Triclinic polymorph of dibenzotetra-thia-fulvalene.

Crystals of the title compound (DBTTF), C(14)H(8)S(4), feature a triclinic polymorph different from two known monoclinic polymorphs. In this form, there are two independent centrosymmetric half-mol-ecules in the asymmetric unit. Although the mol-ecular 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 = 304.46

Triclinic,

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 F 2 > 2σ(F 2)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.110

S = 1.12

2871 reflections

164 parameters

All H-atom parameters refined

Δρmax = 0.56 e Å−3

Δρmin = −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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C14H8S4	Z = 2
Mr = 304.46	F(000) = 312.00
Triclinic, P1	Dx = 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

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

Refinement on F2	All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.0363P)2 + 1.1654P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.110	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 0.56 e Å−3
2871 reflections	Δρmin = −0.46 e Å−3
164 parameters

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).

	x	y	z	Uiso*/Ueq
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*

	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)

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)