Triclinic polymorph of dibenzotetra­thia­fulvalene

Mamada, M.; Yamashita, Y.

doi:10.1107/S1600536809030013

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2083

doi:10.1107/S1600536809030013

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Triclinic polymorph of dibenzotetrathiafulvalene

Masashi Mamada ^a and Yoshiro Yamashita ^a ^*

^aDepartment of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
^*Correspondence e-mail: yoshiro@echem.titech.ac.jp

(Received 24 July 2009; accepted 29 July 2009; online 8 August 2009)

Crystals of the title compound (DBTTF), C₁₄H₈S₄, feature a triclinic polymorph different from two known monoclinic polymorphs. In this form, there are two independent centrosymmetric half-molecules in the asymmetric unit. Although the molecular orientations are relatively similar to one of monoclinic polymorphs, the packing motif is different.

Related literature

For the synthesis, see: Nakayama et al. (1976 ). For the monoclinic polymorphs of DBTTF, see: Emge et al. (1982 ); Brillante et al. (2008 ). For the electronic properties of DBTTF, see: Jigami et al. (1998 ). For the characteristics of field-effect transistors based on DBTTF, see, for example: Mas-Torrent et al. (2005 ); Shibata et al. (2008 ). For related structures, see: Mas-Torrent et al. (2004 ); Naraso et al. (2006 ).

Experimental

Crystal data

C₁₄H₈S₄
M_r = 304.46
Triclinic, $[P \overline 1]$
a = 8.6562 (4) Å
b = 9.4144 (5) Å
c = 9.5144 (4) Å
α = 74.0424 (15)°
β = 63.6158 (13)°
γ = 65.5653 (14)°
V = 628.43 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 93 K
0.35 × 0.25 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.663, T_max = 0.896
6216 measured reflections
2871 independent reflections
2193 reflections with F² > 2σ(F²)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.110
S = 1.12
2871 reflections
164 parameters
All H-atom parameters refined
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2007 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030013/bt5019sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030013/bt5019Isup2.hkl

checkCIF report

Comment top

TTF and its derivatives have been well known as the most dominant electron donors (Jigami et al., 1998). Recently, some TTF derivatives have been used as organic semiconductors for organic field-effect transistors (OFETs) (Mas-Torrent et al., 2004; Naraso et al., 2006), which show high hole mobilities in both the single crystals and thin films. The title compound, dibenzotetrathiafulvalene (I), has also exhibited high mobility (Mas-Torrent et al., 2005; Shibata et al., 2008). Since the strong intermolecular interactions between the molecules are necessary for carrier transportation in organic conductors and semiconductors, the investigation of crystal structures are very important. The crystal structure of compound (I) has been reported as two monoclinic polymorphs, which are space group P2₁/c for α phase (Emge et al., 1982) and Cc for β phase (Brillante et al., 2008). These crystals were grown from solution and the existence of other two polymorphs has been found by means of lattice phonon confocal Raman microscopy and XRD. Herein, we report the single-crystal structure of compound (I) neither the α nor β phase.

The single-crystal of (I) which has been grown by vapour transport contains two crystallographically independent molecules with an inversion center. The molecules have chair-like structures which are slightly distorted from the molecular plane. The maximum deviations from the least-squares plane are 0.206 and 0.222 Å, and the average deviations are 0.085 and 0.111 Å. The molecular geometries in this phase are different from that in the α phase (average deviation: 0.037 Å) and similar to that in the β phase (maximum deviation: 0.235 Å, average deviation: 0.085 Å). The packing structure in this phase is a herringbone type with a tilt angle of 51.11° (Fig. 2), which is also similar to the β phase. However, the long axis is observed to be sliding and the number of intermolecular short contacts between the molecules is increased and the contact distances are shorter compared with the α and the β phase.

Related literature top

For the synthesis, see: Nakayama et al. (1976). For the monoclinic polymorphs of DBTTF, see: Emge et al. (1982); Brillante et al. (2008). For the electronic properties of DBTTF, see: Jigami et al. (1998). For the characteristics of field-effect transistors based on DBTTF, see, for example: Mas-Torrent et al. (2005); Shibata et al. (2008). For related structures, see: Mas-Torrent et al. (2004); Naraso et al. (2006).

Experimental top

To a stirred solution of 1,3-benzodithiolylium tetrafluoroborate (0.83 g, 3.5 mmol) in dichloromethane (30 ml) was added dropwise 1,8-diazabicyclo[5.4.0]undec-7-ene (1 ml) at room temperature. After being stirred for 4 h, the resulting precipitate was filtered, washed with dichloromethane and dried to give 0.30 g (58%) of the title compound. Yellow crystals of (I) suitable for X-ray analysis were obtained from slow vacuum sublimation in a gradient-temperature horizontal glass tube. A temperature of the source material was maintained at 480 K.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku, 2007).

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids. [symmetry codes: (i) 1 - x, 1 - y, 1 - z, (ii) -x, -y, 1 - z.]
	Fig. 2. A packing diagram for (I) viewed along the molecular long axis.

dibenzotetrathiafulvalene top

Crystal data top

C₁₄H₈S₄	Z = 2
M_r = 304.46	F(000) = 312.00
Triclinic, P1	D_x = 1.609 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 8.6562 (4) Å	Cell parameters from 4982 reflections
b = 9.4144 (5) Å	θ = 3.0–27.5°
c = 9.5144 (4) Å	µ = 0.73 mm⁻¹
α = 74.0424 (15)°	T = 93 K
β = 63.6158 (13)°	Platelet, yellow
γ = 65.5653 (14)°	0.35 × 0.25 × 0.15 mm
V = 628.43 (5) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2193 reflections with F² > 2σ(F²)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.028
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
T_min = 0.663, T_max = 0.896	k = −12→12
6216 measured reflections	l = −12→11
2871 independent reflections

Refinement top

Refinement on F²	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0363P)² + 1.1654P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max < 0.001
S = 1.12	Δρ_max = 0.56 e Å⁻³
2871 reflections	Δρ_min = −0.46 e Å⁻³
164 parameters

Crystal data top

C₁₄H₈S₄	γ = 65.5653 (14)°
M_r = 304.46	V = 628.43 (5) Å³
Triclinic, P1	Z = 2
a = 8.6562 (4) Å	Mo Kα radiation
b = 9.4144 (5) Å	µ = 0.73 mm⁻¹
c = 9.5144 (4) Å	T = 93 K
α = 74.0424 (15)°	0.35 × 0.25 × 0.15 mm
β = 63.6158 (13)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2871 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2193 reflections with F² > 2σ(F²)
T_min = 0.663, T_max = 0.896	R_int = 0.028
6216 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	164 parameters
wR(F²) = 0.110	All H-atom parameters refined
S = 1.12	Δρ_max = 0.56 e Å⁻³
2871 reflections	Δρ_min = −0.46 e Å⁻³

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S(1)	0.43963 (10)	0.53797 (9)	0.28891 (8)	0.01843 (17)
S(2)	0.60882 (10)	0.24998 (8)	0.46970 (9)	0.02064 (17)
S(3)	0.07081 (10)	0.20979 (9)	0.46015 (9)	0.01946 (17)
S(4)	−0.11044 (10)	0.02886 (9)	0.75183 (8)	0.01913 (17)
C(1)	0.5095 (3)	0.4558 (3)	0.4497 (3)	0.0156 (5)
C(2)	0.4701 (3)	0.3575 (3)	0.2425 (3)	0.0172 (5)
C(3)	0.5503 (3)	0.2223 (3)	0.3267 (3)	0.0193 (5)
C(4)	0.5830 (4)	0.0743 (3)	0.2954 (4)	0.0241 (6)
C(5)	0.5339 (4)	0.0630 (4)	0.1786 (4)	0.0297 (7)
C(6)	0.4545 (4)	0.1975 (4)	0.0947 (3)	0.0291 (7)
C(7)	0.4203 (4)	0.3460 (4)	0.1263 (3)	0.0232 (6)
C(8)	−0.0073 (3)	0.0491 (3)	0.5443 (3)	0.0161 (5)
C(9)	0.0398 (3)	0.2558 (3)	0.6390 (3)	0.0181 (5)
C(10)	−0.0446 (3)	0.1709 (3)	0.7768 (3)	0.0173 (5)
C(11)	−0.0710 (4)	0.1986 (3)	0.9235 (3)	0.0222 (6)
C(12)	−0.0092 (4)	0.3109 (4)	0.9306 (4)	0.0270 (7)
C(13)	0.0748 (4)	0.3954 (3)	0.7934 (4)	0.0265 (6)
C(14)	0.0984 (4)	0.3703 (3)	0.6477 (3)	0.0211 (6)
H(1)	0.6380	−0.0176	0.3526	0.029*
H(2)	0.5550	−0.0373	0.1565	0.036*
H(3)	0.4231	0.1883	0.0147	0.035*
H(4)	0.3641	0.4378	0.0697	0.028*
H(5)	−0.1302	0.1420	1.0174	0.027*
H(6)	−0.0247	0.3296	1.0299	0.032*
H(7)	0.1166	0.4713	0.7998	0.032*
H(8)	0.1536	0.4299	0.5544	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S(1)	0.0239 (3)	0.0176 (3)	0.0167 (3)	−0.0073 (2)	−0.0113 (2)	0.0003 (2)
S(2)	0.0255 (3)	0.0145 (3)	0.0260 (3)	−0.0040 (2)	−0.0158 (3)	−0.0021 (3)
S(3)	0.0250 (3)	0.0186 (3)	0.0157 (3)	−0.0117 (3)	−0.0055 (2)	−0.0000 (2)
S(4)	0.0247 (3)	0.0210 (3)	0.0144 (3)	−0.0139 (3)	−0.0053 (2)	0.0002 (2)
C(1)	0.0180 (13)	0.0138 (12)	0.0156 (12)	−0.0057 (11)	−0.0079 (10)	0.0008 (11)
C(2)	0.0152 (12)	0.0240 (14)	0.0145 (12)	−0.0101 (11)	−0.0017 (10)	−0.0065 (11)
C(3)	0.0177 (13)	0.0227 (14)	0.0187 (13)	−0.0077 (11)	−0.0043 (11)	−0.0069 (12)
C(4)	0.0185 (14)	0.0227 (15)	0.0308 (16)	−0.0098 (12)	−0.0042 (12)	−0.0068 (13)
C(5)	0.0276 (16)	0.0363 (18)	0.0293 (16)	−0.0187 (15)	−0.0003 (13)	−0.0150 (15)
C(6)	0.0311 (16)	0.048 (2)	0.0188 (14)	−0.0263 (16)	−0.0015 (13)	−0.0121 (15)
C(7)	0.0245 (15)	0.0366 (18)	0.0138 (13)	−0.0180 (14)	−0.0046 (11)	−0.0031 (13)
C(8)	0.0163 (12)	0.0164 (13)	0.0155 (12)	−0.0058 (11)	−0.0077 (10)	0.0017 (11)
C(9)	0.0156 (12)	0.0167 (13)	0.0223 (14)	−0.0043 (11)	−0.0079 (11)	−0.0032 (12)
C(10)	0.0164 (12)	0.0151 (13)	0.0192 (13)	−0.0036 (10)	−0.0058 (11)	−0.0046 (11)
C(11)	0.0209 (14)	0.0243 (15)	0.0194 (14)	−0.0075 (12)	−0.0046 (12)	−0.0049 (13)
C(12)	0.0293 (16)	0.0291 (17)	0.0252 (16)	−0.0077 (14)	−0.0083 (13)	−0.0135 (14)
C(13)	0.0271 (15)	0.0256 (16)	0.0305 (16)	−0.0112 (13)	−0.0073 (13)	−0.0109 (14)
C(14)	0.0193 (13)	0.0197 (14)	0.0253 (15)	−0.0101 (12)	−0.0061 (12)	−0.0024 (12)

Geometric parameters (Å, º) top

S(1)—C(1)	1.758 (3)	C(8)—C(8)ⁱⁱ	1.350 (5)
S(1)—C(2)	1.757 (3)	C(9)—C(10)	1.395 (3)
S(2)—C(1)	1.759 (2)	C(9)—C(14)	1.401 (5)
S(2)—C(3)	1.759 (4)	C(10)—C(11)	1.391 (5)
S(3)—C(8)	1.756 (3)	C(11)—C(12)	1.395 (6)
S(3)—C(9)	1.748 (3)	C(12)—C(13)	1.389 (4)
S(4)—C(8)	1.760 (2)	C(13)—C(14)	1.382 (5)
S(4)—C(10)	1.759 (4)	C(4)—H(1)	0.950
C(1)—C(1)ⁱ	1.349 (5)	C(5)—H(2)	0.950
C(2)—C(3)	1.395 (4)	C(6)—H(3)	0.950
C(2)—C(7)	1.396 (5)	C(7)—H(4)	0.950
C(3)—C(4)	1.391 (5)	C(11)—H(5)	0.950
C(4)—C(5)	1.396 (6)	C(12)—H(6)	0.950
C(5)—C(6)	1.388 (4)	C(13)—H(7)	0.950
C(6)—C(7)	1.393 (6)	C(14)—H(8)	0.950

S(1)···C(7)ⁱⁱⁱ	3.568 (3)	H(1)···C(9)^vi	2.782
S(1)···C(10)^iv	3.578 (2)	H(1)···C(10)^vi	2.985
S(2)···C(8)^v	3.359 (3)	H(1)···C(11)^vi	3.504
S(2)···C(8)^vi	3.407 (2)	H(1)···C(14)^vi	3.156
S(3)···C(6)	3.574 (2)	H(1)···H(1)^vi	2.754
C(1)···C(14)	3.527 (4)	H(1)···H(5)^x	3.260
C(4)···C(4)^vi	3.589 (4)	H(1)···H(8)^vi	3.583
C(4)···C(10)^vi	3.545 (3)	H(2)···S(2)^vi	3.552
C(6)···S(3)	3.574 (2)	H(2)···S(4)ⁱⁱ	3.518
C(7)···S(1)ⁱⁱⁱ	3.568 (3)	H(2)···C(6)^xi	3.202
C(7)···C(7)ⁱⁱⁱ	3.552 (5)	H(2)···C(12)^vi	3.561
C(8)···S(2)^vii	3.359 (3)	H(2)···H(2)^xi	3.329
C(8)···S(2)^vi	3.407 (2)	H(2)···H(3)^xi	2.341
C(10)···S(1)^iv	3.578 (2)	H(2)···H(5)^x	3.376
C(10)···C(4)^vi	3.545 (3)	H(3)···S(1)ⁱⁱⁱ	3.433
C(11)···C(11)^viii	3.523 (4)	H(3)···S(4)^x	3.590
C(14)···C(1)	3.527 (4)	H(3)···C(5)^xi	3.189
S(1)···H(3)ⁱⁱⁱ	3.433	H(3)···H(2)^xi	2.341
S(1)···H(4)ⁱⁱⁱ	3.053	H(3)···H(3)^xi	3.275
S(1)···H(7)ⁱ	3.515	H(3)···H(6)^xiii	3.486
S(1)···H(8)	2.942	H(4)···S(1)ⁱⁱⁱ	3.053
S(2)···H(1)^vi	3.291	H(4)···C(2)ⁱⁱⁱ	3.154
S(2)···H(2)^vi	3.552	H(4)···C(7)ⁱⁱⁱ	3.010
S(2)···H(8)	3.384	H(4)···C(11)^iv	3.309
S(3)···H(1)^vi	3.354	H(4)···C(12)^iv	3.004
S(3)···H(8)^iv	3.135	H(4)···C(13)^iv	3.223
S(4)···H(2)ⁱⁱ	3.518	H(4)···H(4)ⁱⁱⁱ	2.705
S(4)···H(3)^ix	3.590	H(4)···H(6)^iv	3.215
S(4)···H(5)^viii	3.332	H(4)···H(7)^iv	3.555
S(4)···H(6)^viii	3.480	H(5)···S(4)^viii	3.332
C(1)···H(7)	3.532	H(5)···C(2)^ix	3.267
C(1)···H(7)ⁱ	3.271	H(5)···C(3)^ix	3.024
C(1)···H(8)	2.881	H(5)···C(4)^ix	2.848
C(1)···H(8)ⁱ	3.484	H(5)···C(5)^ix	2.925
C(2)···H(4)ⁱⁱⁱ	3.154	H(5)···C(6)^ix	3.169
C(2)···H(5)^x	3.267	H(5)···C(7)^ix	3.351
C(2)···H(8)	3.019	H(5)···C(10)^viii	3.252
C(3)···H(1)^vi	3.259	H(5)···C(11)^viii	2.982
C(3)···H(5)^x	3.024	H(5)···H(1)^ix	3.260
C(3)···H(8)	3.235	H(5)···H(2)^ix	3.376
C(4)···H(1)^vi	3.055	H(5)···H(5)^viii	2.679
C(4)···H(5)^x	2.848	H(6)···S(4)^viii	3.480
C(5)···H(3)^xi	3.189	H(6)···C(13)^xii	3.245
C(5)···H(5)^x	2.925	H(6)···H(3)^xiv	3.486
C(6)···H(2)^xi	3.202	H(6)···H(4)^iv	3.215
C(6)···H(5)^x	3.169	H(6)···H(6)^xii	3.273
C(7)···H(4)ⁱⁱⁱ	3.010	H(6)···H(7)^xii	2.461
C(7)···H(5)^x	3.351	H(7)···S(1)ⁱ	3.515
C(9)···H(1)^vi	2.782	H(7)···C(1)	3.532
C(9)···H(8)^iv	3.254	H(7)···C(1)ⁱ	3.271
C(10)···H(1)^vi	2.985	H(7)···C(12)^xii	3.293
C(10)···H(5)^viii	3.252	H(7)···H(4)^iv	3.555
C(11)···H(1)^vi	3.504	H(7)···H(6)^xii	2.461
C(11)···H(4)^iv	3.309	H(7)···H(7)^xii	3.503
C(11)···H(5)^viii	2.982	H(8)···S(1)	2.942
C(12)···H(2)^vi	3.561	H(8)···S(2)	3.384
C(12)···H(4)^iv	3.004	H(8)···S(3)^iv	3.135
C(12)···H(7)^xii	3.293	H(8)···C(1)	2.881
C(13)···H(4)^iv	3.223	H(8)···C(1)ⁱ	3.484
C(13)···H(6)^xii	3.245	H(8)···C(2)	3.019
C(14)···H(1)^vi	3.156	H(8)···C(3)	3.235
C(14)···H(8)^iv	3.215	H(8)···C(9)^iv	3.254
H(1)···S(2)^vi	3.291	H(8)···C(14)^iv	3.215
H(1)···S(3)^vi	3.354	H(8)···H(1)^vi	3.583
H(1)···C(3)^vi	3.259	H(8)···H(8)^iv	2.946
H(1)···C(4)^vi	3.055

C(1)—S(1)—C(2)	95.02 (15)	S(4)—C(10)—C(9)	116.1 (2)
C(1)—S(2)—C(3)	95.06 (16)	S(4)—C(10)—C(11)	123.3 (2)
C(8)—S(3)—C(9)	95.27 (15)	C(9)—C(10)—C(11)	120.5 (3)
C(8)—S(4)—C(10)	95.27 (16)	C(10)—C(11)—C(12)	119.0 (2)
S(1)—C(1)—S(2)	115.5 (2)	C(11)—C(12)—C(13)	120.5 (3)
S(1)—C(1)—C(1)ⁱ	122.5 (2)	C(12)—C(13)—C(14)	120.7 (4)
S(2)—C(1)—C(1)ⁱ	122.0 (2)	C(9)—C(14)—C(13)	119.3 (2)
S(1)—C(2)—C(3)	116.8 (3)	C(3)—C(4)—H(1)	120.5
S(1)—C(2)—C(7)	122.9 (2)	C(5)—C(4)—H(1)	120.5
C(3)—C(2)—C(7)	120.3 (3)	C(4)—C(5)—H(2)	119.8
S(2)—C(3)—C(2)	116.6 (2)	C(6)—C(5)—H(2)	119.8
S(2)—C(3)—C(4)	122.8 (2)	C(5)—C(6)—H(3)	119.6
C(2)—C(3)—C(4)	120.6 (3)	C(7)—C(6)—H(3)	119.5
C(3)—C(4)—C(5)	119.0 (3)	C(2)—C(7)—H(4)	120.6
C(4)—C(5)—C(6)	120.3 (4)	C(6)—C(7)—H(4)	120.6
C(5)—C(6)—C(7)	120.9 (4)	C(10)—C(11)—H(5)	120.5
C(2)—C(7)—C(6)	118.8 (3)	C(12)—C(11)—H(5)	120.5
S(3)—C(8)—S(4)	115.1 (2)	C(11)—C(12)—H(6)	119.8
S(3)—C(8)—C(8)ⁱⁱ	122.2 (2)	C(13)—C(12)—H(6)	119.8
S(4)—C(8)—C(8)ⁱⁱ	122.6 (2)	C(12)—C(13)—H(7)	119.6
S(3)—C(9)—C(10)	117.1 (3)	C(14)—C(13)—H(7)	119.7
S(3)—C(9)—C(14)	122.9 (2)	C(9)—C(14)—H(8)	120.4
C(10)—C(9)—C(14)	120.0 (3)	C(13)—C(14)—H(8)	120.4

C(1)—S(1)—C(2)—C(3)	−6.4 (2)	C(3)—C(2)—C(7)—C(6)	−0.9 (4)
C(1)—S(1)—C(2)—C(7)	174.5 (2)	C(7)—C(2)—C(3)—S(2)	179.7 (2)
C(2)—S(1)—C(1)—S(2)	10.26 (18)	C(7)—C(2)—C(3)—C(4)	0.5 (4)
C(2)—S(1)—C(1)—C(1)ⁱ	−170.5 (2)	S(2)—C(3)—C(4)—C(5)	−179.3 (2)
C(1)—S(2)—C(3)—C(2)	5.7 (2)	C(2)—C(3)—C(4)—C(5)	−0.2 (4)
C(1)—S(2)—C(3)—C(4)	−175.2 (2)	C(3)—C(4)—C(5)—C(6)	0.3 (4)
C(3)—S(2)—C(1)—S(1)	−10.05 (18)	C(4)—C(5)—C(6)—C(7)	−0.8 (4)
C(3)—S(2)—C(1)—C(1)ⁱ	170.7 (2)	C(5)—C(6)—C(7)—C(2)	1.0 (4)
C(8)—S(3)—C(9)—C(10)	−5.7 (2)	S(3)—C(8)—C(8)ⁱⁱ—S(4)ⁱⁱ	1.6 (3)
C(8)—S(3)—C(9)—C(14)	173.1 (2)	S(4)—C(8)—C(8)ⁱⁱ—S(3)ⁱⁱ	−1.6 (3)
C(9)—S(3)—C(8)—S(4)	10.05 (18)	S(3)—C(9)—C(10)—S(4)	−0.5 (2)
C(9)—S(3)—C(8)—C(8)ⁱⁱ	−171.4 (2)	S(3)—C(9)—C(10)—C(11)	178.8 (2)
C(8)—S(4)—C(10)—C(9)	6.4 (2)	S(3)—C(9)—C(14)—C(13)	−177.6 (2)
C(8)—S(4)—C(10)—C(11)	−172.8 (2)	C(10)—C(9)—C(14)—C(13)	1.3 (4)
C(10)—S(4)—C(8)—S(3)	−10.26 (18)	C(14)—C(9)—C(10)—S(4)	−179.4 (2)
C(10)—S(4)—C(8)—C(8)ⁱⁱ	171.2 (2)	C(14)—C(9)—C(10)—C(11)	−0.1 (3)
S(1)—C(1)—C(1)ⁱ—S(2)ⁱ	0.8 (3)	S(4)—C(10)—C(11)—C(12)	178.2 (2)
S(2)—C(1)—C(1)ⁱ—S(1)ⁱ	−0.8 (3)	C(9)—C(10)—C(11)—C(12)	−1.0 (4)
S(1)—C(2)—C(3)—S(2)	0.5 (2)	C(10)—C(11)—C(12)—C(13)	1.0 (4)
S(1)—C(2)—C(3)—C(4)	−178.7 (2)	C(11)—C(12)—C(13)—C(14)	0.2 (3)
S(1)—C(2)—C(7)—C(6)	178.2 (2)	C(12)—C(13)—C(14)—C(9)	−1.3 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z; (iv) −x, −y+1, −z+1; (v) x+1, y, z; (vi) −x+1, −y, −z+1; (vii) x−1, y, z; (viii) −x, −y, −z+2; (ix) x−1, y, z+1; (x) x+1, y, z−1; (xi) −x+1, −y, −z; (xii) −x, −y+1, −z+2; (xiii) x, y, z−1; (xiv) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₈S₄
M_r	304.46
Crystal system, space group	Triclinic, P1
Temperature (K)	93
a, b, c (Å)	8.6562 (4), 9.4144 (5), 9.5144 (4)
α, β, γ (°)	74.0424 (15), 63.6158 (13), 65.5653 (14)
V (Å³)	628.43 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.663, 0.896
No. of measured, independent and observed [F² > 2σ(F²)] reflections	6216, 2871, 2193
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.110, 1.12
No. of reflections	2871
No. of parameters	164
No. of restraints	?
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.46

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), CrystalStructure (Rigaku, 2007).

Selected geometric parameters (Å, º) top

S(1)—C(1)	1.758 (3)	C(3)—C(4)	1.391 (5)
S(1)—C(2)	1.757 (3)	C(4)—C(5)	1.396 (6)
S(2)—C(1)	1.759 (2)	C(5)—C(6)	1.388 (4)
S(2)—C(3)	1.759 (4)	C(6)—C(7)	1.393 (6)
S(3)—C(8)	1.756 (3)	C(8)—C(8)ⁱⁱ	1.350 (5)
S(3)—C(9)	1.748 (3)	C(9)—C(10)	1.395 (3)
S(4)—C(8)	1.760 (2)	C(9)—C(14)	1.401 (5)
S(4)—C(10)	1.759 (4)	C(10)—C(11)	1.391 (5)
C(1)—C(1)ⁱ	1.349 (5)	C(11)—C(12)	1.395 (6)
C(2)—C(3)	1.395 (4)	C(12)—C(13)	1.389 (4)
C(2)—C(7)	1.396 (5)	C(13)—C(14)	1.382 (5)

C(1)—S(1)—C(2)	95.02 (15)	C(5)—C(6)—C(7)	120.9 (4)
C(1)—S(2)—C(3)	95.06 (16)	C(2)—C(7)—C(6)	118.8 (3)
C(8)—S(3)—C(9)	95.27 (15)	S(3)—C(8)—S(4)	115.1 (2)
C(8)—S(4)—C(10)	95.27 (16)	S(3)—C(8)—C(8)ⁱⁱ	122.2 (2)
S(1)—C(1)—S(2)	115.5 (2)	S(4)—C(8)—C(8)ⁱⁱ	122.6 (2)
S(1)—C(1)—C(1)ⁱ	122.5 (2)	S(3)—C(9)—C(10)	117.1 (3)
S(2)—C(1)—C(1)ⁱ	122.0 (2)	S(3)—C(9)—C(14)	122.9 (2)
S(1)—C(2)—C(3)	116.8 (3)	C(10)—C(9)—C(14)	120.0 (3)
S(1)—C(2)—C(7)	122.9 (2)	S(4)—C(10)—C(9)	116.1 (2)
C(3)—C(2)—C(7)	120.3 (3)	S(4)—C(10)—C(11)	123.3 (2)
S(2)—C(3)—C(2)	116.6 (2)	C(9)—C(10)—C(11)	120.5 (3)
S(2)—C(3)—C(4)	122.8 (2)	C(10)—C(11)—C(12)	119.0 (2)
C(2)—C(3)—C(4)	120.6 (3)	C(11)—C(12)—C(13)	120.5 (3)
C(3)—C(4)—C(5)	119.0 (3)	C(12)—C(13)—C(14)	120.7 (4)
C(4)—C(5)—C(6)	120.3 (4)	C(9)—C(14)—C(13)	119.3 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z+1.

Acknowledgements

This work was supported by a Grant-in-Aid for Scientific Research (No. 19350092) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, the Mizuho Foundation for the Promotion of Sciences, the Global COE program `Education and Research Center for Emergence of New Molecular Chemistry' and the Research Fellows of the Japan Society for the Promotion of Science.

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