Acta Cryst. (2009). E65, o1050 [ doi:10.1107/S160053680901335X ]
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.
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.
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).
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).
![[Figure 1]](./hg2498fig1thm.gif)
| 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]](./hg2498fig2thm.gif)
| Fig. 2. The packing diagram of (I), viewed along the b axis. Dashed lines indicate intermolecular S···S interactions. |
| C7H6S5 | Z = 2 |
| Mr = 250.47 | F(000) = 256 |
| Triclinic, P1 | Dx = 1.654 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
| a = 7.082 (6) Å | Cell parameters from 843 reflections |
| b = 7.126 (6) Å | θ = 3.0–29.7° |
| c = 10.534 (10) Å | µ = 1.09 mm−1 |
| 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 |
| Rigaku/MSC Mercury CCD diffractometer | 785 reflections with I > 2σ(I) |
| Radiation source: Rotating Anode | Rint = 0.117 |
| Confocal | θmax = 31.1°, θmin = 3.0° |
| Detector resolution: 14.63 pixels mm-1 | h = −9→9 |
| φ and ω scans | k = −10→10 |
| 4550 measured reflections | l = −10→15 |
| 2643 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)] = 0.072 | H-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 reflections | Δρmax = 0.46 e Å−3 |
| 112 parameters | Δρmin = −0.50 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.003 (3) |
| C7H6S5 | γ = 71.95 (2)° |
| Mr = 250.47 | V = 502.9 (8) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.082 (6) Å | Mo Kα radiation |
| b = 7.126 (6) Å | µ = 1.09 mm−1 |
| c = 10.534 (10) Å | T = 291 K |
| α = 86.12 (3)° | 0.09 × 0.02 × 0.01 mm |
| β = 84.77 (3)° |
| Rigaku/MSC Mercury CCD diffractometer | 785 reflections with I > 2σ(I) |
| 4550 measured reflections | Rint = 0.117 |
| 2643 independent reflections | θmax = 31.1° |
| R[F2 > 2σ(F2)] = 0.072 | H-atom parameters constrained |
| wR(F2) = 0.246 | Δρmax = 0.46 e Å−3 |
| S = 0.84 | Δρmin = −0.50 e Å−3 |
| 2643 reflections | Absolute structure: ? |
| 112 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.1573 (3) | 1.3556 (3) | −0.12379 (19) | 0.0502 (6) | |
| S2 | 0.2864 (3) | 0.9827 (3) | −0.25144 (18) | 0.0496 (6) | |
| S3 | 0.1902 (3) | 1.1364 (3) | 0.13884 (18) | 0.0452 (6) | |
| S4 | 0.3259 (3) | 0.7524 (3) | 0.00739 (18) | 0.0434 (6) | |
| S5 | 0.1908 (4) | 1.3598 (4) | −0.4066 (2) | 0.0710 (9) | |
| C1 | 0.2089 (11) | 1.2401 (12) | −0.2662 (7) | 0.048 (2) | |
| C2 | 0.2080 (10) | 1.1425 (11) | −0.0257 (7) | 0.0427 (19) | |
| C3 | 0.2706 (10) | 0.8745 (11) | 0.1547 (7) | 0.0407 (18) | |
| C4 | 0.2678 (9) | 0.9729 (12) | −0.0871 (7) | 0.0385 (17) | |
| C5 | 0.2896 (10) | 0.7741 (12) | 0.2681 (8) | 0.045 (2) | |
| C6 | 0.2430 (11) | 0.8811 (12) | 0.3900 (7) | 0.056 (2) | |
| H6A | 0.3602 | 0.8472 | 0.4365 | 0.084* | |
| H6B | 0.1395 | 0.8439 | 0.4405 | 0.084* | |
| H6C | 0.1994 | 1.0210 | 0.3711 | 0.084* | |
| C7 | 0.3596 (11) | 0.5529 (11) | 0.2761 (7) | 0.049 (2) | |
| H7A | 0.3818 | 0.5036 | 0.1917 | 0.073* | |
| H7B | 0.2603 | 0.5056 | 0.3239 | 0.073* | |
| H7C | 0.4816 | 0.5078 | 0.3179 | 0.073* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0512 (13) | 0.0409 (13) | 0.0522 (14) | −0.0080 (10) | −0.0035 (10) | 0.0126 (10) |
| S2 | 0.0551 (14) | 0.0473 (14) | 0.0417 (12) | −0.0113 (11) | 0.0001 (9) | 0.0038 (10) |
| S3 | 0.0519 (13) | 0.0337 (12) | 0.0451 (12) | −0.0077 (10) | 0.0010 (9) | −0.0006 (9) |
| S4 | 0.0513 (13) | 0.0308 (12) | 0.0429 (12) | −0.0058 (10) | −0.0014 (9) | 0.0009 (9) |
| S5 | 0.0751 (18) | 0.078 (2) | 0.0561 (16) | −0.0221 (15) | −0.0135 (12) | 0.0300 (13) |
| C1 | 0.049 (5) | 0.044 (5) | 0.047 (5) | −0.007 (4) | −0.011 (4) | 0.012 (4) |
| C2 | 0.046 (5) | 0.031 (5) | 0.047 (5) | −0.008 (4) | −0.002 (4) | −0.003 (4) |
| C3 | 0.040 (4) | 0.039 (5) | 0.040 (4) | −0.010 (4) | 0.004 (3) | −0.001 (3) |
| C4 | 0.032 (4) | 0.038 (4) | 0.040 (4) | −0.004 (3) | −0.006 (3) | 0.006 (3) |
| C5 | 0.039 (4) | 0.037 (5) | 0.058 (5) | −0.014 (4) | 0.013 (4) | −0.001 (4) |
| C6 | 0.066 (6) | 0.050 (6) | 0.051 (5) | −0.016 (5) | 0.002 (4) | −0.005 (4) |
| C7 | 0.056 (5) | 0.039 (5) | 0.049 (5) | −0.016 (4) | 0.002 (4) | 0.014 (4) |
| S1—C1 | 1.716 (8) | C3—C5 | 1.346 (10) |
| S1—C2 | 1.738 (8) | C5—C6 | 1.496 (10) |
| S2—C4 | 1.723 (7) | C5—C7 | 1.497 (10) |
| S2—C1 | 1.744 (8) | C6—H6A | 0.9600 |
| S3—C2 | 1.725 (8) | C6—H6B | 0.9600 |
| S3—C3 | 1.775 (8) | C6—H6C | 0.9600 |
| S4—C4 | 1.758 (7) | C7—H7A | 0.9600 |
| S4—C3 | 1.783 (7) | C7—H7B | 0.9600 |
| S5—C1 | 1.652 (7) | C7—H7C | 0.9600 |
| C2—C4 | 1.341 (10) | ||
| S1···S1i | 3.581 (4) | S5···S5ii | 3.501 (5) |
| C1—S1—C2 | 96.7 (4) | C3—C5—C6 | 120.7 (8) |
| C4—S2—C1 | 94.9 (4) | C3—C5—C7 | 121.2 (7) |
| C2—S3—C3 | 94.4 (3) | C6—C5—C7 | 118.1 (7) |
| C4—S4—C3 | 94.3 (4) | C5—C6—H6A | 109.5 |
| S5—C1—S1 | 123.5 (5) | C5—C6—H6B | 109.5 |
| S5—C1—S2 | 122.1 (5) | H6A—C6—H6B | 109.5 |
| S1—C1—S2 | 114.4 (4) | C5—C6—H6C | 109.5 |
| C4—C2—S3 | 119.7 (6) | H6A—C6—H6C | 109.5 |
| C4—C2—S1 | 115.0 (6) | H6B—C6—H6C | 109.5 |
| S3—C2—S1 | 125.3 (5) | C5—C7—H7A | 109.5 |
| C5—C3—S3 | 123.3 (6) | C5—C7—H7B | 109.5 |
| C5—C3—S4 | 122.0 (6) | H7A—C7—H7B | 109.5 |
| S3—C3—S4 | 114.6 (4) | C5—C7—H7C | 109.5 |
| C2—C4—S2 | 118.9 (6) | H7A—C7—H7C | 109.5 |
| C2—C4—S4 | 117.0 (6) | H7B—C7—H7C | 109.5 |
| S2—C4—S4 | 124.1 (5) | ||
| C2—S1—C1—S5 | 180.0 (5) | S3—C2—C4—S2 | −179.5 (4) |
| C2—S1—C1—S2 | −0.9 (5) | S1—C2—C4—S2 | −0.4 (8) |
| C4—S2—C1—S5 | 179.9 (5) | S3—C2—C4—S4 | −0.3 (8) |
| C4—S2—C1—S1 | 0.8 (5) | S1—C2—C4—S4 | 178.8 (3) |
| C3—S3—C2—C4 | 0.3 (6) | C1—S2—C4—C2 | −0.2 (6) |
| C3—S3—C2—S1 | −178.7 (5) | C1—S2—C4—S4 | −179.3 (5) |
| C1—S1—C2—C4 | 0.8 (6) | C3—S4—C4—C2 | 0.1 (6) |
| C1—S1—C2—S3 | 179.8 (5) | C3—S4—C4—S2 | 179.2 (4) |
| C2—S3—C3—C5 | 179.6 (7) | S3—C3—C5—C6 | −0.2 (10) |
| C2—S3—C3—S4 | −0.2 (4) | S4—C3—C5—C6 | 179.7 (5) |
| C4—S4—C3—C5 | −179.8 (7) | S3—C3—C5—C7 | −179.5 (5) |
| C4—S4—C3—S3 | 0.1 (4) | S4—C3—C5—C7 | 0.3 (10) |
| Symmetry codes: (i) −x, −y+3, −z; (ii) −x, −y+3, −z−1. |
The authors thank the Instrument Center of the Institute for Molecular Science for the X-ray structure analysis.
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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.