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

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ISSN: 2056-9890

2-(1,3-Di­thian-2-yl­­idene)-1-phenyl­butane-1,3-dione

aCollege of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People's Republic of China
*Correspondence e-mail: zhanglc_07@sina.com

(Received 7 January 2008; accepted 24 January 2008; online 30 January 2008)

The title compound, C13H12O2S2, belonging to the group of dioxoketene cyclic S,S-acetals, was prepared from the corresponding dione in high yield. In the structure, the C=O and C=C bonds are not coplanar, with O=C—C=C torsion angles of −36.8 (4) and −21.0 (4)°. The dithian ring has a twisted conformation.

Related literature

For related literature, see: Choi et al. (1988[Choi, E. B., Youn, I. K. & Pak, C. S. (1988). Synthesis, 7, 792-794.]); Lin et al. (2005[Lin, C., Yu, H. F., Liu, Q. & Hou, D. Y. (2005). Chin. J. Org. Chem. 25, 819-821.]); Zhu et al. (1996[Zhu, Z. M., Wang, Y., Xu, Y. T. & Mei, Z. M. (1996). Chin. Chem. Lett. 7, 95-96.], 1997[Zhu, Z. M., Wang, Y., Xu, Y. T. & Mei, Z. M. (1997). Chin. Chem. Lett. 8, 367-368.]).

[Scheme 1]

Experimental

Crystal data
  • C13H12O2S2

  • Mr = 264.35

  • Monoclinic, P 21

  • a = 7.812 (3) Å

  • b = 5.5115 (18) Å

  • c = 14.628 (5) Å

  • β = 103.876 (4)°

  • V = 611.4 (4) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.42 mm−1

  • T = 298 (2) K

  • 0.14 × 0.10 × 0.01 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.956, Tmax = 0.993

  • 3073 measured reflections

  • 1948 independent reflections

  • 1887 reflections with I > 2σ(I)

  • Rint = 0.015

Refinement
  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.073

  • S = 1.04

  • 1948 reflections

  • 154 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.17 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), with 741 Friedel pairs

  • Flack parameter: −0.01 (8)

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2 (Version 1.27) and SAINT (Version 7.12A). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2 (Version 1.27) and SAINT (Version 7.12A). 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.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The dioxo ketene cyclic S,S-acetals have been known as a precursor for the synthesis of not only unsaturated ketones and keto esters, but also heterocyclic compounds (Choi et al., 1988; Lin et al., 2005; Zhu et al., 1996; Zhu et al., 1997). We have synthesized the title compound, 1-phenyl-2-(1,3-dithian -2-ylidene)-butane-1,3-dione and determined its molecular structure (Fig. 1). In the structure, the C=O bonds, the benzene ring, and the C2=C5 double bond are not co-planar. The O1—C1—C8—C13 torsion angle is -24.3 (4)°. The dihedral angle between the planes C2_C1_O1 and C2_C3_O2 is 50.7 (4)°, and is 7.6 (4) ° between the C1_C2_C3 and S1_C5_S2 planes.

Related literature top

For related literature, see: Choi et al. (1988); Lin et al. (2005); Zhu et al. (1996, 1997).

Experimental top

To a suspension of 1-phenyl-butane-1,3-dione(21 mmol) and anhydrous K2CO3(60 mmol)in DMF(20 ml was added CS2(30 mmol) at room temperature. After stirring for about 1 h, 1,2-dibromoethane (22 mmol) was added in full. Stirring was continued another 10 min at room temperature. Water(250 ml) was added to precipitate the yellow block-shaped product, which was recrystallized from ethanol, providing analytically pure compound suitable for single-crystal X-ray diffraction. M.p. 404 K°. Analysis: Found: C: 59.15, H: 4.50; calculated: C: 59.06, H: 4.58%. IR spectra: 3083,1647,1615,1418 and 1240 cm-1. 1H-NMR: 2.08(3H,s,CH3), 3.43(4H,m, 2*SCH2), 7.70(5H,m, ph)

Refinement top

All H atoms were placed in calculated positions (C—H = 0.93 Å, 0.97 Å, 0.96Å of –CH, –CH2 and-CH3 respectively) and included in the refinement in the riding-model approximation with Uiso(H) = 1.2Ueq(carrier atom) (1.5Ueq for methyl H atoms).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing diagram of the compound. viewed down the c axis. H atoms have been omitted for clarity.
2-(1,3-Dithian-2-ylidene)-1-phenylbutane-1,3-dione top
Crystal data top
C13H12O2S2F(000) = 276
Mr = 264.35Dx = 1.436 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 3425 reflections
a = 7.812 (3) Åθ = 2.7–27.8°
b = 5.5115 (18) ŵ = 0.42 mm1
c = 14.628 (5) ÅT = 298 K
β = 103.876 (4)°Block, yellow
V = 611.4 (4) Å30.14 × 0.10 × 0.01 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer
1948 independent reflections
Radiation source: fine-focus sealed tube1887 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 89
Tmin = 0.956, Tmax = 0.993k = 66
3073 measured reflectionsl = 1717
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.073 w = 1/[σ2(Fo2) + (0.0405P)2 + 0.1246P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1948 reflectionsΔρmax = 0.24 e Å3
154 parametersΔρmin = 0.17 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (8)
Crystal data top
C13H12O2S2V = 611.4 (4) Å3
Mr = 264.35Z = 2
Monoclinic, P21Mo Kα radiation
a = 7.812 (3) ŵ = 0.42 mm1
b = 5.5115 (18) ÅT = 298 K
c = 14.628 (5) Å0.14 × 0.10 × 0.01 mm
β = 103.876 (4)°
Data collection top
Bruker APEXII CCD
diffractometer
1948 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1887 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.993Rint = 0.015
3073 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.073Δρmax = 0.24 e Å3
S = 1.05Δρmin = 0.17 e Å3
1948 reflectionsAbsolute structure: Flack (1983)
154 parametersAbsolute structure parameter: 0.01 (8)
1 restraint
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
S10.45599 (7)0.16653 (13)0.16380 (4)0.04320 (18)
S20.11323 (8)0.39993 (14)0.08953 (4)0.04637 (18)
O10.4104 (2)0.2094 (4)0.27828 (13)0.0563 (5)
O20.1208 (2)0.2157 (4)0.17817 (13)0.0531 (5)
C10.2829 (3)0.1090 (5)0.29623 (15)0.0361 (5)
C20.1629 (3)0.0454 (5)0.22544 (15)0.0342 (5)
C30.0288 (3)0.0456 (5)0.21677 (16)0.0377 (6)
C40.1148 (3)0.1726 (6)0.24704 (18)0.0482 (7)
H4A0.23880.14300.23800.072*
H4B0.06360.20460.31240.072*
H4C0.09710.31020.21010.072*
C50.2343 (3)0.1860 (5)0.16689 (14)0.0348 (5)
C60.4601 (4)0.4458 (6)0.1000 (2)0.0532 (7)
H6A0.47880.58240.14310.064*
H6B0.55520.44230.06790.064*
C70.2864 (4)0.4705 (7)0.0300 (2)0.0614 (9)
H7A0.28070.35970.02220.074*
H7B0.27200.63460.00550.074*
C80.2575 (3)0.1219 (5)0.39431 (15)0.0328 (5)
C90.3325 (3)0.3133 (5)0.45259 (16)0.0390 (5)
H9A0.38920.43780.42860.047*
C100.3233 (3)0.3194 (6)0.54551 (17)0.0459 (6)
H10A0.37140.44950.58360.055*
C110.2424 (3)0.1316 (6)0.58230 (17)0.0461 (7)
H11A0.23900.13370.64540.055*
C120.1671 (3)0.0579 (6)0.52532 (17)0.0438 (6)
H12A0.11110.18250.54970.053*
C130.1749 (3)0.0631 (5)0.43144 (16)0.0368 (5)
H13A0.12430.19170.39320.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0350 (3)0.0536 (4)0.0445 (3)0.0025 (3)0.0165 (2)0.0021 (3)
S20.0403 (3)0.0550 (4)0.0434 (3)0.0041 (3)0.0093 (3)0.0130 (3)
O10.0513 (11)0.0737 (14)0.0483 (10)0.0252 (10)0.0205 (8)0.0065 (10)
O20.0350 (9)0.0578 (14)0.0650 (12)0.0054 (9)0.0091 (8)0.0119 (10)
C10.0330 (11)0.0399 (13)0.0353 (12)0.0004 (12)0.0078 (9)0.0035 (12)
C20.0309 (11)0.0423 (15)0.0298 (11)0.0007 (10)0.0082 (9)0.0025 (11)
C30.0344 (12)0.0467 (16)0.0318 (11)0.0004 (11)0.0073 (10)0.0018 (12)
C40.0393 (13)0.059 (2)0.0466 (14)0.0102 (12)0.0099 (12)0.0019 (13)
C50.0331 (11)0.0413 (14)0.0294 (10)0.0005 (11)0.0066 (9)0.0056 (11)
C60.0499 (15)0.058 (2)0.0607 (16)0.0052 (13)0.0302 (13)0.0006 (15)
C70.0612 (17)0.077 (2)0.0520 (16)0.0039 (16)0.0259 (14)0.0197 (16)
C80.0279 (10)0.0354 (13)0.0341 (11)0.0003 (10)0.0052 (8)0.0013 (11)
C90.0346 (11)0.0368 (14)0.0460 (13)0.0028 (12)0.0103 (10)0.0009 (12)
C100.0345 (11)0.0525 (16)0.0487 (13)0.0018 (13)0.0062 (10)0.0188 (15)
C110.0402 (12)0.0626 (19)0.0346 (12)0.0066 (14)0.0071 (10)0.0035 (14)
C120.0490 (14)0.0475 (16)0.0358 (13)0.0020 (12)0.0117 (11)0.0068 (12)
C130.0384 (12)0.0347 (13)0.0352 (12)0.0033 (10)0.0050 (10)0.0007 (10)
Geometric parameters (Å, º) top
S1—C51.746 (2)C6—H6A0.9700
S1—C61.804 (3)C6—H6B0.9700
S2—C51.747 (3)C7—H7A0.9700
S2—C71.817 (3)C7—H7B0.9700
O1—C11.221 (3)C8—C131.385 (3)
O2—C31.233 (3)C8—C91.394 (3)
C1—C21.487 (3)C9—C101.378 (3)
C1—C81.496 (3)C9—H9A0.9300
C2—C51.369 (3)C10—C111.387 (4)
C2—C31.472 (3)C10—H10A0.9300
C3—C41.495 (4)C11—C121.377 (4)
C4—H4A0.9600C11—H11A0.9300
C4—H4B0.9600C12—C131.389 (3)
C4—H4C0.9600C12—H12A0.9300
C6—C71.497 (4)C13—H13A0.9300
C5—S1—C695.83 (12)H6A—C6—H6B108.5
C5—S2—C796.03 (13)C6—C7—S2108.04 (19)
O1—C1—C2121.3 (2)C6—C7—H7A110.1
O1—C1—C8119.2 (2)S2—C7—H7A110.1
C2—C1—C8119.2 (2)C6—C7—H7B110.1
C5—C2—C3120.3 (2)S2—C7—H7B110.1
C5—C2—C1118.4 (2)H7A—C7—H7B108.4
C3—C2—C1121.3 (2)C13—C8—C9119.0 (2)
O2—C3—C2120.6 (2)C13—C8—C1121.5 (2)
O2—C3—C4119.5 (2)C9—C8—C1119.3 (2)
C2—C3—C4119.6 (2)C10—C9—C8120.5 (2)
C3—C4—H4A109.5C10—C9—H9A119.7
C3—C4—H4B109.5C8—C9—H9A119.7
H4A—C4—H4B109.5C9—C10—C11120.1 (3)
C3—C4—H4C109.5C9—C10—H10A120.0
H4A—C4—H4C109.5C11—C10—H10A120.0
H4B—C4—H4C109.5C12—C11—C10120.0 (2)
C2—C5—S1122.47 (19)C12—C11—H11A120.0
C2—C5—S2123.26 (17)C10—C11—H11A120.0
S1—C5—S2114.27 (14)C11—C12—C13120.0 (3)
C7—C6—S1107.8 (2)C11—C12—H12A120.0
C7—C6—H6A110.1C13—C12—H12A120.0
S1—C6—H6A110.1C8—C13—C12120.5 (2)
C7—C6—H6B110.1C8—C13—H13A119.8
S1—C6—H6B110.1C12—C13—H13A119.8
O1—C1—C2—C536.8 (4)C5—S1—C6—C736.6 (2)
C8—C1—C2—C5137.1 (2)S1—C6—C7—S245.7 (3)
O1—C1—C2—C3142.2 (3)C5—S2—C7—C632.4 (3)
C8—C1—C2—C343.9 (3)O1—C1—C8—C13149.8 (3)
C5—C2—C3—O221.0 (4)C2—C1—C8—C1324.2 (3)
C1—C2—C3—O2160.0 (2)O1—C1—C8—C924.3 (4)
C5—C2—C3—C4153.3 (2)C2—C1—C8—C9161.7 (2)
C1—C2—C3—C425.7 (3)C13—C8—C9—C100.6 (3)
C3—C2—C5—S1172.03 (19)C1—C8—C9—C10174.8 (2)
C1—C2—C5—S17.0 (3)C8—C9—C10—C111.4 (4)
C3—C2—C5—S28.2 (3)C9—C10—C11—C121.7 (4)
C1—C2—C5—S2172.79 (18)C10—C11—C12—C131.1 (4)
C6—S1—C5—C2165.4 (2)C9—C8—C13—C120.0 (3)
C6—S1—C5—S214.38 (17)C1—C8—C13—C12174.0 (2)
C7—S2—C5—C2172.7 (2)C11—C12—C13—C80.2 (4)
C7—S2—C5—S17.48 (18)

Experimental details

Crystal data
Chemical formulaC13H12O2S2
Mr264.35
Crystal system, space groupMonoclinic, P21
Temperature (K)298
a, b, c (Å)7.812 (3), 5.5115 (18), 14.628 (5)
β (°) 103.876 (4)
V3)611.4 (4)
Z2
Radiation typeMo Kα
µ (mm1)0.42
Crystal size (mm)0.14 × 0.10 × 0.01
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.956, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
3073, 1948, 1887
Rint0.015
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.073, 1.05
No. of reflections1948
No. of parameters154
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.24, 0.17
Absolute structureFlack (1983)
Absolute structure parameter0.01 (8)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

The authors are grateful to Professor Wan-Shen You and Guang-Ning Zhang for their generous help with this work.

References

First citationBruker (2005). APEX2 (Version 1.27) and SAINT (Version 7.12A). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChoi, E. B., Youn, I. K. & Pak, C. S. (1988). Synthesis, 7, 792–794.  CrossRef Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationLin, C., Yu, H. F., Liu, Q. & Hou, D. Y. (2005). Chin. J. Org. Chem. 25, 819–821.  CAS Google Scholar
First citationSheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhu, Z. M., Wang, Y., Xu, Y. T. & Mei, Z. M. (1996). Chin. Chem. Lett. 7, 95–96.  CAS Google Scholar
First citationZhu, Z. M., Wang, Y., Xu, Y. T. & Mei, Z. M. (1997). Chin. Chem. Lett. 8, 367–368.  CAS Google Scholar

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ISSN: 2056-9890
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