)0.0287 (11)0.0286 (10)0.0006 (9)0.0169 (9)0.0018 (8)
O30.0258 (10)0.0334 (11)0.0269 (10)−0.0006 (8)0.0060 (8)0.0009 (8)
O40.0248 (10)0.0282 (10)0.0251 (10)0.0013 (8)0.0043 (8)0.0022 (8)
S10.0306 (4)0.0433 (4)0.0182 (3)−0.0024 (3)0.0068 (3)0.0020 (3)
S20.0317 (4)0.0357 (4)0.0204 (3)−0.0016 (3)0.0052 (3)0.0034 (3)
Geometric parameters (Å, º) top
C1—C151.509 (3)C11—C121.384 (4)
C1—S11.821 (3)C11—C161.390 (3)
C1—H1A0.97C12—C131.383 (4)
C1—H1B0.97C12—H120.93
C2—C31.507 (3)C13—O11.371 (3)
C2—S11.826 (3)C13—C141.389 (3)
C2—H2A0.97C14—C151.381 (4)
C2—H2B0.97C14—H140.93
C3—C41.386 (4)C15—C161.394 (4)
C3—C81.384 (4)C16—H160.93
C4—C51.390 (3)C17—C181.488 (4)
C4—H40.93C17—H17A0.96
C5—C61.385 (4)C17—H17B0.96
C5—O21.372 (3)C17—H17C0.96
C6—C71.382 (4)C18—O31.216 (3)
C6—H60.93C18—O41.328 (3)
C7—C81.390 (3)C19—O41.451 (3)
C7—C91.508 (4)C19—C201.491 (4)
C8—H80.93C19—H19A0.97
C9—S21.820 (3)C19—H19B0.97
C9—H9A0.97C20—H20A0.96
C9—H9B0.97C20—H20B0.96
C10—C111.504 (4)C20—H20C0.96
C10—S21.820 (3)O1—H1O0.82
C10—H10A0.97O2—H2O0.82
C10—H10B0.97
C15—C1—S1115.46 (18)C12—C11—C10120.1 (2)
C15—C1—H1A108.4C16—C11—C10120.5 (2)
S1—C1—H1A108.4C11—C12—C13120.2 (2)
C15—C1—H1B108.4C11—C12—H12119.9
S1—C1—H1B108.4C13—C12—H12119.9
H1A—C1—H1B107.5O1—C13—C14117.2 (2)
C3—C2—S1114.70 (18)O1—C13—C12122.5 (2)
C3—C2—H2A108.6C14—C13—C12120.2 (2)
S1—C2—H2A108.6C15—C14—C13120.1 (2)
C3—C2—H2B108.6C15—C14—H14119.9
S1—C2—H2B108.6C13—C14—H14119.9
H2A—C2—H2B107.6C14—C15—C16119.3 (2)
C4—C3—C8119.4 (2)C14—C15—C1120.1 (2)
C4—C3—C2120.1 (2)C16—C15—C1120.6 (2)
C8—C3—C2120.5 (2)C11—C16—C15120.6 (3)
C3—C4—C5119.4 (2)C11—C16—H16119.7
C3—C4—H4120.3C15—C16—H16119.7
C5—C4—H4120.3C18—C17—H17A109.5
C6—C5—O2117.7 (2)C18—C17—H17B109.5
C6—C5—C4120.6 (2)H17A—C17—H17B109.5
O2—C5—C4121.7 (2)C18—C17—H17C109.5
C5—C6—C7120.2 (2)H17A—C17—H17C109.5
C5—C6—H6119.9H17B—C17—H17C109.5
C7—C6—H6119.9O3—C18—O4122.4 (2)
C6—C7—C8118.8 (2)O3—C18—C17125.1 (2)
C6—C7—C9120.3 (2)O4—C18—C17112.6 (2)
C8—C7—C9120.9 (2)O4—C19—C20107.5 (2)
C3—C8—C7121.4 (2)O4—C19—H19A110.2
C3—C8—H8119.3C20—C19—H19A110.2
C7—C8—H8119.3O4—C19—H19B110.2
C7—C9—S2115.30 (18)C20—C19—H19B110.2
C7—C9—H9A108.4H19A—C19—H19B108.5
S2—C9—H9A108.4C19—C20—H20A109.5
C7—C9—H9B108.4C19—C20—H20B109.5
S2—C9—H9B108.4H20A—C20—H20B109.5
H9A—C9—H9B107.5C19—C20—H20C109.5
C11—C10—S2115.02 (19)H20A—C20—H20C109.5
C11—C10—H10A108.5H20B—C20—H20C109.5
S2—C10—H10A108.5C13—O1—H1O109.5
C11—C10—H10B108.5C5—O2—H2O109.5
S2—C10—H10B108.5C18—O4—C19115.8 (2)
H10A—C10—H10B107.5C1—S1—C2103.45 (13)
C12—C11—C16119.3 (2)C9—S2—C10102.34 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2i0.821.912.732 (3)176
O2—H2O···O3ii0.821.842.656 (3)172
Symmetry codes: (i) −x+2, −y, −z; (ii) x, y−1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···O2i0.821.912.732 (3)176
O2—H2O···O3ii0.821.842.656 (3)172
Symmetry codes: (i) −x+2, −y, −z; (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formulaC16H16O2S2·C4H8O2
Mr392.51
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)12.1691 (9), 13.1263 (10), 12.2750 (9)
β (°) 99.818 (1)
V (Å3)1932.0 (2)
Z4
Radiation typeMo Kα
µ (mm−1)0.30
Crystal size (mm)0.40 × 0.40 × 0.40
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2009)
Tmin, Tmax0.770, 0.886
No. of measured, independent and
observed [I > 2σ(I)] reflections		18213, 3400, 2628
Rint0.055
(sin θ/λ)max (Å−1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.100, 1.00
No. of reflections3400
No. of parameters239
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.04, −0.21

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008).

 

Acknowledgements

We are grateful to the Center for Instrumental Analysis, Kyushu Institute of Technology (KITCIA), for the X-ray analysis.

References

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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 1| Part 1| January 2016| x160082
doi:10.1107/S2414314616000821
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