organic compounds
syn-6,15-Dihydroxy-2,11-dithia[3.3]metacyclophane ethyl acetate monosolvate
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
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.
Keywords: crystal structure; cyclophane; solvate; hydrogen bonding.
CCDC reference: 1447490
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). 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 ) 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.
(Fig. 2Synthesis and crystallization
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 (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
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1447490
10.1107/S2414314616000821/bh4001sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616000821/bh4001Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616000821/bh4001Isup3.cml
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
(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.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
(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.Crystal data, data collection and structure
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.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
(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.The synthesis and molecular structure analysis of short-bridged
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 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
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
(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.Data collection: APEX2 (Bruker, 2009); cell
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).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. | |
Fig. 2. Crystal packing diagram of the title compound, viewed along the a axis, with H atoms omitted for clarity. | |
Fig. 3. Reaction scheme for the synthesis of the title compound. |
C16H16O2S2·C4H8O2 | F(000) = 832 |
Mr = 392.51 | Dx = 1.349 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.1691 (9) Å | Cell parameters from 3174 reflections |
b = 13.1263 (10) Å | θ = 2.2–24.1° |
c = 12.2750 (9) Å | µ = 0.30 mm−1 |
β = 99.818 (1)° | T = 120 K |
V = 1932.0 (2) Å3 | Prism, colorless |
Z = 4 | 0.40 × 0.40 × 0.40 mm |
Bruker APEXII CCD diffractometer | 3400 independent reflections |
Radiation source: fine focus sealed tube | 2628 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 16.6666 pixels mm-1 | θmax = 25.0°, θmin = 2.2° |
ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −15→15 |
Tmin = 0.770, Tmax = 0.886 | l = −14→14 |
18213 measured reflections |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H-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 parameters | Δρmax = 1.04 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C16H16O2S2·C4H8O2 | V = 1932.0 (2) Å3 |
Mr = 392.51 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.1691 (9) Å | µ = 0.30 mm−1 |
b = 13.1263 (10) Å | T = 120 K |
c = 12.2750 (9) Å | 0.40 × 0.40 × 0.40 mm |
β = 99.818 (1)° |
Bruker APEXII CCD diffractometer | 3400 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 2628 reflections with I > 2σ(I) |
Tmin = 0.770, Tmax = 0.886 | Rint = 0.055 |
18213 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters constrained |
S = 1.00 | Δρmax = 1.04 e Å−3 |
3400 reflections | Δρmin = −0.21 e Å−3 |
239 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8223 (2) | 0.2151 (2) | 0.3808 (2) | 0.0318 (6) | |
H1A | 0.7478 | 0.2052 | 0.3971 | 0.038* | |
H1B | 0.8456 | 0.2835 | 0.4043 | 0.038* | |
C2 | 1.0536 (2) | 0.1794 (2) | 0.4633 (2) | 0.0316 (6) | |
H2A | 1.0528 | 0.2497 | 0.4875 | 0.038* | |
H2B | 1.107 | 0.1429 | 0.5171 | 0.038* | |
C3 | 1.0928 (2) | 0.1765 (2) | 0.35338 (19) | 0.0251 (6) | |
C4 | 1.1255 (2) | 0.0850 (2) | 0.3124 (2) | 0.0251 (6) | |
H4 | 1.1277 | 0.0259 | 0.3544 | 0.03* | |
C5 | 1.1548 (2) | 0.0824 (2) | 0.2078 (2) | 0.0235 (6) | |
C6 | 1.1500 (2) | 0.1698 (2) | 0.1439 (2) | 0.0251 (6) | |
H6 | 1.1667 | 0.1666 | 0.0729 | 0.03* | |
C7 | 1.1204 (2) | 0.2618 (2) | 0.1855 (2) | 0.0239 (6) | |
C8 | 1.0939 (2) | 0.2643 (2) | 0.2912 (2) | 0.0264 (6) | |
H8 | 1.0766 | 0.3263 | 0.3208 | 0.032* | |
C9 | 1.1167 (2) | 0.3573 (2) | 0.1168 (2) | 0.0293 (6) | |
H9A | 1.1916 | 0.3719 | 0.1039 | 0.035* | |
H9B | 1.0939 | 0.4135 | 0.1591 | 0.035* | |
C10 | 0.8876 (2) | 0.3704 (2) | 0.0228 (2) | 0.0319 (6) | |
H10A | 0.8899 | 0.4312 | 0.0679 | 0.038* | |
H10B | 0.8335 | 0.382 | −0.0438 | 0.038* | |
C11 | 0.8478 (2) | 0.2830 (2) | 0.0851 (2) | 0.0262 (6) | |
C12 | 0.8177 (2) | 0.1917 (2) | 0.0317 (2) | 0.0258 (6) | |
H12 | 0.819 | 0.1855 | −0.0435 | 0.031* | |
C13 | 0.7856 (2) | 0.1099 (2) | 0.0899 (2) | 0.0245 (6) | |
C14 | 0.7863 (2) | 0.1176 (2) | 0.2029 (2) | 0.0259 (6) | |
H14 | 0.7663 | 0.0619 | 0.2419 | 0.031* | |
C15 | 0.8169 (2) | 0.2080 (2) | 0.2573 (2) | 0.0262 (6) | |
C16 | 0.8450 (2) | 0.2915 (2) | 0.1975 (2) | 0.0285 (6) | |
H16 | 0.862 | 0.3535 | 0.233 | 0.034* | |
C17 | 0.9315 (2) | 0.8870 (2) | 0.2122 (3) | 0.0384 (7) | |
H17A | 0.9419 | 0.9452 | 0.2602 | 0.058* | |
H17B | 0.8602 | 0.8568 | 0.2148 | 0.058* | |
H17C | 0.9347 | 0.908 | 0.1379 | 0.058* | |
C18 | 1.0211 (2) | 0.8112 (2) | 0.2489 (2) | 0.0253 (6) | |
C19 | 1.0648 (2) | 0.6477 (2) | 0.3228 (2) | 0.0288 (6) | |
H19A | 1.1163 | 0.6716 | 0.3868 | 0.035* | |
H19B | 1.1069 | 0.6315 | 0.2647 | 0.035* | |
C20 | 1.0040 (2) | 0.5557 (2) | 0.3521 (3) | 0.0409 (7) | |
H20A | 0.9601 | 0.5734 | 0.4073 | 0.061* | |
H20B | 1.0568 | 0.5039 | 0.3805 | 0.061* | |
H20C | 0.956 | 0.5308 | 0.2873 | 0.061* | |
O1 | 0.75162 (15) | 0.01893 (14) | 0.04032 (14) | 0.0315 (5) | |
H1O | 0.7668 | 0.0177 | −0.0222 | 0.047* | |
O2 | 1.19101 (16) | −0.00557 (14) | 0.16493 (15) | 0.0322 (5) | |
H2O | 1.1684 | −0.0549 | 0.1956 | 0.048* | |
O3 | 1.11964 (14) | 0.82409 (13) | 0.24655 (14) | 0.0285 (4) | |
O4 | 0.98224 (14) | 0.72552 (13) | 0.28542 (14) | 0.0260 (4) | |
S1 | 0.91552 (6) | 0.12469 (6) | 0.46261 (5) | 0.03039 (19) | |
S2 | 1.02408 (6) | 0.35251 (5) | −0.01616 (5) | 0.02919 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0282 (15) | 0.0450 (18) | 0.0238 (14) | 0.0036 (13) | 0.0087 (11) | −0.0031 (12) |
C2 | 0.0305 (15) | 0.0429 (17) | 0.0212 (14) | −0.0031 (13) | 0.0037 (11) | −0.0043 (12) |
C3 | 0.0176 (13) | 0.0401 (16) | 0.0165 (12) | −0.0027 (11) | −0.0004 (10) | −0.0038 (11) |
C4 | 0.0219 (13) | 0.0339 (15) | 0.0188 (13) | −0.0039 (11) | 0.0012 (10) | 0.0039 (11) |
C5 | 0.0198 (13) | 0.0307 (15) | 0.0199 (13) | −0.0011 (11) | 0.0028 (10) | −0.0039 (11) |
C6 | 0.0204 (13) | 0.0370 (16) | 0.0181 (13) | −0.0025 (11) | 0.0036 (10) | 0.0007 (11) |
C7 | 0.0172 (13) | 0.0322 (15) | 0.0213 (13) | −0.0027 (11) | 0.0003 (10) | 0.0000 (11) |
C8 | 0.0208 (13) | 0.0337 (16) | 0.0240 (14) | −0.0013 (11) | 0.0012 (11) | −0.0060 (12) |
C9 | 0.0261 (14) | 0.0338 (16) | 0.0270 (14) | −0.0055 (12) | 0.0017 (11) | 0.0007 (12) |
C10 | 0.0282 (15) | 0.0358 (16) | 0.0304 (15) | 0.0029 (12) | 0.0012 (12) | 0.0031 (13) |
C11 | 0.0185 (13) | 0.0353 (16) | 0.0243 (14) | 0.0041 (11) | 0.0020 (10) | 0.0031 (12) |
C12 | 0.0204 (13) | 0.0380 (16) | 0.0186 (13) | 0.0038 (12) | 0.0023 (10) | 0.0032 (12) |
C13 | 0.0180 (13) | 0.0333 (15) | 0.0214 (13) | 0.0012 (11) | 0.0014 (10) | −0.0029 (11) |
C14 | 0.0182 (13) | 0.0372 (16) | 0.0232 (13) | 0.0009 (11) | 0.0061 (10) | 0.0039 (12) |
C15 | 0.0189 (13) | 0.0377 (16) | 0.0224 (13) | 0.0048 (11) | 0.0050 (10) | 0.0007 (12) |
C16 | 0.0222 (14) | 0.0347 (16) | 0.0275 (14) | 0.0020 (12) | 0.0016 (11) | −0.0053 (12) |
C17 | 0.0296 (16) | 0.0331 (16) | 0.0498 (18) | 0.0004 (13) | −0.0007 (14) | 0.0057 (14) |
C18 | 0.0267 (15) | 0.0304 (15) | 0.0184 (13) | 0.0008 (12) | 0.0029 (11) | −0.0015 (11) |
C19 | 0.0260 (14) | 0.0341 (16) | 0.0259 (14) | 0.0055 (12) | 0.0033 (11) | 0.0042 (12) |
C20 | 0.0348 (17) | 0.0374 (18) | 0.0510 (19) | 0.0059 (14) | 0.0090 (14) | 0.0095 (15) |
O1 | 0.0362 (11) | 0.0373 (11) | 0.0218 (10) | −0.0073 (9) | 0.0074 (8) | −0.0031 (8) |
O2 | 0.0430 (12) | 0.0287 (11) | 0.0286 (10) | 0.0006 (9) | 0.0169 (9) | 0.0018 (8) |
O3 | 0.0258 (10) | 0.0334 (11) | 0.0269 (10) | −0.0006 (8) | 0.0060 (8) | 0.0009 (8) |
O4 | 0.0248 (10) | 0.0282 (10) | 0.0251 (10) | 0.0013 (8) | 0.0043 (8) | 0.0022 (8) |
S1 | 0.0306 (4) | 0.0433 (4) | 0.0182 (3) | −0.0024 (3) | 0.0068 (3) | 0.0020 (3) |
S2 | 0.0317 (4) | 0.0357 (4) | 0.0204 (3) | −0.0016 (3) | 0.0052 (3) | 0.0034 (3) |
C1—C15 | 1.509 (3) | C11—C12 | 1.384 (4) |
C1—S1 | 1.821 (3) | C11—C16 | 1.390 (3) |
C1—H1A | 0.97 | C12—C13 | 1.383 (4) |
C1—H1B | 0.97 | C12—H12 | 0.93 |
C2—C3 | 1.507 (3) | C13—O1 | 1.371 (3) |
C2—S1 | 1.826 (3) | C13—C14 | 1.389 (3) |
C2—H2A | 0.97 | C14—C15 | 1.381 (4) |
C2—H2B | 0.97 | C14—H14 | 0.93 |
C3—C4 | 1.386 (4) | C15—C16 | 1.394 (4) |
C3—C8 | 1.384 (4) | C16—H16 | 0.93 |
C4—C5 | 1.390 (3) | C17—C18 | 1.488 (4) |
C4—H4 | 0.93 | C17—H17A | 0.96 |
C5—C6 | 1.385 (4) | C17—H17B | 0.96 |
C5—O2 | 1.372 (3) | C17—H17C | 0.96 |
C6—C7 | 1.382 (4) | C18—O3 | 1.216 (3) |
C6—H6 | 0.93 | C18—O4 | 1.328 (3) |
C7—C8 | 1.390 (3) | C19—O4 | 1.451 (3) |
C7—C9 | 1.508 (4) | C19—C20 | 1.491 (4) |
C8—H8 | 0.93 | C19—H19A | 0.97 |
C9—S2 | 1.820 (3) | C19—H19B | 0.97 |
C9—H9A | 0.97 | C20—H20A | 0.96 |
C9—H9B | 0.97 | C20—H20B | 0.96 |
C10—C11 | 1.504 (4) | C20—H20C | 0.96 |
C10—S2 | 1.820 (3) | O1—H1O | 0.82 |
C10—H10A | 0.97 | O2—H2O | 0.82 |
C10—H10B | 0.97 | ||
C15—C1—S1 | 115.46 (18) | C12—C11—C10 | 120.1 (2) |
C15—C1—H1A | 108.4 | C16—C11—C10 | 120.5 (2) |
S1—C1—H1A | 108.4 | C11—C12—C13 | 120.2 (2) |
C15—C1—H1B | 108.4 | C11—C12—H12 | 119.9 |
S1—C1—H1B | 108.4 | C13—C12—H12 | 119.9 |
H1A—C1—H1B | 107.5 | O1—C13—C14 | 117.2 (2) |
C3—C2—S1 | 114.70 (18) | O1—C13—C12 | 122.5 (2) |
C3—C2—H2A | 108.6 | C14—C13—C12 | 120.2 (2) |
S1—C2—H2A | 108.6 | C15—C14—C13 | 120.1 (2) |
C3—C2—H2B | 108.6 | C15—C14—H14 | 119.9 |
S1—C2—H2B | 108.6 | C13—C14—H14 | 119.9 |
H2A—C2—H2B | 107.6 | C14—C15—C16 | 119.3 (2) |
C4—C3—C8 | 119.4 (2) | C14—C15—C1 | 120.1 (2) |
C4—C3—C2 | 120.1 (2) | C16—C15—C1 | 120.6 (2) |
C8—C3—C2 | 120.5 (2) | C11—C16—C15 | 120.6 (3) |
C3—C4—C5 | 119.4 (2) | C11—C16—H16 | 119.7 |
C3—C4—H4 | 120.3 | C15—C16—H16 | 119.7 |
C5—C4—H4 | 120.3 | C18—C17—H17A | 109.5 |
C6—C5—O2 | 117.7 (2) | C18—C17—H17B | 109.5 |
C6—C5—C4 | 120.6 (2) | H17A—C17—H17B | 109.5 |
O2—C5—C4 | 121.7 (2) | C18—C17—H17C | 109.5 |
C5—C6—C7 | 120.2 (2) | H17A—C17—H17C | 109.5 |
C5—C6—H6 | 119.9 | H17B—C17—H17C | 109.5 |
C7—C6—H6 | 119.9 | O3—C18—O4 | 122.4 (2) |
C6—C7—C8 | 118.8 (2) | O3—C18—C17 | 125.1 (2) |
C6—C7—C9 | 120.3 (2) | O4—C18—C17 | 112.6 (2) |
C8—C7—C9 | 120.9 (2) | O4—C19—C20 | 107.5 (2) |
C3—C8—C7 | 121.4 (2) | O4—C19—H19A | 110.2 |
C3—C8—H8 | 119.3 | C20—C19—H19A | 110.2 |
C7—C8—H8 | 119.3 | O4—C19—H19B | 110.2 |
C7—C9—S2 | 115.30 (18) | C20—C19—H19B | 110.2 |
C7—C9—H9A | 108.4 | H19A—C19—H19B | 108.5 |
S2—C9—H9A | 108.4 | C19—C20—H20A | 109.5 |
C7—C9—H9B | 108.4 | C19—C20—H20B | 109.5 |
S2—C9—H9B | 108.4 | H20A—C20—H20B | 109.5 |
H9A—C9—H9B | 107.5 | C19—C20—H20C | 109.5 |
C11—C10—S2 | 115.02 (19) | H20A—C20—H20C | 109.5 |
C11—C10—H10A | 108.5 | H20B—C20—H20C | 109.5 |
S2—C10—H10A | 108.5 | C13—O1—H1O | 109.5 |
C11—C10—H10B | 108.5 | C5—O2—H2O | 109.5 |
S2—C10—H10B | 108.5 | C18—O4—C19 | 115.8 (2) |
H10A—C10—H10B | 107.5 | C1—S1—C2 | 103.45 (13) |
C12—C11—C16 | 119.3 (2) | C9—S2—C10 | 102.34 (12) |
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. |
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. |
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 |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
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), 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.
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