1,3-Dimethyl-5,6,7,8-tetra­hydro-4H-cyclo­hepta­[c]thio­phene-4,8-dione

Yu, L.; Yin, Y.; Zhou, X.; Li, R.; Peng, T.

doi:10.1107/S1600536810047331

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3231

https://doi.org/10.1107/S1600536810047331

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1,3-Dimethyl-5,6,7,8-tetrahydro-4H-cyclohepta[c]thiophene-4,8-dione

Lijuan Yu,^a Yinghui Yin,^a Xiaole Zhou,^a Renjie Li ^a ^* and Tianyou Peng ^a ^*

^aCollege of Chemistry and Molecular Science, Wuhan University, Wuhan 430072, People's Republic of China
^*Correspondence e-mail: lirj@whu.edu.cn,

(Received 8 November 2010; accepted 15 November 2010; online 20 November 2010)

In the title compound, C₁₁H₁₂O₂S, the C and S atoms of the central thiophene and the methyl groups, and the two carbonyl groups of the cycloheptanedione are almost coplanar [maximum deviation from the mean plane = 0.221 (2) Å]. The packing is stabilized by π–π interactions between the conjugated thiophenes, the shortest centroid–centroid distance between thiophene rings being 3.9759 (10) Å.

Related literature

The title compound was obtained as the product of our ongoing research of conjugated thiophenes for electronic devices and dye-sensitized solar cells (DSSCs). For applications of conjugated thiophenes, see: Amaresh et al. (2002 ); Nielsen & Bjonholm (2004 ). For related structures, see: Dufresne et al. (2007 ); Kuroda et al. (2005 ).

Experimental

Crystal data

C₁₁H₁₂O₂S
M_r = 208.27
Orthorhombic, P b c a
a = 15.9875 (6) Å
b = 7.6354 (3) Å
c = 16.9963 (6) Å
V = 2074.75 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.920, T_max = 0.951
15732 measured reflections
1822 independent reflections
1430 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.109
S = 1.02
1822 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810047331/vm2059sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810047331/vm2059Isup2.hkl

checkCIF report

Comment top

Since the sulfur atom can contribute to the peripheral conjugation either by two p-electron moieties with its lone pair electrons or by p-sulfurane type conjugation, conjugated thiophenes have received much attention because of many new possibilities for constructing devices displaying unique optical, electrical, and mechanical properties (Nielsen et al., 2004). Certain applications of conjugated thiophenes involve organic light emitting diodes and molecular wires, to be used in flexible light displays and/or low power consumption products (Amaresh et al., 2002). Here, we report the structure of a novel conjugated thiophenes.

The crystal structure of the title compound is given in Fig.1. The crystallographic analysis confirms that the title compound consists of a central thiophene capped by two methyl groups. The molecular symmetry can be described by point group C2. The cycloheptane ring shows a twisted boat conformation. The C—C bond lengths with each methyl are almost equal, with an average value of 1.506 (3) Å. Futhermore, π-π interactions stabilize the packing (Fig. 2). The closest centroid distance of approximate paraller thiophene rings is 3.9759 (10) Å.

Related literature top

The title compound, C₁₁H₁₂O₂S, was obtained as the product of our ongoing research of conjugated thiophenes for electronic devices and dye-sensitized solar cells (DSSCs) For applications of conjugated thiophenes, see: Amaresh et al. (2002); Nielsen et al. (2004). For related structures, see: Dufresne et al. (2007); Kuroda et al. (2005).

Experimental top

The title compound was prepared according to the literature (Kuroda et al., 2005), using diffusion of hexane into a toluene solution of the title compound at room temperature. ¹H NMR (CDCl₃, δ, p.p.m.): 2.45 (m, 4H), 2.32 (s, 6H), 1.93 (m, 2H). Analysis calculated (%): C 63.43, H 5.81; found (%): C 63.20, H 6.05.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: 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-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I) viewed along the b-direction.

1,3-Dimethyl-5,6,7,8-tetrahydro-4H-cyclohepta[c]thiophene- 4,8-dione top

Crystal data top

C₁₁H₁₂O₂S	F(000) = 880
M_r = 208.27	D_x = 1.333 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4563 reflections
a = 15.9875 (6) Å	θ = 2.4–22.2°
b = 7.6354 (3) Å	µ = 0.28 mm⁻¹
c = 16.9963 (6) Å	T = 298 K
V = 2074.75 (13) Å³	Block, yellow
Z = 8	0.30 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1822 independent reflections
Radiation source: fine-focus sealed tube	1430 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
phi and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −16→19
T_min = 0.920, T_max = 0.951	k = −9→8
15732 measured reflections	l = −20→20

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0555P)² + 0.5349P] where P = (F_o² + 2F_c²)/3
1822 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₁H₁₂O₂S	V = 2074.75 (13) Å³
M_r = 208.27	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.9875 (6) Å	µ = 0.28 mm⁻¹
b = 7.6354 (3) Å	T = 298 K
c = 16.9963 (6) Å	0.30 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1822 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1430 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.951	R_int = 0.034
15732 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.02	Δρ_max = 0.16 e Å⁻³
1822 reflections	Δρ_min = −0.29 e Å⁻³
129 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
S1	0.20027 (4)	0.11743 (8)	0.72032 (3)	0.0670 (2)
C2	0.35875 (12)	0.1124 (2)	0.70942 (10)	0.0496 (5)
C3	0.32681 (12)	0.1405 (2)	0.63092 (10)	0.0493 (5)
C1	0.29639 (14)	0.0980 (3)	0.76406 (11)	0.0575 (5)
C9	0.37901 (14)	0.1832 (3)	0.56162 (11)	0.0614 (5)
O2	0.35621 (12)	0.1474 (2)	0.49522 (8)	0.0898 (6)
C4	0.24140 (14)	0.1457 (2)	0.62814 (11)	0.0557 (5)
O1	0.47614 (12)	0.0907 (2)	0.79362 (10)	0.0882 (5)
C5	0.44794 (14)	0.0756 (3)	0.72741 (12)	0.0593 (5)
C6	0.50182 (13)	0.0112 (3)	0.66046 (14)	0.0688 (6)
H6A	0.4706	−0.0746	0.6303	0.083*
H6B	0.5508	−0.0467	0.6819	0.083*
C11	0.18386 (16)	0.1778 (3)	0.55955 (15)	0.0779 (7)
H11A	0.2030	0.2778	0.5305	0.117*
H11B	0.1282	0.1991	0.5785	0.117*
H11C	0.1836	0.0768	0.5259	0.117*
C10	0.30152 (17)	0.0610 (4)	0.85104 (12)	0.0842 (7)
H10A	0.3411	−0.0312	0.8602	0.126*
H10B	0.2475	0.0258	0.8700	0.126*
H10C	0.3192	0.1648	0.8782	0.126*
C8	0.45990 (15)	0.2776 (3)	0.57771 (14)	0.0766 (7)
H8A	0.4501	0.3667	0.6174	0.092*
H8B	0.4778	0.3364	0.5300	0.092*
C7	0.53003 (16)	0.1575 (3)	0.60577 (16)	0.0838 (7)
H7A	0.5568	0.1056	0.5601	0.101*
H7B	0.5716	0.2277	0.6328	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0548 (4)	0.0684 (4)	0.0779 (4)	0.0012 (3)	0.0116 (3)	−0.0081 (3)
C2	0.0545 (12)	0.0435 (10)	0.0509 (10)	0.0014 (8)	−0.0025 (8)	−0.0017 (8)
C3	0.0536 (12)	0.0423 (10)	0.0520 (10)	0.0016 (8)	−0.0011 (8)	−0.0048 (8)
C1	0.0666 (14)	0.0511 (12)	0.0549 (11)	0.0028 (9)	0.0053 (9)	−0.0034 (8)
C9	0.0753 (15)	0.0547 (12)	0.0542 (12)	0.0090 (11)	0.0068 (10)	0.0051 (9)
O2	0.1081 (14)	0.1103 (15)	0.0510 (9)	0.0094 (11)	0.0021 (8)	0.0020 (8)
C4	0.0569 (13)	0.0482 (11)	0.0620 (11)	0.0026 (9)	−0.0061 (9)	−0.0085 (8)
O1	0.0824 (12)	0.1029 (13)	0.0792 (11)	0.0074 (10)	−0.0269 (9)	0.0002 (9)
C5	0.0603 (13)	0.0496 (11)	0.0679 (12)	−0.0008 (10)	−0.0089 (10)	0.0025 (9)
C6	0.0524 (13)	0.0577 (13)	0.0962 (16)	0.0081 (10)	−0.0042 (11)	−0.0077 (11)
C11	0.0685 (15)	0.0810 (16)	0.0841 (16)	0.0095 (12)	−0.0247 (12)	−0.0115 (13)
C10	0.105 (2)	0.0922 (17)	0.0554 (13)	0.0103 (15)	0.0135 (12)	0.0038 (12)
C8	0.0785 (16)	0.0637 (14)	0.0875 (16)	−0.0077 (13)	0.0204 (13)	0.0109 (12)
C7	0.0628 (15)	0.0810 (17)	0.1076 (18)	−0.0070 (13)	0.0210 (14)	−0.0048 (14)

Geometric parameters (Å, º) top

S1—C4	1.713 (2)	C6—H6A	0.9700
S1—C1	1.714 (2)	C6—H6B	0.9700
C2—C1	1.367 (3)	C11—H11A	0.9600
C2—C3	1.445 (2)	C11—H11B	0.9600
C2—C5	1.485 (3)	C11—H11C	0.9600
C3—C4	1.367 (3)	C10—H10A	0.9600
C3—C9	1.480 (3)	C10—H10B	0.9600
C1—C10	1.507 (3)	C10—H10C	0.9600
C9—O2	1.217 (2)	C8—C7	1.525 (4)
C9—C8	1.506 (3)	C8—H8A	0.9700
C4—C11	1.505 (3)	C8—H8B	0.9700
O1—C5	1.218 (2)	C7—H7A	0.9700
C5—C6	1.509 (3)	C7—H7B	0.9700
C6—C7	1.521 (3)

C4—S1—C1	93.64 (10)	C4—C11—H11A	109.5
C1—C2—C3	112.43 (18)	C4—C11—H11B	109.5
C1—C2—C5	123.04 (18)	H11A—C11—H11B	109.5
C3—C2—C5	123.89 (17)	C4—C11—H11C	109.5
C4—C3—C2	112.91 (17)	H11A—C11—H11C	109.5
C4—C3—C9	121.98 (17)	H11B—C11—H11C	109.5
C2—C3—C9	124.64 (18)	C1—C10—H10A	109.5
C2—C1—C10	129.9 (2)	C1—C10—H10B	109.5
C2—C1—S1	110.63 (15)	H10A—C10—H10B	109.5
C10—C1—S1	119.38 (16)	C1—C10—H10C	109.5
O2—C9—C3	121.3 (2)	H10A—C10—H10C	109.5
O2—C9—C8	122.2 (2)	H10B—C10—H10C	109.5
C3—C9—C8	116.45 (18)	C9—C8—C7	113.58 (19)
C3—C4—C11	129.9 (2)	C9—C8—H8A	108.8
C3—C4—S1	110.39 (14)	C7—C8—H8A	108.8
C11—C4—S1	119.62 (18)	C9—C8—H8B	108.8
O1—C5—C2	121.9 (2)	C7—C8—H8B	108.8
O1—C5—C6	121.1 (2)	H8A—C8—H8B	107.7
C2—C5—C6	117.02 (17)	C6—C7—C8	114.50 (19)
C5—C6—C7	113.00 (18)	C6—C7—H7A	108.6
C5—C6—H6A	109.0	C8—C7—H7A	108.6
C7—C6—H6A	109.0	C6—C7—H7B	108.6
C5—C6—H6B	109.0	C8—C7—H7B	108.6
C7—C6—H6B	109.0	H7A—C7—H7B	107.6
H6A—C6—H6B	107.8

C1—C2—C3—C4	−0.3 (2)	C9—C3—C4—C11	5.3 (3)
C5—C2—C3—C4	170.75 (18)	C2—C3—C4—S1	0.23 (19)
C1—C2—C3—C9	171.89 (18)	C9—C3—C4—S1	−172.24 (14)
C5—C2—C3—C9	−17.0 (3)	C1—S1—C4—C3	−0.06 (15)
C3—C2—C1—C10	177.1 (2)	C1—S1—C4—C11	−177.88 (17)
C5—C2—C1—C10	5.9 (3)	C1—C2—C5—O1	−26.3 (3)
C3—C2—C1—S1	0.3 (2)	C3—C2—C5—O1	163.48 (19)
C5—C2—C1—S1	−170.90 (15)	C1—C2—C5—C6	151.22 (19)
C4—S1—C1—C2	−0.14 (16)	C3—C2—C5—C6	−19.0 (3)
C4—S1—C1—C10	−177.35 (18)	O1—C5—C6—C7	−103.5 (2)
C4—C3—C9—O2	−34.1 (3)	C2—C5—C6—C7	78.9 (2)
C2—C3—C9—O2	154.3 (2)	O2—C9—C8—C7	−102.1 (3)
C4—C3—C9—C8	144.01 (19)	C3—C9—C8—C7	79.8 (2)
C2—C3—C9—C8	−27.6 (3)	C5—C6—C7—C8	−49.7 (3)
C2—C3—C4—C11	177.76 (19)	C9—C8—C7—C6	−37.6 (3)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂O₂S
M_r	208.27
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	15.9875 (6), 7.6354 (3), 16.9963 (6)
V (Å³)	2074.75 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.30 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.920, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	15732, 1822, 1430
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.109, 1.02
No. of reflections	1822
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.29

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Acknowledgements

This work was supported by the NSFC, the SRFDP (20090141120052) and the Fundamental Research Funds for Central Universities (2082001).

References

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