Acta Cryst. (2009). E65, o1253 [ doi:10.1107/S1600536809016869 ]
The asymmetric unit of the title compound, C18H12N6S2, contains one half-molecule situated on a twofold rotational axis that passes through the mid-point of the S-S bond. In the molecule, the C-S-S-C torsion angle is 81.33 (7)°. The crystal packing exhibits no significantly short intermolecular contacts.
A solution of SO2Cl2 (0.5 mL) in CH2Cl2 (20 ml) was added dropwise into the suspension containing 4-(pyridin-3-yl)pyrimidine-2-thiol (1.89 g) and 30 ml of CH2Cl2.Upon addition, the mixture was stirred at room temperature for 30 min. The solid was collected by filtration and dissolved into 30 ml of H2O. The solution PH was adjusted into the range of 8–9 to give white precipitates. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of the CH2Cl2 solution of the title compound.
All H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./cv2555fig1thm.gif)
| Fig. 1. The molecular structure of the title compound showing the atomic numbering and 40% probability displacement ellipsoids [symmetry code: (A) -x, y, 1/2 - z]. |
| C18H12N6S2 | F000 = 776 |
| Mr = 376.48 | Dx = 1.454 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2091 reflections |
| a = 19.480 (3) Å | θ = 2.3–25.5º |
| b = 5.4192 (9) Å | µ = 0.33 mm−1 |
| c = 17.979 (3) Å | T = 298 K |
| β = 115.034 (2)º | Block, yellow |
| V = 1719.6 (5) Å3 | 0.12 × 0.11 × 0.09 mm |
| Z = 4 |
| Bruker APEXII CCD area-detector diffractometer | 2091 independent reflections |
| Radiation source: fine-focus sealed tube | 1590 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.054 |
| T = 298 K | θmax = 28.2º |
| φ and ω scans | θmin = 2.3º |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −15→25 |
| Tmin = 0.884, Tmax = 0.920 | k = −7→6 |
| 5331 measured reflections | l = −23→21 |
| 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)] = 0.039 | H-atom parameters constrained |
| wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.07 | (Δ/σ)max < 0.001 |
| 2091 reflections | Δρmax = 0.20 e Å−3 |
| 118 parameters | Δρmin = −0.25 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C18H12N6S2 | V = 1719.6 (5) Å3 |
| Mr = 376.48 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 19.480 (3) Å | µ = 0.33 mm−1 |
| b = 5.4192 (9) Å | T = 298 K |
| c = 17.979 (3) Å | 0.12 × 0.11 × 0.09 mm |
| β = 115.034 (2)º |
| Bruker APEXII CCD area-detector diffractometer | 2091 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1590 reflections with I > 2σ(I) |
| Tmin = 0.884, Tmax = 0.920 | Rint = 0.054 |
| 5331 measured reflections |
| R[F2 > 2σ(F2)] = 0.039 | 118 parameters |
| wR(F2) = 0.106 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.20 e Å−3 |
| 2091 reflections | Δρmin = −0.25 e Å−3 |
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 | 0.03745 (2) | 0.82831 (7) | 0.22489 (2) | 0.05022 (17) | |
| N3 | 0.09221 (7) | 0.4611 (2) | 0.33598 (7) | 0.0431 (3) | |
| C5 | 0.13449 (9) | 0.1539 (3) | 0.44158 (9) | 0.0494 (4) | |
| C6 | 0.14360 (8) | 0.2851 (3) | 0.37363 (9) | 0.0449 (4) | |
| N2 | 0.15519 (8) | 0.5576 (3) | 0.25070 (8) | 0.0560 (4) | |
| C9 | 0.10152 (8) | 0.5858 (3) | 0.27763 (8) | 0.0436 (3) | |
| C7 | 0.20210 (9) | 0.2385 (3) | 0.35106 (10) | 0.0549 (4) | |
| H7A | 0.2380 | 0.1168 | 0.3769 | 0.066* | |
| C8 | 0.20481 (10) | 0.3797 (3) | 0.28883 (11) | 0.0599 (5) | |
| H8A | 0.2434 | 0.3493 | 0.2725 | 0.072* | |
| C4 | 0.09033 (11) | 0.2523 (4) | 0.47734 (10) | 0.0617 (5) | |
| H4A | 0.0642 | 0.3995 | 0.4582 | 0.074* | |
| C1 | 0.17081 (12) | −0.0663 (3) | 0.47231 (10) | 0.0668 (5) | |
| H1A | 0.2002 | −0.1334 | 0.4479 | 0.080* | |
| N1 | 0.16688 (12) | −0.1900 (3) | 0.53450 (11) | 0.0827 (6) | |
| C3 | 0.08571 (12) | 0.1278 (5) | 0.54219 (11) | 0.0771 (6) | |
| H3B | 0.0569 | 0.1906 | 0.5679 | 0.092* | |
| C2 | 0.12428 (14) | −0.0895 (5) | 0.56778 (12) | 0.0858 (7) | |
| H2B | 0.1204 | −0.1720 | 0.6112 | 0.103* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0489 (3) | 0.0576 (3) | 0.0448 (2) | −0.00386 (18) | 0.02041 (19) | 0.00495 (17) |
| N3 | 0.0412 (7) | 0.0496 (7) | 0.0378 (6) | −0.0045 (6) | 0.0159 (5) | −0.0041 (5) |
| C5 | 0.0477 (9) | 0.0511 (9) | 0.0405 (8) | −0.0095 (7) | 0.0101 (7) | −0.0034 (6) |
| C6 | 0.0417 (8) | 0.0475 (8) | 0.0394 (8) | −0.0074 (7) | 0.0113 (7) | −0.0102 (6) |
| N2 | 0.0466 (8) | 0.0760 (10) | 0.0524 (8) | −0.0031 (7) | 0.0278 (7) | −0.0019 (7) |
| C9 | 0.0389 (7) | 0.0533 (8) | 0.0375 (7) | −0.0080 (7) | 0.0150 (6) | −0.0080 (6) |
| C7 | 0.0427 (9) | 0.0596 (9) | 0.0578 (10) | 0.0013 (8) | 0.0170 (8) | −0.0079 (8) |
| C8 | 0.0454 (9) | 0.0795 (12) | 0.0626 (10) | −0.0025 (9) | 0.0304 (8) | −0.0114 (9) |
| C4 | 0.0586 (11) | 0.0721 (11) | 0.0550 (10) | −0.0076 (9) | 0.0246 (9) | 0.0058 (8) |
| C1 | 0.0716 (12) | 0.0599 (11) | 0.0551 (10) | −0.0021 (10) | 0.0133 (9) | 0.0008 (9) |
| N1 | 0.0928 (14) | 0.0723 (11) | 0.0631 (10) | −0.0090 (10) | 0.0137 (10) | 0.0172 (8) |
| C3 | 0.0734 (14) | 0.1040 (16) | 0.0558 (11) | −0.0123 (12) | 0.0292 (10) | 0.0095 (10) |
| C2 | 0.0838 (16) | 0.1026 (17) | 0.0541 (11) | −0.0319 (14) | 0.0129 (11) | 0.0196 (11) |
| S1—C9 | 1.7840 (16) | C7—H7A | 0.9300 |
| S1—S1i | 2.0148 (8) | C8—H8A | 0.9300 |
| N3—C9 | 1.3233 (17) | C4—C3 | 1.383 (2) |
| N3—C6 | 1.3402 (19) | C4—H4A | 0.9300 |
| C5—C1 | 1.378 (2) | C1—N1 | 1.333 (2) |
| C5—C4 | 1.380 (2) | C1—H1A | 0.9300 |
| C5—C6 | 1.488 (2) | N1—C2 | 1.328 (3) |
| C6—C7 | 1.385 (2) | C3—C2 | 1.367 (3) |
| N2—C9 | 1.334 (2) | C3—H3B | 0.9300 |
| N2—C8 | 1.332 (2) | C2—H2B | 0.9300 |
| C7—C8 | 1.375 (2) | ||
| C9—S1—S1i | 103.78 (5) | N2—C8—H8A | 118.2 |
| C9—N3—C6 | 116.12 (13) | C7—C8—H8A | 118.2 |
| C1—C5—C4 | 117.59 (17) | C5—C4—C3 | 118.7 (2) |
| C1—C5—C6 | 121.58 (16) | C5—C4—H4A | 120.7 |
| C4—C5—C6 | 120.81 (15) | C3—C4—H4A | 120.7 |
| N3—C6—C7 | 120.87 (14) | N1—C1—C5 | 124.72 (19) |
| N3—C6—C5 | 115.57 (13) | N1—C1—H1A | 117.6 |
| C7—C6—C5 | 123.53 (15) | C5—C1—H1A | 117.6 |
| C9—N2—C8 | 113.93 (13) | C2—N1—C1 | 116.12 (18) |
| N3—C9—N2 | 128.37 (15) | C2—C3—C4 | 118.8 (2) |
| N3—C9—S1 | 119.86 (11) | C2—C3—H3B | 120.6 |
| N2—C9—S1 | 111.77 (11) | C4—C3—H3B | 120.6 |
| C8—C7—C6 | 117.17 (16) | N1—C2—C3 | 124.10 (19) |
| C8—C7—H7A | 121.4 | N1—C2—H2B | 118.0 |
| C6—C7—H7A | 121.4 | C3—C2—H2B | 118.0 |
| N2—C8—C7 | 123.54 (15) |
| Symmetry codes: (i) −x, y, −z+1/2. |
The authors acknowledge the finanical support of the National Natural Science Foundation of China (grant No. 20801011) and the Young Teachers' Starting Fund of Southeast University.
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2007). APEX2 andSAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
Higashi, L. S., Lundeen, M. & Seff, J. (1978). J. Am. Chem. Soc. 100, 8101–8106.
Horikoshi, R. & Mochida, T. (2006). Coord. Chem. Rev. 250, 2595–2609.
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Tabellion, F. M., Seidel, S. R., Arif, A. M. & Stang, P. J. (2001). J. Am Chem. Soc. 123, 7740–7741.
Heterocyclic disulfide ligands have attracted considerable attention due to its conformationally defined torison angle and axial chirality (Horikoshi & Mochida, 2006). Herein, we report the molecular structure of the title compound (I) - the newly synthesized disulfide ligand.
In (I) (Fig. 1), the dihedral angle between the pyrimidinyl and pyrdinyl rings is 17.62 (6)°. The C—S—S—C torsion angle of 81.33 (7)° and S—S bond length of 2.0148 (8) Å are comparable to those of typical aromatic disulfides (Higashi et al., 1978; Tabellion et al., 2001).