2-(1,3-Di-thiol-2-yl-idene)-1,3-di-thiole-4-carbaldehyde.

The structure of the title compound, C7H4OS4, at 100 K has ortho-rhom-bic symmetry. In the crystal, tetra-thia-fulvalene mol-ecules form π-stacks along the a axis, with a stacking distance of 3.4736 (6) Å. Along the b axis, parallel stacks are inter-connected with each other through a network of weak C-H⋯O hydrogen bonds and short S⋯S contacts [3.4813 (7) Å]. Additional short S⋯S contacts [3.4980 (9) Å] join parallel stacks along the c axis.

Related literature

For tetra­thia­fulvalene derivatives and their applications, see: Yamada & Sugimoto (2004 ▶); Segura & Martín (2001 ▶). For a review on synthetic chemistry of tetra­thia­fulvalenes, see: Fabre (2004 ▶). For a previous synthesis of the title compound, see: Garín et al. (1994 ▶). For reviews on ‘weak’ non-classical hydrogen bonding, see: Steiner (2002 ▶); Desiraju (2005 ▶). For reviews on halogen–halogen contacts, see: Metrangolo et al. (2008 ▶).

Experimental

Crystal data

C7H4OS4

M = 232.34

Orthorhombic,

a = 3.8466 (3) Å

b = 7.4052 (7) Å

c = 30.577 (3) Å

V = 870.99 (13) Å3

Z = 4

Mo Kα radiation

μ = 1.03 mm−1

T = 100 K

0.50 × 0.21 × 0.13 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2012 ▶) T min = 0.675, T max = 0.746

6998 measured reflections

2734 independent reflections

2663 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.057

S = 1.13

2734 reflections

109 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.25 e Å−3

Absolute structure: Flack x determined using 985 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004 ▶), 1024 Friedel pairs

Flack parameter: 0.01 (4)

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013 ▶) and SHELXLE (Hübschle et al., 2011 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶) and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681301711X/pk2488sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681301711X/pk2488Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681301711X/pk2488Isup3.cml

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

C7H4OS4	Dx = 1.772 Mg m−3
Mr = 232.34	Melting point: 383 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
a = 3.8466 (3) Å	Cell parameters from 4789 reflections
b = 7.4052 (7) Å	θ = 2.8–31.4°
c = 30.577 (3) Å	µ = 1.03 mm−1
V = 870.99 (13) Å3	T = 100 K
Z = 4	Plate, red
F(000) = 472	0.50 × 0.21 × 0.13 mm

Bruker SMART APEX CCD diffractometer	2663 reflections with I > 2σ(I)
Radiation source: fine focus sealed tube	Rint = 0.015
ω and φ scans	θmax = 31.9°, θmin = 1.3°
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2012)	h = −5→5
Tmin = 0.675, Tmax = 0.746	k = −10→10
6998 measured reflections	l = −42→44
2734 independent reflections

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)] = 0.024	H-atom parameters constrained
wR(F2) = 0.057	w = 1/[σ2(Fo2) + (0.0237P)2 + 0.4121P] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max < 0.001
2734 reflections	Δρmax = 0.45 e Å−3
109 parameters	Δρmin = −0.25 e Å−3
0 restraints	Absolute structure: Flack x determined using 985 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004), 1024 Friedel pairs.
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (4)

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.

	x	y	z	Uiso*/Ueq
C1	0.1960 (6)	0.3626 (3)	0.24133 (7)	0.0229 (4)
H1	0.0987	0.4745	0.2504	0.027*
C2	0.3148 (6)	0.3446 (3)	0.19636 (7)	0.0178 (4)
C3	0.3234 (6)	0.4823 (3)	0.16743 (7)	0.0188 (4)
H3	0.2417	0.5992	0.1751	0.023*
C4	0.5823 (5)	0.2086 (3)	0.12667 (7)	0.0154 (4)
C5	0.7332 (5)	0.1004 (3)	0.09665 (7)	0.0154 (4)
C6	0.9971 (6)	−0.1700 (3)	0.05523 (7)	0.0213 (4)
H6	1.0784	−0.2866	0.0473	0.026*
C7	1.0078 (7)	−0.0331 (3)	0.02682 (7)	0.0213 (4)
H7	1.0959	−0.0492	−0.0019	0.026*
O1	0.2158 (5)	0.2405 (2)	0.26790 (5)	0.0275 (4)
S1	0.47171 (14)	0.13395 (6)	0.17941 (2)	0.01732 (10)
S2	0.48840 (15)	0.43791 (6)	0.11609 (2)	0.01750 (10)
S3	0.85438 (14)	0.17653 (7)	0.04434 (2)	0.01774 (11)
S4	0.82962 (14)	−0.12822 (7)	0.10718 (2)	0.01786 (11)

	U11	U22	U33	U12	U13	U23
C1	0.0258 (11)	0.0227 (9)	0.0202 (10)	0.0009 (9)	−0.0027 (8)	−0.0048 (8)
C2	0.0168 (9)	0.0174 (9)	0.0190 (9)	0.0009 (8)	−0.0026 (7)	−0.0033 (7)
C3	0.0204 (10)	0.0154 (8)	0.0206 (10)	0.0022 (8)	−0.0014 (9)	−0.0033 (7)
C4	0.0151 (9)	0.0134 (8)	0.0177 (9)	−0.0006 (6)	−0.0023 (7)	0.0024 (6)
C5	0.0150 (9)	0.0132 (8)	0.0180 (9)	−0.0011 (6)	−0.0020 (7)	0.0027 (7)
C6	0.0193 (9)	0.0186 (9)	0.0260 (10)	0.0023 (9)	−0.0008 (9)	−0.0069 (7)
C7	0.0201 (10)	0.0217 (9)	0.0221 (10)	0.0006 (9)	0.0005 (9)	−0.0056 (7)
O1	0.0359 (10)	0.0274 (8)	0.0192 (7)	−0.0016 (8)	−0.0012 (7)	−0.0002 (6)
S1	0.0208 (2)	0.01368 (19)	0.0175 (2)	0.00034 (19)	0.00125 (19)	0.00193 (17)
S2	0.0205 (2)	0.01230 (18)	0.0197 (2)	0.00120 (19)	−0.0006 (2)	0.00242 (16)
S3	0.0183 (2)	0.0181 (2)	0.0169 (2)	0.00035 (19)	0.00033 (19)	0.00149 (17)
S4	0.0192 (2)	0.01267 (19)	0.0217 (2)	0.00182 (19)	−0.00120 (19)	0.00094 (17)

C1—O1	1.218 (3)	C4—S2	1.7661 (19)
C1—C2	1.455 (3)	C5—S3	1.759 (2)
C1—H1	0.9500	C5—S4	1.763 (2)
C2—C3	1.350 (3)	C6—C7	1.336 (3)
C2—S1	1.751 (2)	C6—S4	1.742 (2)
C3—S2	1.725 (2)	C6—H6	0.9500
C3—H3	0.9500	C7—S3	1.745 (2)
C4—C5	1.349 (3)	C7—H7	0.9500
C4—S1	1.757 (2)
O1—C1—C2	122.9 (2)	C4—C5—S4	122.44 (15)
O1—C1—H1	118.6	S3—C5—S4	114.71 (12)
C2—C1—H1	118.6	C7—C6—S4	118.03 (16)
C3—C2—C1	123.9 (2)	C7—C6—H6	121.0
C3—C2—S1	118.05 (16)	S4—C6—H6	121.0
C1—C2—S1	118.02 (16)	C6—C7—S3	117.70 (17)
C2—C3—S2	117.48 (16)	C6—C7—H7	121.1
C2—C3—H3	121.3	S3—C7—H7	121.1
S2—C3—H3	121.3	C2—S1—C4	94.30 (10)
C5—C4—S1	122.80 (15)	C3—S2—C4	95.26 (10)
C5—C4—S2	122.29 (15)	C7—S3—C5	94.82 (10)
S1—C4—S2	114.90 (11)	C6—S4—C5	94.69 (10)
C4—C5—S3	122.85 (15)
O1—C1—C2—C3	−174.0 (2)	C5—C4—S1—C2	178.23 (18)
O1—C1—C2—S1	3.4 (3)	S2—C4—S1—C2	−0.66 (13)
C1—C2—C3—S2	177.51 (17)	C2—C3—S2—C4	−0.5 (2)
S1—C2—C3—S2	0.1 (3)	C5—C4—S2—C3	−178.19 (18)
S1—C4—C5—S3	−178.29 (12)	S1—C4—S2—C3	0.71 (13)
S2—C4—C5—S3	0.5 (3)	C6—C7—S3—C5	−1.6 (2)
S1—C4—C5—S4	0.8 (3)	C4—C5—S3—C7	−178.51 (18)
S2—C4—C5—S4	179.63 (12)	S4—C5—S3—C7	2.32 (14)
S4—C6—C7—S3	0.3 (3)	C7—C6—S4—C5	1.2 (2)
C3—C2—S1—C4	0.3 (2)	C4—C5—S4—C6	178.61 (18)
C1—C2—S1—C4	−177.22 (18)	S3—C5—S4—C6	−2.21 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1i	0.95	2.38	3.228 (3)	149
C3—H3···O1i	0.95	2.69	3.445 (3)	137

System S···S	S···S	Symmetry code
S3···S3ii	3.4980 (9)	(ii) -1/2+x, 1/2-y, -z
S3···S3iii	3.4980 (9)	(iii) 1/2+x, 1/2-y, -z
S2···S4iv	3.4813 (7)	(iv) x, 1+y, z

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1i	0.95	2.38	3.228 (3)	149
C3—H3⋯O1i	0.95	2.69	3.445 (3)	137

Symmetry code: (i) .