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

Zhang, L.-C.; Li, N.; Li, X.-H.; Huang, C.-Y.; Zhou, G.-H.

doi:10.1107/S160053680800264X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o534

doi:10.1107/S160053680800264X

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

Lan-Cui Zhang,^a ^* Na Li,^a Xiao-Hui Li,^a Cui-Ying Huang ^a and Guang-Hua Zhou ^a

^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 ); Lin et al. (2005 ); Zhu et al. (1996 , 1997 ).

Experimental

Crystal data

C₁₃H₁₂O₂S₂
M_r = 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 ) T_min = 0.956, T_max = 0.993
3073 measured reflections
1948 independent reflections
1887 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), with 741 Friedel pairs
Flack parameter: −0.01 (8)

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800264X/hg2371sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800264X/hg2371Isup2.hkl

checkCIF report

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. 1}H-NMR: 2.08(3H,s,CH₃), 3.43(4H,m, 2*SCH₂), 7.70(5H,m, ph)

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

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	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

C₁₃H₁₂O₂S₂	F(000) = 276
M_r = 264.35	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3425 reflections
a = 7.812 (3) Å	θ = 2.7–27.8°
b = 5.5115 (18) Å	µ = 0.42 mm⁻¹
c = 14.628 (5) Å	T = 298 K
β = 103.876 (4)°	Block, yellow
V = 611.4 (4) Å³	0.14 × 0.10 × 0.01 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1948 independent reflections
Radiation source: fine-focus sealed tube	1887 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→9
T_min = 0.956, T_max = 0.993	k = −6→6
3073 measured reflections	l = −17→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0405P)² + 0.1246P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1948 reflections	Δρ_max = 0.24 e Å⁻³
154 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (8)

Crystal data top

C₁₃H₁₂O₂S₂	V = 611.4 (4) Å³
M_r = 264.35	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 7.812 (3) Å	µ = 0.42 mm⁻¹
b = 5.5115 (18) Å	T = 298 K
c = 14.628 (5) Å	0.14 × 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)
T_min = 0.956, T_max = 0.993	R_int = 0.015
3073 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.073	Δρ_max = 0.24 e Å⁻³
S = 1.05	Δρ_min = −0.17 e Å⁻³
1948 reflections	Absolute structure: Flack (1983)
154 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
S1	0.45599 (7)	0.16653 (13)	0.16380 (4)	0.04320 (18)
S2	0.11323 (8)	0.39993 (14)	0.08953 (4)	0.04637 (18)
O1	0.4104 (2)	−0.2094 (4)	0.27828 (13)	0.0563 (5)
O2	−0.1208 (2)	0.2157 (4)	0.17817 (13)	0.0531 (5)
C1	0.2829 (3)	−0.1090 (5)	0.29623 (15)	0.0361 (5)
C2	0.1629 (3)	0.0454 (5)	0.22544 (15)	0.0342 (5)
C3	−0.0288 (3)	0.0456 (5)	0.21677 (16)	0.0377 (6)
C4	−0.1148 (3)	−0.1726 (6)	0.24704 (18)	0.0482 (7)
H4A	−0.2388	−0.1430	0.2380	0.072*
H4B	−0.0636	−0.2046	0.3124	0.072*
H4C	−0.0971	−0.3102	0.2101	0.072*
C5	0.2343 (3)	0.1860 (5)	0.16689 (14)	0.0348 (5)
C6	0.4601 (4)	0.4458 (6)	0.1000 (2)	0.0532 (7)
H6A	0.4788	0.5824	0.1431	0.064*
H6B	0.5552	0.4423	0.0679	0.064*
C7	0.2864 (4)	0.4705 (7)	0.0300 (2)	0.0614 (9)
H7A	0.2807	0.3597	−0.0222	0.074*
H7B	0.2720	0.6346	0.0055	0.074*
C8	0.2575 (3)	−0.1219 (5)	0.39431 (15)	0.0328 (5)
C9	0.3325 (3)	−0.3133 (5)	0.45259 (16)	0.0390 (5)
H9A	0.3892	−0.4378	0.4286	0.047*
C10	0.3233 (3)	−0.3194 (6)	0.54551 (17)	0.0459 (6)
H10A	0.3714	−0.4495	0.5836	0.055*
C11	0.2424 (3)	−0.1316 (6)	0.58230 (17)	0.0461 (7)
H11A	0.2390	−0.1337	0.6454	0.055*
C12	0.1671 (3)	0.0579 (6)	0.52532 (17)	0.0438 (6)
H12A	0.1111	0.1825	0.5497	0.053*
C13	0.1749 (3)	0.0631 (5)	0.43144 (16)	0.0368 (5)
H13A	0.1243	0.1917	0.3932	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0350 (3)	0.0536 (4)	0.0445 (3)	0.0025 (3)	0.0165 (2)	0.0021 (3)
S2	0.0403 (3)	0.0550 (4)	0.0434 (3)	0.0041 (3)	0.0093 (3)	0.0130 (3)
O1	0.0513 (11)	0.0737 (14)	0.0483 (10)	0.0252 (10)	0.0205 (8)	0.0065 (10)
O2	0.0350 (9)	0.0578 (14)	0.0650 (12)	0.0054 (9)	0.0091 (8)	0.0119 (10)
C1	0.0330 (11)	0.0399 (13)	0.0353 (12)	0.0004 (12)	0.0078 (9)	−0.0035 (12)
C2	0.0309 (11)	0.0423 (15)	0.0298 (11)	0.0007 (10)	0.0082 (9)	−0.0025 (11)
C3	0.0344 (12)	0.0467 (16)	0.0318 (11)	−0.0004 (11)	0.0073 (10)	−0.0018 (12)
C4	0.0393 (13)	0.059 (2)	0.0466 (14)	−0.0102 (12)	0.0099 (12)	0.0019 (13)
C5	0.0331 (11)	0.0413 (14)	0.0294 (10)	−0.0005 (11)	0.0066 (9)	−0.0056 (11)
C6	0.0499 (15)	0.058 (2)	0.0607 (16)	−0.0052 (13)	0.0302 (13)	−0.0006 (15)
C7	0.0612 (17)	0.077 (2)	0.0520 (16)	0.0039 (16)	0.0259 (14)	0.0197 (16)
C8	0.0279 (10)	0.0354 (13)	0.0341 (11)	−0.0003 (10)	0.0052 (8)	0.0013 (11)
C9	0.0346 (11)	0.0368 (14)	0.0460 (13)	0.0028 (12)	0.0103 (10)	0.0009 (12)
C10	0.0345 (11)	0.0525 (16)	0.0487 (13)	0.0018 (13)	0.0062 (10)	0.0188 (15)
C11	0.0402 (12)	0.0626 (19)	0.0346 (12)	−0.0066 (14)	0.0071 (10)	0.0035 (14)
C12	0.0490 (14)	0.0475 (16)	0.0358 (13)	0.0020 (12)	0.0117 (11)	−0.0068 (12)
C13	0.0384 (12)	0.0347 (13)	0.0352 (12)	0.0033 (10)	0.0050 (10)	0.0007 (10)

Geometric parameters (Å, º) top

S1—C5	1.746 (2)	C6—H6A	0.9700
S1—C6	1.804 (3)	C6—H6B	0.9700
S2—C5	1.747 (3)	C7—H7A	0.9700
S2—C7	1.817 (3)	C7—H7B	0.9700
O1—C1	1.221 (3)	C8—C13	1.385 (3)
O2—C3	1.233 (3)	C8—C9	1.394 (3)
C1—C2	1.487 (3)	C9—C10	1.378 (3)
C1—C8	1.496 (3)	C9—H9A	0.9300
C2—C5	1.369 (3)	C10—C11	1.387 (4)
C2—C3	1.472 (3)	C10—H10A	0.9300
C3—C4	1.495 (4)	C11—C12	1.377 (4)
C4—H4A	0.9600	C11—H11A	0.9300
C4—H4B	0.9600	C12—C13	1.389 (3)
C4—H4C	0.9600	C12—H12A	0.9300
C6—C7	1.497 (4)	C13—H13A	0.9300

C5—S1—C6	95.83 (12)	H6A—C6—H6B	108.5
C5—S2—C7	96.03 (13)	C6—C7—S2	108.04 (19)
O1—C1—C2	121.3 (2)	C6—C7—H7A	110.1
O1—C1—C8	119.2 (2)	S2—C7—H7A	110.1
C2—C1—C8	119.2 (2)	C6—C7—H7B	110.1
C5—C2—C3	120.3 (2)	S2—C7—H7B	110.1
C5—C2—C1	118.4 (2)	H7A—C7—H7B	108.4
C3—C2—C1	121.3 (2)	C13—C8—C9	119.0 (2)
O2—C3—C2	120.6 (2)	C13—C8—C1	121.5 (2)
O2—C3—C4	119.5 (2)	C9—C8—C1	119.3 (2)
C2—C3—C4	119.6 (2)	C10—C9—C8	120.5 (2)
C3—C4—H4A	109.5	C10—C9—H9A	119.7
C3—C4—H4B	109.5	C8—C9—H9A	119.7
H4A—C4—H4B	109.5	C9—C10—C11	120.1 (3)
C3—C4—H4C	109.5	C9—C10—H10A	120.0
H4A—C4—H4C	109.5	C11—C10—H10A	120.0
H4B—C4—H4C	109.5	C12—C11—C10	120.0 (2)
C2—C5—S1	122.47 (19)	C12—C11—H11A	120.0
C2—C5—S2	123.26 (17)	C10—C11—H11A	120.0
S1—C5—S2	114.27 (14)	C11—C12—C13	120.0 (3)
C7—C6—S1	107.8 (2)	C11—C12—H12A	120.0
C7—C6—H6A	110.1	C13—C12—H12A	120.0
S1—C6—H6A	110.1	C8—C13—C12	120.5 (2)
C7—C6—H6B	110.1	C8—C13—H13A	119.8
S1—C6—H6B	110.1	C12—C13—H13A	119.8

O1—C1—C2—C5	−36.8 (4)	C5—S1—C6—C7	−36.6 (2)
C8—C1—C2—C5	137.1 (2)	S1—C6—C7—S2	45.7 (3)
O1—C1—C2—C3	142.2 (3)	C5—S2—C7—C6	−32.4 (3)
C8—C1—C2—C3	−43.9 (3)	O1—C1—C8—C13	149.8 (3)
C5—C2—C3—O2	−21.0 (4)	C2—C1—C8—C13	−24.2 (3)
C1—C2—C3—O2	160.0 (2)	O1—C1—C8—C9	−24.3 (4)
C5—C2—C3—C4	153.3 (2)	C2—C1—C8—C9	161.7 (2)
C1—C2—C3—C4	−25.7 (3)	C13—C8—C9—C10	0.6 (3)
C3—C2—C5—S1	−172.03 (19)	C1—C8—C9—C10	174.8 (2)
C1—C2—C5—S1	7.0 (3)	C8—C9—C10—C11	−1.4 (4)
C3—C2—C5—S2	8.2 (3)	C9—C10—C11—C12	1.7 (4)
C1—C2—C5—S2	−172.79 (18)	C10—C11—C12—C13	−1.1 (4)
C6—S1—C5—C2	−165.4 (2)	C9—C8—C13—C12	0.0 (3)
C6—S1—C5—S2	14.38 (17)	C1—C8—C13—C12	−174.0 (2)
C7—S2—C5—C2	−172.7 (2)	C11—C12—C13—C8	0.2 (4)
C7—S2—C5—S1	7.48 (18)

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂O₂S₂
M_r	264.35
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	7.812 (3), 5.5115 (18), 14.628 (5)
β (°)	103.876 (4)
V (Å³)	611.4 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.14 × 0.10 × 0.01

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.956, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	3073, 1948, 1887
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.073, 1.05
No. of reflections	1948
No. of parameters	154
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.17
Absolute structure	Flack (1983)
Absolute structure parameter	−0.01 (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

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