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The title compound, C7H6S5, contains a 5-yl­idene-1,3-dithiolo[4,5-d][1,3]dithiole-2-thione framework, which is an important synthetic precursor of multi-dimensional organic superconductors and conductors. The mol­ecular framework is planar with an r.m.s. deviation of 0.012 Å for the non-H atoms. In the crystal structure, mol­ecules are linked by short inter­molecular S...S inter­actions [3.501 (5) and 3.581 (4) Å], constructing a zigzag mol­ecular tape network along the c axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680901335X/hg2498sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680901335X/hg2498Isup2.hkl
Contains datablock I

CCDC reference: 731281

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](C-C) = 0.011 Å
  • R factor = 0.072
  • wR factor = 0.246
  • Data-to-parameter ratio = 23.6

checkCIF/PLATON results

No syntax errors found



Alert level A REFLT03_ALERT_3_A Reflection count < 85% complete (theta max?) From the CIF: _diffrn_reflns_theta_max 31.11 From the CIF: _diffrn_reflns_theta_full 31.11 From the CIF: _reflns_number_total 2643 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3236 Completeness (_total/calc) 81.67%
Author Response: Extremely small crystal dimensions (0.09 x 0.02 x 0.01 mm3) caused these problems. We used a CCD X-ray diffractometer equipped with confocal mirror optics, however, these values could not be improved in spite of the long-time exposure.
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.82
Author Response: Extremely small crystal dimensions (0.09 x 0.02 x 0.01 mm3) caused these problems. We used a CCD X-ray diffractometer equipped with confocal mirror optics, however, these values could not be improved in spite of the long-time exposure.

Alert level B PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 30 Perc. PLAT340_ALERT_3_B Low Bond Precision on C-C Bonds (x 1000) Ang ... 11 PLAT031_ALERT_4_B Refined Extinction Parameter within Range ...... 1.00 Sigma
Alert level C Value of measurement temperature given = 291.000 Value of melting point given = 0.000 PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C6
2 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Molecules containing an 5-ylidene-[1,3]dithiolo[4,5-d][1,3]dithiole-2-thione framework are important synthetic precursors of multi-dimensional organic superconductors and conductors. Intermolecular S···S interactions involving peripheral sulfir atoms may increase the dimensionality in solid states and suppress metal-insulator transitions (Williams et al., 1992; Ishiguro et al., 1998). A search for the molecular framework in the Cambridge Structural Database (Version 5.30; Allen, 2002) gave only three examples (Bryce et al., 2000; Hock et al., 2002; Beck et al., 2006). Thus, we report here the molecular and crystal structures of the title compound (I).

The compound (I) crystallizes in the P1 space group with one molecule in the asymmetric unit. The molecular structure is shown in Fig. 1. The bond lengths are within the normal ranges (Allen et al., 1987). The molecular framework is planar with an r.m.s. deviation of 0.012 Å from the least-squares plane. In the crystal structure, the molecules are linked via short intermolecular S···S interactions [3.581 (4) for S1—S1(-x, -y + 3, -z) and 3.501 (5) Å for S5—S5(-x, -y + 3, -z - 1)] to construct a zigzag molecular tape network along the c axis (Fig. 2). The S···S interactions are 0.5–2.8% shorter than the sum of the corresponding van der Waals radii (Bondi, 1964). The molecules also form a π-stacking along the a axis with an interplanar distance of 3.54 (1) Å.

Related literature top

For general background, see: Williams et al. (1992); Ishiguro et al. (1998). For the synthesis of the title compound, see: Misaki et al. (1992). For related structures with a 5-ylidene-[1,3]dithiolo[4,5-d][1,3]dithiole-2-thione framework, see: Bryce et al. (2000); Hock et al. (2002); Beck et al. (2006). For bond-length data, see: Allen et al. (1987). For values of van der Waals radii, see: Bondi (1964). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The title compound (I) was synthesized according to the literature method (Misaki et al., 1992). Brown crystals of (I) suitable for X-ray analysis were grown from a dichloromethane solution.

Refinement top

All H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: TEXSAN (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing diagram of (I), viewed along the b axis. Dashed lines indicate intermolecular S···S interactions.
5-Isopropylidene-1,3-dithiolo[4,5-d][1,3]dithiole-2-thione top
Crystal data top
C7H6S5Z = 2
Mr = 250.47F(000) = 256
Triclinic, P1Dx = 1.654 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71070 Å
a = 7.082 (6) ÅCell parameters from 843 reflections
b = 7.126 (6) Åθ = 3.0–29.7°
c = 10.534 (10) ŵ = 1.09 mm1
α = 86.12 (3)°T = 291 K
β = 84.77 (3)°Needle, brown
γ = 71.95 (2)°0.09 × 0.02 × 0.01 mm
V = 502.9 (8) Å3
Data collection top
Rigaku/MSC Mercury CCD
diffractometer
785 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.117
Confocal monochromatorθmax = 31.1°, θmin = 3.0°
Detector resolution: 14.63 pixels mm-1h = 99
ϕ and ω scansk = 1010
4550 measured reflectionsl = 1015
2643 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.072H-atom parameters constrained
wR(F2) = 0.246 w = 1/[σ2(Fo2) + (0.0747P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.84(Δ/σ)max < 0.001
2643 reflectionsΔρmax = 0.46 e Å3
112 parametersΔρmin = 0.50 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.003 (3)
Crystal data top
C7H6S5γ = 71.95 (2)°
Mr = 250.47V = 502.9 (8) Å3
Triclinic, P1Z = 2
a = 7.082 (6) ÅMo Kα radiation
b = 7.126 (6) ŵ = 1.09 mm1
c = 10.534 (10) ÅT = 291 K
α = 86.12 (3)°0.09 × 0.02 × 0.01 mm
β = 84.77 (3)°
Data collection top
Rigaku/MSC Mercury CCD
diffractometer
785 reflections with I > 2σ(I)
4550 measured reflectionsRint = 0.117
2643 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0720 restraints
wR(F2) = 0.246H-atom parameters constrained
S = 0.84Δρmax = 0.46 e Å3
2643 reflectionsΔρmin = 0.50 e Å3
112 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
xyzUiso*/Ueq
S10.1573 (3)1.3556 (3)0.12379 (19)0.0502 (6)
S20.2864 (3)0.9827 (3)0.25144 (18)0.0496 (6)
S30.1902 (3)1.1364 (3)0.13884 (18)0.0452 (6)
S40.3259 (3)0.7524 (3)0.00739 (18)0.0434 (6)
S50.1908 (4)1.3598 (4)0.4066 (2)0.0710 (9)
C10.2089 (11)1.2401 (12)0.2662 (7)0.048 (2)
C20.2080 (10)1.1425 (11)0.0257 (7)0.0427 (19)
C30.2706 (10)0.8745 (11)0.1547 (7)0.0407 (18)
C40.2678 (9)0.9729 (12)0.0871 (7)0.0385 (17)
C50.2896 (10)0.7741 (12)0.2681 (8)0.045 (2)
C60.2430 (11)0.8811 (12)0.3900 (7)0.056 (2)
H6A0.36020.84720.43650.084*
H6B0.13950.84390.44050.084*
H6C0.19941.02100.37110.084*
C70.3596 (11)0.5529 (11)0.2761 (7)0.049 (2)
H7A0.38180.50360.19170.073*
H7B0.26030.50560.32390.073*
H7C0.48160.50780.31790.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0512 (13)0.0409 (13)0.0522 (14)0.0080 (10)0.0035 (10)0.0126 (10)
S20.0551 (14)0.0473 (14)0.0417 (12)0.0113 (11)0.0001 (9)0.0038 (10)
S30.0519 (13)0.0337 (12)0.0451 (12)0.0077 (10)0.0010 (9)0.0006 (9)
S40.0513 (13)0.0308 (12)0.0429 (12)0.0058 (10)0.0014 (9)0.0009 (9)
S50.0751 (18)0.078 (2)0.0561 (16)0.0221 (15)0.0135 (12)0.0300 (13)
C10.049 (5)0.044 (5)0.047 (5)0.007 (4)0.011 (4)0.012 (4)
C20.046 (5)0.031 (5)0.047 (5)0.008 (4)0.002 (4)0.003 (4)
C30.040 (4)0.039 (5)0.040 (4)0.010 (4)0.004 (3)0.001 (3)
C40.032 (4)0.038 (4)0.040 (4)0.004 (3)0.006 (3)0.006 (3)
C50.039 (4)0.037 (5)0.058 (5)0.014 (4)0.013 (4)0.001 (4)
C60.066 (6)0.050 (6)0.051 (5)0.016 (5)0.002 (4)0.005 (4)
C70.056 (5)0.039 (5)0.049 (5)0.016 (4)0.002 (4)0.014 (4)
Geometric parameters (Å, º) top
S1—C11.716 (8)C3—C51.346 (10)
S1—C21.738 (8)C5—C61.496 (10)
S2—C41.723 (7)C5—C71.497 (10)
S2—C11.744 (8)C6—H6A0.9600
S3—C21.725 (8)C6—H6B0.9600
S3—C31.775 (8)C6—H6C0.9600
S4—C41.758 (7)C7—H7A0.9600
S4—C31.783 (7)C7—H7B0.9600
S5—C11.652 (7)C7—H7C0.9600
C2—C41.341 (10)
S1···S1i3.581 (4)S5···S5ii3.501 (5)
C1—S1—C296.7 (4)C3—C5—C6120.7 (8)
C4—S2—C194.9 (4)C3—C5—C7121.2 (7)
C2—S3—C394.4 (3)C6—C5—C7118.1 (7)
C4—S4—C394.3 (4)C5—C6—H6A109.5
S5—C1—S1123.5 (5)C5—C6—H6B109.5
S5—C1—S2122.1 (5)H6A—C6—H6B109.5
S1—C1—S2114.4 (4)C5—C6—H6C109.5
C4—C2—S3119.7 (6)H6A—C6—H6C109.5
C4—C2—S1115.0 (6)H6B—C6—H6C109.5
S3—C2—S1125.3 (5)C5—C7—H7A109.5
C5—C3—S3123.3 (6)C5—C7—H7B109.5
C5—C3—S4122.0 (6)H7A—C7—H7B109.5
S3—C3—S4114.6 (4)C5—C7—H7C109.5
C2—C4—S2118.9 (6)H7A—C7—H7C109.5
C2—C4—S4117.0 (6)H7B—C7—H7C109.5
S2—C4—S4124.1 (5)
C2—S1—C1—S5180.0 (5)S3—C2—C4—S2179.5 (4)
C2—S1—C1—S20.9 (5)S1—C2—C4—S20.4 (8)
C4—S2—C1—S5179.9 (5)S3—C2—C4—S40.3 (8)
C4—S2—C1—S10.8 (5)S1—C2—C4—S4178.8 (3)
C3—S3—C2—C40.3 (6)C1—S2—C4—C20.2 (6)
C3—S3—C2—S1178.7 (5)C1—S2—C4—S4179.3 (5)
C1—S1—C2—C40.8 (6)C3—S4—C4—C20.1 (6)
C1—S1—C2—S3179.8 (5)C3—S4—C4—S2179.2 (4)
C2—S3—C3—C5179.6 (7)S3—C3—C5—C60.2 (10)
C2—S3—C3—S40.2 (4)S4—C3—C5—C6179.7 (5)
C4—S4—C3—C5179.8 (7)S3—C3—C5—C7179.5 (5)
C4—S4—C3—S30.1 (4)S4—C3—C5—C70.3 (10)
Symmetry codes: (i) x, y+3, z; (ii) x, y+3, z1.

Experimental details

Crystal data
Chemical formulaC7H6S5
Mr250.47
Crystal system, space groupTriclinic, P1
Temperature (K)291
a, b, c (Å)7.082 (6), 7.126 (6), 10.534 (10)
α, β, γ (°)86.12 (3), 84.77 (3), 71.95 (2)
V3)502.9 (8)
Z2
Radiation typeMo Kα
µ (mm1)1.09
Crystal size (mm)0.09 × 0.02 × 0.01
Data collection
DiffractometerRigaku/MSC Mercury CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4550, 2643, 785
Rint0.117
(sin θ/λ)max1)0.727
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.072, 0.246, 0.84
No. of reflections2643
No. of parameters112
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.50

Computer programs: CrystalClear (Rigaku/MSC, 2006), TEXSAN (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006).

 

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