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access4,4′-Di-3-pyridyl-2,2′-dithiodipyrimidine
aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
*Correspondence e-mail: zhuhaibin@seu.edu.cn
The 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.
Related literature
For general background to heterocyclic disulfides, see Horikoshi & Mochida (2006![[Horikoshi, R. & Mochida, T. (2006). Coord. Chem. Rev. 250, 2595-2609.]](../../../../../../logos/arrows/e_arr.gif "Horikoshi, R. & Mochida, T. (2006). Coord. Chem. Rev. 250, 2595-2609.")
). For related crystal structures, see: Higashi et al. (1978); Tabellion et al. (2001).
![[Scheme 1]](cv2555scheme1.gif)
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2007); cell SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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.
Supporting information
contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809016869/cv2555sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809016869/cv2555Isup2.hkl
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 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 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 | F(000) = 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 = 2.3–25.5° |
| b = 5.4192 (9) Å | µ = 0.33 mm−1 |
| c = 17.979 (3) Å | T = 298 K |
| β = 115.034 (2)° | 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) |
| Graphite monochromator | Rint = 0.054 |
| ϕ and ω scans | θmax = 28.2°, θmin = 2.3° |
| 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 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.106 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3 |
| 2091 reflections | (Δ/σ)max < 0.001 |
| 118 parameters | Δρmax = 0.20 e Å−3 |
| 0 restraints | Δρmin = −0.25 e Å−3 |
| C18H12N6S2 | V = 1719.6 (5) Å3 |
| Mr = 376.48 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| 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)° |
| 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 | 0 restraints |
| 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 |
| 118 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. |
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 code: (i) −x, y, −z+1/2. |
Experimental details
| Crystal data | |
| Chemical formula | C18H12N6S2 |
| Mr | 376.48 |
| Crystal system, space group | Monoclinic, C2/c |
| Temperature (K) | 298 |
| a, b, c (Å) | 19.480 (3), 5.4192 (9), 17.979 (3) |
| β (°) | 115.034 (2) |
| V (Å3) | 1719.6 (5) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.33 |
| Crystal size (mm) | 0.12 × 0.11 × 0.09 |
| Data collection | |
| Diffractometer | Bruker APEXII CCD area-detector diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
| Tmin, Tmax | 0.884, 0.920 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5331, 2091, 1590 |
| Rint | 0.054 |
| (sin θ/λ)max (Å−1) | 0.665 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.106, 1.07 |
| No. of reflections | 2091 |
| No. of parameters | 118 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.20, −0.25 |
Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
The authors acknowledge the financial support of the National Natural Science Foundation of China (grant No. 20801011) and the Young Teachers' Starting Fund of Southeast University.
References
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Higashi, L. S., Lundeen, M. & Seff, J. (1978). J. Am. Chem. Soc. 100, 8101–8106. CSD CrossRef CAS Web of Science Google Scholar
Horikoshi, R. & Mochida, T. (2006). Coord. Chem. Rev. 250, 2595–2609. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tabellion, F. M., Seidel, S. R., Arif, A. M. & Stang, P. J. (2001). J. Am Chem. Soc. 123, 7740–7741. Web of Science CSD CrossRef PubMed CAS Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
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).