organic compounds
2,6-Bis(4-methoxyphenyl)-1,4-dithiine
aDepartment of Chemistry, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China
*Correspondence e-mail: pzh7251@yahoo.com, deliean@hnu.edu.cn
The title molecule, C18H16O2S2, reveals crystallographic twofold rotation symmetry (with both S atoms lying on the axis) and one half-molecule defines an The dithiine ring is in a boat conformation. The aromatic ring and the C=C bond are nearly coplanar, with small torsion angles of −171.26 (19) and 8.5 (3)°. The two S—C bond lengths [1.7391 (19) and 1.7795 (18) Å] are shorter than single C—S bonds and longer than analogous C=S double bonds, which indicates a certain degree of conjugation between the lone pair on the S atom and π electrons of the C=C bond. The crystal packing only features van der Waals interactions.
CCDC reference: 969198
Related literature
For a similar et al. (2004). For background to 1,4-dithiine derivatives, see: Kobayashi & Gajurel (1986); Scott et al. (2000). For the synthesis of a similar compound, see: Nakayama et al. (1984). For standard bond lengths, see: Allen et al. (1987).
2,6-diphenyl-1,4-dithiine, see: PiaoExperimental
Crystal data
|
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); 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); software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 969198
10.1107/S1600536814000397/kp2462sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814000397/kp2462Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814000397/kp2462Isup3.cml
NaOEt (224 mg, 3.3 mmol) was dissolved in alcohol (10 mL), and then added to bis(4-methoxyphenylethynyl) sulfide (97.8 mg,0.33 mmol). After the mixture was stirred at room temperature for 10 min, Na2S·9H2O (159 mg, 0.66 mmol) was added. The resulting mixture was then stirred at reflux temperature for 2 h. The reaction mixture was cooled to room temperature and quenched by water and extracted with dichloromethane. The extract was then washed with brine, dried over Na2SO4, and filtered. The solvent was evaporated in vacuo, and the residue was chromatographed (SiO2; δ = 3.83 (s, 6H; OCH3), 6.42 (s, 2H; CH), 6.89(d, J = 8.8 Hz, 4H; Ar—H), 7.58 (d, J = 8.8 Hz, 4H; Ar—H); 13C NMR (100 MHz, CDCl3): δ = 55.50 (OCH3), 114.07 (CH), 116.40 (CH), 128.45 (CH), 129.83 (C), 139.52 (C), 160.10 (C); IR (KBr): ν = 3020, 2959, 2914, 1607, 1508, 1457, 1258, 1191, 832 cm-1; MS (EI): m/z (%): 328.2 (M+, 100), 313.1 (43); HRMS (EI): m/z Calcd for C18H16O2S2 328.0584, Found 328.0586.
ether/dichloromethane, 4: 1) to give 93 mg of compound I (85%) as a yellow solid: mp 401–403 K; 1H NMR (400 MHz, CDCl3):Single crystals of (I) suitable for X-ray
was obtained by slow diffusion of petroleum ether into a dichloromethane solution at 298 K.H atoms were refined with fixed individual displacement parameters [Uiso (H) = 1.2 Ueq (C) and Uiso (H) = 1.5 Ueq (C methyl)] using a riding model, with aromatic C—H = 0.93 Å, methyl C—H = 0.96 Å.
1,4-Dithiine derivatives are very important intermediates in organic synthesis and can be used as versatile building blocks for a variety of chemical purposes (Kobayashi & Gajurel, 1986). In addition, some 1,4-dithiine derivatives have exhibited good biological activities, For example, Scott et al. showed that 2,3-dihydro-2-phenyl-1,4-dithiin-1,1,4,4-tetroxide could be used as nonpeptide antagonist of the human Galanin hGAL-1 receptor (Scott et al., 2000). Unfortunately, there are very few acceptable methods to prepare 1,4-dithiine compounds thus far, and, in most cases, a successful protocol must use bis(arylethanonyl)
compounds as precursors. Herein we report a new synthetic approaches and of 2,6-bis(4-methoxyphenyl)-1,4-dithiine.The molecular structure of the title compound(I) (Fig. 1) exhibits a twofold rotation axes symmetry. The dithiine ring is in a boat conformation. In the crystal, dominate columns of assembled molecules, however, their separation distances are larger than 5.5402 (13) Å (Fig. 2). The bond lengths of C1—C2 in heterocyclic ring presents a characteristic of the C=C double bond. An aromatic ring and the C=C bond are nearly coplanar, with small torsion angles of -171.26 (19)° and 8.5 (3)° for C1—C2—C3—C4 and C1—C2—C3—C8,respectively ·. The two characteristic bond lengths of S1—C2 and S2—C1 are shorter than C—S single bonds and longer than analogous C=S double bonds (Allen et al., 1987), which indicates a certain degree of conjugation between the lone pair on the sulfur atom and π electrons of the C=C bond.
For a similar
2,6-diphenyl-1,4-dithiine, see: Piao et al. (2004). For background to 1,4-dithiine derivatives, see: Kobayashi & Gajurel (1986); Scott et al. (2000). For the synthesis of a similar compound, see: Nakayama et al. (1984). For standard bond lengths, see: Allen et al. (1987).Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C18H16O2S2 | F(000) = 688 |
Mr = 328.43 | Dx = 1.422 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 1658 reflections |
a = 10.1330 (11) Å | θ = 7.5–53.8° |
b = 27.318 (3) Å | µ = 0.35 mm−1 |
c = 5.5402 (6) Å | T = 293 K |
V = 1533.6 (3) Å3 | Prismatic, yellow |
Z = 4 | 0.21 × 0.18 × 0.09 mm |
Bruker SMART CCD area-detector diffractometer | 1541 independent reflections |
Radiation source: fine-focus sealed tube | 1258 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
phi and ω scans | θmax = 26.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −12→12 |
Tmin = 0.121, Tmax = 1.000 | k = −33→32 |
8513 measured reflections | l = −5→6 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0554P)2 + 0.3159P] where P = (Fo2 + 2Fc2)/3 |
1541 reflections | (Δ/σ)max < 0.001 |
104 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C18H16O2S2 | V = 1533.6 (3) Å3 |
Mr = 328.43 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 10.1330 (11) Å | µ = 0.35 mm−1 |
b = 27.318 (3) Å | T = 293 K |
c = 5.5402 (6) Å | 0.21 × 0.18 × 0.09 mm |
Bruker SMART CCD area-detector diffractometer | 1541 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1258 reflections with I > 2σ(I) |
Tmin = 0.121, Tmax = 1.000 | Rint = 0.043 |
8513 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.29 e Å−3 |
1541 reflections | Δρmin = −0.16 e Å−3 |
104 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.49280 (7) | 0.2500 | 0.16602 (12) | 0.0352 (2) | |
S2 | 0.70856 (7) | 0.2500 | −0.24173 (15) | 0.0423 (2) | |
O1 | 0.14361 (14) | 0.45648 (5) | 0.0468 (3) | 0.0484 (4) | |
C1 | 0.60102 (19) | 0.29896 (6) | −0.2021 (4) | 0.0364 (5) | |
H1 | 0.6115 | 0.3262 | −0.3011 | 0.044* | |
C2 | 0.50486 (19) | 0.29989 (6) | −0.0393 (3) | 0.0307 (4) | |
C3 | 0.40701 (18) | 0.33990 (6) | −0.0143 (3) | 0.0296 (4) | |
C4 | 0.3199 (2) | 0.34206 (7) | 0.1786 (4) | 0.0364 (5) | |
H4 | 0.3213 | 0.3172 | 0.2931 | 0.044* | |
C5 | 0.2311 (2) | 0.38017 (7) | 0.2059 (3) | 0.0372 (5) | |
H5 | 0.1746 | 0.3808 | 0.3381 | 0.045* | |
C6 | 0.22660 (19) | 0.41714 (7) | 0.0376 (3) | 0.0352 (5) | |
C7 | 0.31115 (19) | 0.41530 (7) | −0.1595 (4) | 0.0395 (5) | |
H7 | 0.3083 | 0.4399 | −0.2753 | 0.047* | |
C8 | 0.3984 (2) | 0.37754 (7) | −0.1841 (4) | 0.0371 (5) | |
H8 | 0.4537 | 0.3769 | −0.3180 | 0.044* | |
C9 | 0.0549 (2) | 0.45883 (8) | 0.2462 (5) | 0.0556 (6) | |
H9A | 0.0005 | 0.4301 | 0.2479 | 0.083* | |
H9B | 0.0002 | 0.4874 | 0.2311 | 0.083* | |
H9C | 0.1043 | 0.4606 | 0.3938 | 0.083* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0430 (4) | 0.0328 (4) | 0.0297 (4) | 0.000 | −0.0017 (3) | 0.000 |
S2 | 0.0266 (4) | 0.0405 (4) | 0.0599 (5) | 0.000 | 0.0101 (3) | 0.000 |
O1 | 0.0487 (9) | 0.0401 (8) | 0.0563 (10) | 0.0129 (7) | 0.0112 (7) | 0.0073 (7) |
C1 | 0.0326 (10) | 0.0306 (9) | 0.0459 (12) | −0.0035 (8) | 0.0042 (9) | 0.0016 (8) |
C2 | 0.0304 (9) | 0.0287 (9) | 0.0332 (11) | −0.0063 (8) | −0.0021 (8) | −0.0015 (7) |
C3 | 0.0290 (10) | 0.0274 (9) | 0.0324 (10) | −0.0058 (8) | −0.0013 (8) | −0.0028 (7) |
C4 | 0.0416 (11) | 0.0314 (9) | 0.0361 (11) | −0.0007 (8) | 0.0067 (8) | 0.0043 (8) |
C5 | 0.0397 (11) | 0.0362 (10) | 0.0357 (11) | 0.0002 (9) | 0.0093 (9) | 0.0000 (8) |
C6 | 0.0333 (10) | 0.0305 (10) | 0.0420 (11) | −0.0001 (8) | −0.0015 (9) | −0.0015 (8) |
C7 | 0.0421 (11) | 0.0382 (10) | 0.0381 (11) | 0.0000 (9) | 0.0019 (9) | 0.0095 (9) |
C8 | 0.0383 (11) | 0.0397 (10) | 0.0331 (11) | 0.0004 (9) | 0.0062 (8) | 0.0030 (8) |
C9 | 0.0548 (14) | 0.0493 (13) | 0.0627 (15) | 0.0180 (11) | 0.0168 (12) | 0.0019 (12) |
S1—C2 | 1.7795 (18) | C4—C5 | 1.384 (3) |
S1—C2i | 1.7795 (18) | C4—H4 | 0.9300 |
S2—C1 | 1.7391 (19) | C5—C6 | 1.375 (3) |
S2—C1i | 1.7391 (19) | C5—H5 | 0.9300 |
O1—C6 | 1.365 (2) | C6—C7 | 1.389 (3) |
O1—C9 | 1.426 (3) | C7—C8 | 1.365 (3) |
C1—C2 | 1.328 (3) | C7—H7 | 0.9300 |
C1—H1 | 0.9300 | C8—H8 | 0.9300 |
C2—C3 | 1.482 (3) | C9—H9A | 0.9600 |
C3—C4 | 1.387 (3) | C9—H9B | 0.9600 |
C3—C8 | 1.397 (3) | C9—H9C | 0.9600 |
C2—S1—C2i | 99.97 (12) | C4—C5—H5 | 120.0 |
C1—S2—C1i | 100.54 (13) | O1—C6—C5 | 124.98 (18) |
C6—O1—C9 | 116.92 (16) | O1—C6—C7 | 115.96 (17) |
C2—C1—S2 | 124.07 (15) | C5—C6—C7 | 119.06 (18) |
C2—C1—H1 | 118.0 | C8—C7—C6 | 120.36 (18) |
S2—C1—H1 | 118.0 | C8—C7—H7 | 119.8 |
C1—C2—C3 | 124.65 (16) | C6—C7—H7 | 119.8 |
C1—C2—S1 | 118.03 (15) | C7—C8—C3 | 121.97 (18) |
C3—C2—S1 | 117.32 (14) | C7—C8—H8 | 119.0 |
C4—C3—C8 | 116.60 (17) | C3—C8—H8 | 119.0 |
C4—C3—C2 | 121.94 (16) | O1—C9—H9A | 109.5 |
C8—C3—C2 | 121.46 (16) | O1—C9—H9B | 109.5 |
C5—C4—C3 | 121.98 (17) | H9A—C9—H9B | 109.5 |
C5—C4—H4 | 119.0 | O1—C9—H9C | 109.5 |
C3—C4—H4 | 119.0 | H9A—C9—H9C | 109.5 |
C6—C5—C4 | 120.00 (18) | H9B—C9—H9C | 109.5 |
C6—C5—H5 | 120.0 | ||
C1i—S2—C1—C2 | 39.0 (2) | C3—C4—C5—C6 | 0.6 (3) |
S2—C1—C2—C3 | −175.75 (14) | C9—O1—C6—C5 | −0.4 (3) |
S2—C1—C2—S1 | 4.9 (2) | C9—O1—C6—C7 | 179.31 (19) |
C2i—S1—C2—C1 | −48.1 (2) | C4—C5—C6—O1 | −179.75 (18) |
C2i—S1—C2—C3 | 132.49 (11) | C4—C5—C6—C7 | 0.6 (3) |
C1—C2—C3—C4 | −171.26 (19) | O1—C6—C7—C8 | 179.64 (18) |
S1—C2—C3—C4 | 8.1 (2) | C5—C6—C7—C8 | −0.7 (3) |
C1—C2—C3—C8 | 8.5 (3) | C6—C7—C8—C3 | −0.5 (3) |
S1—C2—C3—C8 | −172.18 (14) | C4—C3—C8—C7 | 1.6 (3) |
C8—C3—C4—C5 | −1.7 (3) | C2—C3—C8—C7 | −178.16 (18) |
C2—C3—C4—C5 | 178.07 (17) |
Symmetry code: (i) x, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C18H16O2S2 |
Mr | 328.43 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 10.1330 (11), 27.318 (3), 5.5402 (6) |
V (Å3) | 1533.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.21 × 0.18 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.121, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8513, 1541, 1258 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.102, 1.04 |
No. of reflections | 1541 |
No. of parameters | 104 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.16 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The work was supported financially by the National Natural Science Foundation of China (No. 21072052) and the Hunan Provincial Science and Technology Department Program (No. 2011 W K4007).
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kobayashi, K. & Gajurel, C. L. (1986). Sulfur Rep. 7, 123–148. CrossRef CAS Google Scholar
Nakayama, J., Motoyama, H., Machida, H., Shimomura, M. & Hoshino, M. (1984). Heterocycles, 22, 1527–1530. CrossRef CAS Google Scholar
Piao, X. H., Sugihara, Y. & Nakayama, J. (2004). Heteroat. Chem. 15, 424–427. Web of Science CSD CrossRef CAS Google Scholar
Scott, M. K., Ross, T. M., Lee, D. H. S., Wang, H., Shank, R. P., Wild, K. D., Davis, C. B., Crooke, J. J., Potocki, A. C. & Reitz, A. B. (2000). Bioorg. Med. Chem. 8, 1383–1391. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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.
1,4-Dithiine derivatives are very important intermediates in organic synthesis and can be used as versatile building blocks for a variety of chemical purposes (Kobayashi & Gajurel, 1986). In addition, some 1,4-dithiine derivatives have exhibited good biological activities, For example, Scott et al. showed that 2,3-dihydro-2-phenyl-1,4-dithiin-1,1,4,4-tetroxide could be used as nonpeptide antagonist of the human Galanin hGAL-1 receptor (Scott et al., 2000). Unfortunately, there are very few acceptable methods to prepare 1,4-dithiine compounds thus far, and, in most cases, a successful protocol must use bis(arylethanonyl) sulfides compounds as precursors. Herein we report a new synthetic approaches and crystal structure of 2,6-bis(4-methoxyphenyl)-1,4-dithiine.
The molecular structure of the title compound(I) (Fig. 1) exhibits a twofold rotation axes symmetry. The dithiine ring is in a boat conformation. In the crystal, dominate columns of assembled molecules, however, their separation distances are larger than 5.5402 (13) Å (Fig. 2). The bond lengths of C1—C2 in heterocyclic ring presents a characteristic of the C=C double bond. An aromatic ring and the C=C bond are nearly coplanar, with small torsion angles of -171.26 (19)° and 8.5 (3)° for C1—C2—C3—C4 and C1—C2—C3—C8,respectively ·. The two characteristic bond lengths of S1—C2 and S2—C1 are shorter than C—S single bonds and longer than analogous C=S double bonds (Allen et al., 1987), which indicates a certain degree of conjugation between the lone pair on the sulfur atom and π electrons of the C=C bond.