6,6-Dimethyl-2H,5H,6H,7H-1,3-dithiolo[4,5-f][1,5,3]dithia­silepin-2-one

Li, H.; Zhang, X.; Zhang, Z.; Chen, Z.; Peng, J.

doi:10.1107/S1600536812011142

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1122

doi:10.1107/S1600536812011142

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6,6-Dimethyl-2H,5H,6H,7H-1,3-dithiolo[4,5-f][1,5,3]dithiasilepin-2-one

Hongqi Li,^a ^* Xuebin Zhang,^a Zhongbao Zhang,^a Zhen Chen ^a and Jiajian Peng ^b

^aKey Laboratory of Science & Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering & Biotechnology, Donghua University, Shanghai 201620, People's Republic of China, and ^bKey Laboratory of Organosilicon Chemistry and Material Technology of the Ministry of Education, Hangzhou Normal University, Hangzhou 310012, People's Republic of China
^*Correspondence e-mail: hongqili@dhu.edu.cn

(Received 28 February 2012; accepted 14 March 2012; online 21 March 2012)

In the structure of the title compound, C₇H₁₀OS₄Si, the carbonyl O atom lies in the plane of the five-membered dithiole ring with a deviation of only 0.022 (2) Å. The seven-membered ring adopts a chair conformation. The crystal packing is stabilized by S⋯O [3.096 (4) Å] and S⋯S [3.620 (4) Å] contacts, together with C—H⋯S interactions.

Related literature

For silicon-containing tetrathiafulvalene (TTF) derivatives as ligands, see: Guyon et al. (2005 ), and as precursors for the construction of polymetallic arrays, see: Hameau et al. (2008 ). For their use in the preparation of conducting charge-transfer complexes and radical-cation salts, see: Biaso et al. (2007 ). For the synthesis, see: Li et al. (2012 ). For related structures, see: Arumugam et al. (2011 ); Hou et al. (2009 ).

Experimental

Crystal data

C₇H₁₀OS₄Si
M_r = 266.48
Triclinic, $[P \overline 1]$
a = 6.148 (7) Å
b = 8.569 (10) Å
c = 11.846 (14) Å
α = 69.292 (12)°
β = 85.821 (13)°
γ = 83.129 (13)°
V = 579.2 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 296 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.901, T_max = 0.933
4000 measured reflections
2012 independent reflections
1628 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.072
S = 1.01
2012 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5B⋯S1ⁱ	0.97	2.89	3.673 (5)	138
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812011142/sj5206sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011142/sj5206Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812011142/sj5206Isup3.cml

checkCIF report

Comment top

Silicon-containing tetrathiafulvalene (TTF) derivatives have been synthesized and used as novel assembling ligands for the construction of bimetallic transition metal complexes (Guyon et al., 2005), as very promising precursors for the construction of polymetallic arrays (Hameau et al., 2008), or for the preparation of conducting charge transfer complexes and radical-cation salts (Biaso et al., 2007). 4,5-(2,2-Dimethyl-2-silapropylene)dithio-1,3-dithiole-2-one is useful in the synthesis of new silyl-substituted TTF derivatives. Its single crystal structure has not been reported yet, though crystal structures of analogous 1,3-dithiole-2-one and 1,3-dithiole-2-thione compounds have been studied (Arumugam et al., 2011; Hou et al., 2009). Herein we present the single crystal structure of the title compound.

In the title compound the carbonyl-oxygen atom (O1) lies in the plane of the five-membered dithiole ring (C1-C3/S1/S2/O1) with a deviation of only -0.022 (2)Å. The seven-membered ring adopts a chair conformation. Crystal packing is characterized by intermolecular S···O interaction with S1···O1 distance of 3.096 (4)Å and S···S contacts at 3.620 (4)Å. In addition, short intermolecular C—H···.S contacts are also observed (Table 1).

Related literature top

For silicon-containing tetrathiafulvalene (TTF) derivatives as ligands, see: Guyon et al. (2005), and as precursors for the construction of polymetallic arrays, see: Hameau et al. (2008). For their use in the preparation of conducting charge-transfer complexes and radical-cation salts, see: Biaso et al. (2007). For the synthesis, see: Li et al. (2012). For related structures, see: Arumugam et al. (2011); Hou et al. (2009).

Experimental top

The title compound was prepared as reported in the literature (Li et al., 2012). Single crystals suitable for X-ray diffraction measurement was obtained by slow evaporation from a solution of petroleum ether and ethyl acetate (1:1).

Structure description top

For silicon-containing tetrathiafulvalene (TTF) derivatives as ligands, see: Guyon et al. (2005), and as precursors for the construction of polymetallic arrays, see: Hameau et al. (2008). For their use in the preparation of conducting charge-transfer complexes and radical-cation salts, see: Biaso et al. (2007). For the synthesis, see: Li et al. (2012). For related structures, see: Arumugam et al. (2011); Hou et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. A view of the molecule of the title compound. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal structure of the title compound, viewed along a axis

6,6-Dimethyl-2H,5H,6H,7H-1,3- dithiolo[4,5-f][1,5,3]dithiasilepin-2-one top

Crystal data top

C₇H₁₀OS₄Si	Z = 2
M_r = 266.48	F(000) = 276
Triclinic, P1	D_x = 1.528 Mg m⁻³
Hall symbol: -P 1	Melting point = 325–326 K
a = 6.148 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.569 (10) Å	Cell parameters from 1863 reflections
c = 11.846 (14) Å	θ = 2.6–27.4°
α = 69.292 (12)°	µ = 0.88 mm⁻¹
β = 85.821 (13)°	T = 296 K
γ = 83.129 (13)°	Block, colorless
V = 579.2 (12) Å³	0.12 × 0.10 × 0.08 mm

Data collection top

Bruker APEXII CCD diffractometer	2012 independent reflections
Radiation source: fine-focus sealed tube	1628 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
φ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −7→7
T_min = 0.901, T_max = 0.933	k = −10→10
4000 measured reflections	l = −14→12

Refinement top

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.027P)² + 0.3021P] where P = (F_o² + 2F_c²)/3
2012 reflections	(Δ/σ)_max = 0.001
120 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₇H₁₀OS₄Si	γ = 83.129 (13)°
M_r = 266.48	V = 579.2 (12) Å³
Triclinic, P1	Z = 2
a = 6.148 (7) Å	Mo Kα radiation
b = 8.569 (10) Å	µ = 0.88 mm⁻¹
c = 11.846 (14) Å	T = 296 K
α = 69.292 (12)°	0.12 × 0.10 × 0.08 mm
β = 85.821 (13)°

Data collection top

Bruker APEXII CCD diffractometer	2012 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1628 reflections with I > 2σ(I)
T_min = 0.901, T_max = 0.933	R_int = 0.019
4000 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.01	Δρ_max = 0.25 e Å⁻³
2012 reflections	Δρ_min = −0.26 e Å⁻³
120 parameters

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
C1	1.2928 (4)	0.0788 (3)	0.3530 (2)	0.0504 (7)
C2	0.9211 (4)	0.2483 (3)	0.2614 (2)	0.0417 (6)
C3	0.9299 (4)	0.2691 (3)	0.3675 (2)	0.0406 (6)
C4	0.7687 (4)	0.5515 (3)	0.0965 (2)	0.0439 (6)
H4A	0.7085	0.6027	0.0167	0.053*
H4B	0.9260	0.5568	0.0873	0.053*
C5	0.7677 (4)	0.5943 (3)	0.3452 (2)	0.0476 (7)
H5A	0.9237	0.6060	0.3372	0.057*
H5B	0.7013	0.6636	0.3904	0.057*
C6	0.7323 (5)	0.8941 (3)	0.1163 (3)	0.0650 (8)
H6A	0.6818	0.9381	0.0351	0.097*
H6B	0.8890	0.8919	0.1147	0.097*
H6C	0.6672	0.9640	0.1601	0.097*
C7	0.3523 (4)	0.6708 (4)	0.2051 (3)	0.0597 (8)
H7A	0.2889	0.7372	0.2519	0.090*
H7B	0.3200	0.5568	0.2443	0.090*
H7C	0.2920	0.7145	0.1261	0.090*
O1	1.4633 (3)	−0.0091 (3)	0.37000 (19)	0.0718 (6)
S1	1.16208 (11)	0.17662 (9)	0.45212 (6)	0.0500 (2)
S2	1.14230 (12)	0.12822 (9)	0.22118 (7)	0.0539 (2)
S3	0.71611 (11)	0.33291 (8)	0.15538 (7)	0.0519 (2)
S4	0.72980 (11)	0.37770 (10)	0.43285 (6)	0.0561 (2)
Si1	0.65327 (11)	0.67844 (9)	0.19121 (7)	0.04113 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0479 (16)	0.0476 (16)	0.0509 (17)	0.0014 (13)	−0.0094 (13)	−0.0116 (13)
C2	0.0408 (14)	0.0361 (14)	0.0462 (15)	−0.0036 (11)	−0.0095 (11)	−0.0106 (12)
C3	0.0349 (13)	0.0416 (14)	0.0396 (14)	−0.0054 (11)	−0.0040 (11)	−0.0063 (12)
C4	0.0450 (15)	0.0410 (15)	0.0408 (15)	0.0001 (11)	−0.0060 (12)	−0.0085 (12)
C5	0.0355 (13)	0.0572 (17)	0.0579 (17)	−0.0006 (12)	0.0021 (12)	−0.0317 (14)
C6	0.0622 (19)	0.0425 (16)	0.087 (2)	−0.0083 (14)	0.0008 (17)	−0.0189 (16)
C7	0.0345 (14)	0.0643 (19)	0.078 (2)	0.0007 (13)	−0.0026 (14)	−0.0239 (17)
O1	0.0599 (13)	0.0760 (15)	0.0739 (15)	0.0266 (11)	−0.0219 (11)	−0.0261 (12)
S1	0.0450 (4)	0.0574 (4)	0.0450 (4)	0.0013 (3)	−0.0140 (3)	−0.0141 (3)
S2	0.0602 (4)	0.0494 (4)	0.0527 (4)	0.0113 (3)	−0.0155 (3)	−0.0214 (3)
S3	0.0549 (4)	0.0422 (4)	0.0610 (5)	−0.0007 (3)	−0.0273 (3)	−0.0176 (3)
S4	0.0457 (4)	0.0701 (5)	0.0429 (4)	0.0004 (3)	0.0075 (3)	−0.0114 (4)
Si1	0.0305 (3)	0.0406 (4)	0.0525 (4)	−0.0031 (3)	0.0015 (3)	−0.0171 (3)

Geometric parameters (Å, º) top

C1—O1	1.200 (3)	C5—S4	1.812 (3)
C1—S1	1.768 (3)	C5—Si1	1.865 (3)
C1—S2	1.767 (3)	C5—H5A	0.9700
C2—C3	1.336 (4)	C5—H5B	0.9700
C2—S2	1.747 (3)	C6—Si1	1.852 (3)
C2—S3	1.749 (3)	C6—H6A	0.9600
C3—S1	1.746 (3)	C6—H6B	0.9600
C3—S4	1.753 (3)	C6—H6C	0.9600
C4—S3	1.813 (3)	C7—Si1	1.853 (3)
C4—Si1	1.873 (3)	C7—H7A	0.9600
C4—H4A	0.9700	C7—H7B	0.9600
C4—H4B	0.9700	C7—H7C	0.9600

O1—C1—S1	125.6 (2)	Si1—C6—H6B	109.5
O1—C1—S2	122.9 (2)	H6A—C6—H6B	109.5
S1—C1—S2	111.47 (17)	Si1—C6—H6C	109.5
C3—C2—S2	116.77 (19)	H6A—C6—H6C	109.5
C3—C2—S3	127.3 (2)	H6B—C6—H6C	109.5
S2—C2—S3	115.90 (16)	Si1—C7—H7A	109.5
C2—C3—S1	117.2 (2)	Si1—C7—H7B	109.5
C2—C3—S4	126.9 (2)	H7A—C7—H7B	109.5
S1—C3—S4	115.92 (16)	Si1—C7—H7C	109.5
S3—C4—Si1	115.17 (15)	H7A—C7—H7C	109.5
S3—C4—H4A	108.5	H7B—C7—H7C	109.5
Si1—C4—H4A	108.5	C3—S1—C1	97.14 (15)
S3—C4—H4B	108.5	C2—S2—C1	97.32 (14)
Si1—C4—H4B	108.5	C2—S3—C4	100.85 (12)
H4A—C4—H4B	107.5	C3—S4—C5	102.02 (14)
S4—C5—Si1	116.21 (14)	C6—Si1—C7	112.72 (14)
S4—C5—H5A	108.2	C6—Si1—C5	107.85 (14)
Si1—C5—H5A	108.2	C7—Si1—C5	108.97 (14)
S4—C5—H5B	108.2	C6—Si1—C4	107.65 (15)
Si1—C5—H5B	108.2	C7—Si1—C4	107.94 (13)
H5A—C5—H5B	107.4	C5—Si1—C4	111.76 (14)
Si1—C6—H6A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···S1ⁱ	0.97	2.89	3.673 (5)	138

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₁₀OS₄Si
M_r	266.48
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.148 (7), 8.569 (10), 11.846 (14)
α, β, γ (°)	69.292 (12), 85.821 (13), 83.129 (13)
V (Å³)	579.2 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.901, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	4000, 2012, 1628
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.072, 1.01
No. of reflections	2012
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.26

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5B···S1ⁱ	0.97	2.89	3.673 (5)	138

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

Financial support of the project by the Fundamental Research Funds for the Central Universities is acknowledged.

References

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