Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003701/ob6031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003701/ob6031Isup2.hkl |
CCDC reference: 162810
The title compound (I) was synthesized according to the literature method if Papavassiliou et al. (1988). Crystals of (I) were grown from a dichloromethane solution.
All H atoms were placed in geometrically calculated positions and refined by using a riding model with C—H distances set to 0.93 Å.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
C8H4N2S4 | Dx = 1.706 Mg m−3 |
Mr = 256.37 | Melting point: 182 K |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
a = 8.481 (2) Å | Cell parameters from 24 reflections |
b = 9.1928 (9) Å | θ = 9.7–42.8° |
c = 12.8980 (14) Å | µ = 8.39 mm−1 |
β = 96.89 (2)° | T = 296 K |
V = 998.4 (3) Å3 | Needle, orange |
Z = 4 | 0.40 × 0.05 × 0.05 mm |
F(000) = 520 |
Enraf-Nonius CAD-4 diffractometer | 663 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.084 |
Graphite monochromator | θmax = 74.2°, θmin = 5.9° |
ω scans | h = −10→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→11 |
Tmin = 0.134, Tmax = 0.679 | l = 0→16 |
2060 measured reflections | 3 standard reflections every 120 min |
2026 independent reflections | intensity decay: 4.9% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.079 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.198 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0473P)2] where P = (Fo2 + 2Fc2)/3 |
2026 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.62 e Å−3 |
C8H4N2S4 | V = 998.4 (3) Å3 |
Mr = 256.37 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 8.481 (2) Å | µ = 8.39 mm−1 |
b = 9.1928 (9) Å | T = 296 K |
c = 12.8980 (14) Å | 0.40 × 0.05 × 0.05 mm |
β = 96.89 (2)° |
Enraf-Nonius CAD-4 diffractometer | 663 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.084 |
Tmin = 0.134, Tmax = 0.679 | 3 standard reflections every 120 min |
2060 measured reflections | intensity decay: 4.9% |
2026 independent reflections |
R[F2 > 2σ(F2)] = 0.079 | 0 restraints |
wR(F2) = 0.198 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.47 e Å−3 |
2026 reflections | Δρmin = −0.62 e Å−3 |
127 parameters |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 5.6601 (0.0091) x - 0.3727 (0.0120) y + 8.4888 (0.0135) z = 3.8673 (0.0096) * -0.0118 (0.0047) S1 * 0.0204 (0.0050) S2 * -0.0759 (0.0042) S3 * -0.0631 (0.0044) S4 * 0.0266 (0.0079) N1 * -0.0190 (0.0076) N2 * 0.0090 (0.0092) C1 * 0.0240 (0.0101) C2 * 0.0392 (0.0102) C3 * -0.0118 (0.0096) C4 * -0.0114 (0.0098) C5 * -0.0231 (0.0100) C6 * 0.0619 (0.0094) C7 * 0.0351 (0.0093) C8 Rms deviation of fitted atoms = 0.0372 |
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 | 0.6493 (3) | 0.1589 (3) | 0.0282 (2) | 0.0674 (10) | |
S2 | 0.8472 (3) | 0.3437 (3) | −0.0918 (2) | 0.0654 (10) | |
S3 | 0.7875 (3) | −0.1295 (3) | −0.0841 (2) | 0.0624 (9) | |
S4 | 0.9782 (4) | 0.0714 (3) | −0.2010 (2) | 0.0691 (10) | |
N1 | 0.9250 (10) | −0.3509 (10) | −0.1734 (7) | 0.066 (3) | |
N2 | 1.1014 (9) | −0.1626 (10) | −0.2882 (6) | 0.057 (2) | |
C1 | 0.7889 (11) | 0.1682 (12) | −0.0620 (7) | 0.050 (3) | |
C2 | 0.6431 (15) | 0.3437 (12) | 0.0447 (9) | 0.079 (4) | |
H2 | 0.5781 | 0.3828 | 0.0908 | 0.095* | |
C3 | 0.7305 (15) | 0.4331 (13) | −0.0079 (10) | 0.082 (4) | |
H3 | 0.7293 | 0.5337 | −0.0005 | 0.098* | |
C4 | 0.8439 (11) | 0.0490 (13) | −0.1063 (7) | 0.053 (3) | |
C5 | 0.9170 (12) | −0.2081 (13) | −0.1663 (8) | 0.052 (3) | |
C6 | 1.0049 (12) | −0.1131 (11) | −0.2221 (8) | 0.056 (3) | |
C7 | 1.0256 (13) | −0.3999 (13) | −0.2385 (9) | 0.070 (4) | |
H7 | 1.0386 | −0.4996 | −0.2465 | 0.084* | |
C8 | 1.1105 (13) | −0.3038 (15) | −0.2941 (9) | 0.069 (4) | |
H8 | 1.1782 | −0.3430 | −0.3384 | 0.083* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.068 (2) | 0.084 (2) | 0.0552 (19) | 0.0057 (18) | 0.0270 (16) | 0.0009 (17) |
S2 | 0.069 (2) | 0.061 (2) | 0.069 (2) | 0.0031 (17) | 0.0229 (18) | −0.0044 (18) |
S3 | 0.067 (2) | 0.0610 (19) | 0.066 (2) | −0.0009 (16) | 0.0368 (16) | 0.0047 (16) |
S4 | 0.072 (2) | 0.0667 (19) | 0.077 (2) | −0.0049 (17) | 0.0468 (18) | 0.0043 (18) |
N1 | 0.054 (6) | 0.067 (7) | 0.076 (7) | 0.002 (6) | 0.004 (5) | −0.004 (6) |
N2 | 0.049 (5) | 0.075 (7) | 0.049 (6) | 0.012 (5) | 0.018 (4) | −0.015 (5) |
C1 | 0.037 (6) | 0.079 (8) | 0.033 (6) | −0.002 (6) | 0.005 (5) | −0.001 (6) |
C2 | 0.102 (10) | 0.086 (9) | 0.052 (8) | 0.048 (8) | 0.020 (7) | −0.012 (7) |
C3 | 0.098 (11) | 0.067 (8) | 0.082 (10) | 0.028 (8) | 0.021 (8) | −0.011 (8) |
C4 | 0.040 (6) | 0.079 (8) | 0.040 (7) | −0.003 (6) | 0.004 (5) | −0.002 (6) |
C5 | 0.051 (7) | 0.064 (8) | 0.043 (7) | 0.005 (6) | 0.014 (5) | 0.000 (6) |
C6 | 0.047 (7) | 0.065 (7) | 0.059 (7) | 0.017 (6) | 0.015 (6) | −0.010 (6) |
C7 | 0.063 (9) | 0.073 (8) | 0.079 (10) | 0.004 (7) | 0.025 (7) | −0.018 (7) |
C8 | 0.051 (8) | 0.092 (10) | 0.060 (8) | 0.022 (7) | −0.010 (6) | −0.026 (8) |
S1—C2 | 1.714 (11) | N2—C8 | 1.304 (12) |
S1—C1 | 1.760 (9) | N2—C6 | 1.330 (11) |
S2—C3 | 1.756 (11) | C1—C4 | 1.345 (13) |
S2—C1 | 1.744 (10) | C2—C3 | 1.343 (14) |
S3—C5 | 1.769 (10) | C2—H2 | 0.9300 |
S3—C4 | 1.743 (11) | C3—H3 | 0.9300 |
S4—C6 | 1.737 (10) | C5—C6 | 1.402 (13) |
S4—C4 | 1.779 (9) | C7—C8 | 1.391 (14) |
N1—C7 | 1.345 (12) | C7—H7 | 0.9300 |
N1—C5 | 1.318 (11) | C8—H8 | 0.9300 |
C2—S1—C1 | 93.8 (6) | C1—C4—S3 | 125.6 (7) |
C3—S2—C1 | 95.8 (5) | C1—C4—S4 | 118.7 (8) |
C5—S3—C4 | 94.8 (5) | S3—C4—S4 | 115.7 (6) |
C6—S4—C4 | 95.8 (5) | N1—C5—C6 | 123.3 (9) |
C7—N1—C5 | 114.8 (10) | N1—C5—S3 | 119.3 (8) |
C8—N2—C6 | 115.1 (10) | C6—C5—S3 | 117.4 (8) |
C4—C1—S2 | 122.6 (7) | N2—C6—C5 | 121.4 (9) |
C4—C1—S1 | 122.5 (8) | N2—C6—S4 | 122.4 (8) |
S2—C1—S1 | 115.0 (6) | C5—C6—S4 | 116.1 (8) |
C3—C2—S1 | 121.1 (9) | N1—C7—C8 | 121.0 (11) |
C3—C2—H2 | 119.4 | N1—C7—H7 | 119.5 |
S1—C2—H2 | 119.4 | C8—C7—H7 | 119.5 |
C2—C3—S2 | 114.3 (9) | N2—C8—C7 | 124.3 (11) |
C2—C3—H3 | 122.9 | N2—C8—H8 | 117.8 |
S2—C3—H3 | 122.9 | C7—C8—H8 | 117.8 |
Experimental details
Crystal data | |
Chemical formula | C8H4N2S4 |
Mr | 256.37 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 8.481 (2), 9.1928 (9), 12.8980 (14) |
β (°) | 96.89 (2) |
V (Å3) | 998.4 (3) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 8.39 |
Crystal size (mm) | 0.40 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.134, 0.679 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2060, 2026, 663 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.198, 1.07 |
No. of reflections | 2026 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.62 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1992), CAD-4 EXPRESS, HELENA (Spek, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
It is known that S···N inte-rheteroatom contacts work to construct unique molecular networks (Yamashita & Tomura, 1998). In the title compound, (I), short S···N inter-heteroatom contacts [3.10 (1) Å for S2···N1(x, y + 1, z)] are observed between the two π–π dimers, as shown in Fig. 2. Two molecules in a dimer are related by an inversion center. A planar π-conjugated molecule prefers to overlap with a single molecule at both sides of the molecular plane to form a one-dimensional column. In the two-dimensional column of (I), however, one dimer bridges two other dimers through the overlap of the pyrazine and 1,3-dithiole rings (Fig. 3). The angle between the dimers is 111 (1)°. This type of a unique multi-dimensional structure is important for the construction of organic conducting materials (Barclay et al., 2000; Kato et al., 1988; Morimoto & Inabe, 1995; Tomura & Yamashita, 2000; Yamashita et al., 1997, 1998).