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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1588.
Published online 2009 June 17. doi:  10.1107/S1600536809022004
PMCID: PMC2969497

4,4′-Di-4-pyridyl-2,2′-dithio­dipyrimidine

Abstract

In the title mol­ecule, C18H12N6S2, the C—S—S—C torsion angle is 96.12 (9)°. The dihedral angles between the pyridyl and pyrimidinyl rings are 16.7 (1) and 1.27 (9)°. In the crystal, inter­molecular π–π inter­actions between the aromatic rings [centroid–centroid distances = 3.888 (2) and 3.572 (1) Å] link mol­ecules into chains propagating in [011].

Related literature

For related crystal structures, see: Ji et al. (2009 [triangle]); Higashi et al. (1978 [triangle]); Tabellion et al. (2001 [triangle]). For general background to heterocyclic disulfides, see: Horikoshi & Mochida (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1588-scheme1.jpg

Experimental

Crystal data

  • C18H12N6S2
  • M r = 376.48
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1588-efi1.jpg
  • a = 9.1060 (8) Å
  • b = 9.3861 (9) Å
  • c = 10.9176 (10) Å
  • α = 84.228 (1)°
  • β = 74.926 (1)°
  • γ = 72.983 (1)°
  • V = 861.27 (14) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.32 mm−1
  • T = 298 K
  • 0.14 × 0.12 × 0.10 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.884, T max = 0.920 (expected range = 0.930–0.968)
  • 5665 measured reflections
  • 3982 independent reflections
  • 3283 reflections with I > 2σ(I)
  • R int = 0.093

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.158
  • S = 1.12
  • 3982 reflections
  • 235 parameters
  • H-atom parameters constrained
  • Δρmax = 0.63 e Å−3
  • Δρmin = −0.50 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022004/cv2571sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022004/cv2571Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the support of the National Natural Science Foundation of China (grant No. 20801011).

supplementary crystallographic information

Comment

Heterocylic disulfide ligands have been considerably studied in the field of supramolecular chemistry over past years (Horikoshi & Mochida, 2006). Herein, we report the molecular structure of the title compound (I) - the newly synthesized disulfide ligand.

In (I) (Fig. 1), the C—S—S—C torsion angle of 96.12 (9)° is much larger than that in its analogue, namely 2,2'-dithiobis(4-pyridin-3-yl-pyrimidine) (Ji et al., 2009).The S—S bond length of 2.0239 (8) Å in (I) is within the normal range (Higashi et al., 1978; Tabellion et al., 2001). In the crystal, molecules are linked into chains through intermolecular aromatic π-π interactions (Table 1) .

Experimental

A solution of SO2Cl2 (0.5 ml) in CH2Cl2 (20 ml) was added dropwise into the suspension containing 4-(pyridin-4-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.

Refinement

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).

Figures

Fig. 1.
The molecular structure of the title compound showing the atomic numbering and 30% probability displacement ellipsoids.

Crystal data

C18H12N6S2Z = 2
Mr = 376.48F(000) = 388
Triclinic, P1Dx = 1.452 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.1060 (8) ÅCell parameters from 3982 reflections
b = 9.3861 (9) Åθ = 2.3–25.5°
c = 10.9176 (10) ŵ = 0.32 mm1
α = 84.228 (1)°T = 298 K
β = 74.926 (1)°Block, yellow
γ = 72.983 (1)°0.14 × 0.12 × 0.10 mm
V = 861.27 (14) Å3

Data collection

Bruker APEXII CCD area-detector diffractometer3982 independent reflections
Radiation source: fine-focus sealed tube3283 reflections with I > 2σ(I)
graphiteRint = 0.093
[var phi] and ω scansθmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −11→12
Tmin = 0.884, Tmax = 0.920k = −10→11
5665 measured reflectionsl = −14→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.158H-atom parameters constrained
S = 1.12w = 1/[σ2(Fo2) + (0.092P)2] where P = (Fo2 + 2Fc2)/3
3982 reflections(Δ/σ)max = 0.026
235 parametersΔρmax = 0.63 e Å3
0 restraintsΔρmin = −0.50 e Å3

Special details

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)

xyzUiso*/Ueq
S10.17317 (7)0.15307 (5)0.45673 (4)0.04865 (18)
S20.04746 (6)0.10746 (6)0.34511 (5)0.05008 (19)
N50.33888 (18)−0.04716 (16)0.21420 (13)0.0350 (3)
N30.23093 (18)0.39811 (16)0.49060 (14)0.0390 (3)
C130.4305 (2)−0.12822 (18)0.11230 (16)0.0350 (4)
C100.1865 (2)0.00258 (19)0.21737 (17)0.0372 (4)
C140.6028 (2)−0.18393 (19)0.10565 (16)0.0359 (4)
N40.1100 (2)−0.01902 (19)0.13474 (17)0.0465 (4)
N20.1638 (2)0.39133 (19)0.29373 (16)0.0488 (4)
C180.7094 (2)−0.2658 (2)0.00391 (19)0.0450 (4)
H18A0.6733−0.2889−0.06180.054*
C90.1901 (2)0.3355 (2)0.40474 (17)0.0391 (4)
C150.6663 (2)−0.1528 (2)0.19982 (18)0.0445 (4)
H15A0.6009−0.09760.26950.053*
C60.2505 (2)0.53454 (19)0.45950 (17)0.0382 (4)
C50.2986 (2)0.6052 (2)0.55342 (17)0.0398 (4)
N60.9295 (2)−0.2845 (2)0.09198 (18)0.0547 (5)
C10.3575 (2)0.7282 (2)0.5210 (2)0.0477 (5)
H1A0.36890.76920.43910.057*
C170.8683 (3)−0.3123 (3)0.0009 (2)0.0537 (5)
H17A0.9372−0.3662−0.06840.064*
C110.2021 (2)−0.0998 (2)0.03537 (19)0.0481 (5)
H11A0.1556−0.1189−0.02540.058*
C70.2231 (3)0.6050 (2)0.3465 (2)0.0510 (5)
H7A0.23370.70050.32530.061*
C120.3641 (2)−0.1563 (2)0.01909 (19)0.0445 (4)
H12A0.4265−0.2112−0.05170.053*
C160.8274 (3)−0.2050 (3)0.1883 (2)0.0525 (5)
H16A0.8673−0.18310.25220.063*
C40.2837 (3)0.5510 (3)0.6763 (2)0.0586 (6)
H4B0.24500.46860.70180.070*
N10.3860 (3)0.7375 (2)0.7322 (2)0.0695 (6)
C80.1796 (3)0.5286 (2)0.2664 (2)0.0546 (5)
H8A0.16050.57470.19040.066*
C20.3989 (3)0.7884 (3)0.6135 (2)0.0584 (6)
H2B0.43870.87040.59050.070*
C30.3270 (4)0.6206 (3)0.7623 (2)0.0737 (8)
H3B0.31420.58370.84550.088*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0729 (4)0.0372 (3)0.0380 (3)−0.0224 (2)−0.0072 (2)−0.0058 (2)
S20.0442 (3)0.0486 (3)0.0559 (3)−0.0174 (2)0.0021 (2)−0.0188 (2)
N50.0447 (8)0.0311 (7)0.0309 (7)−0.0148 (6)−0.0068 (6)−0.0009 (6)
N30.0498 (9)0.0321 (7)0.0342 (7)−0.0121 (6)−0.0061 (6)−0.0053 (6)
C130.0472 (9)0.0291 (8)0.0291 (8)−0.0153 (7)−0.0047 (7)−0.0005 (6)
C100.0462 (10)0.0306 (8)0.0372 (9)−0.0179 (7)−0.0061 (7)−0.0008 (7)
C140.0467 (10)0.0302 (8)0.0311 (8)−0.0141 (7)−0.0065 (7)0.0013 (6)
N40.0465 (9)0.0481 (9)0.0506 (9)−0.0194 (7)−0.0123 (7)−0.0064 (7)
N20.0622 (11)0.0463 (9)0.0425 (9)−0.0183 (8)−0.0164 (8)−0.0035 (7)
C180.0487 (11)0.0450 (10)0.0391 (9)−0.0091 (8)−0.0082 (8)−0.0087 (8)
C90.0438 (9)0.0359 (9)0.0345 (8)−0.0099 (7)−0.0032 (7)−0.0071 (7)
C150.0516 (11)0.0480 (11)0.0344 (9)−0.0162 (8)−0.0078 (8)−0.0036 (8)
C60.0430 (9)0.0324 (8)0.0372 (9)−0.0090 (7)−0.0062 (7)−0.0047 (7)
C50.0448 (10)0.0307 (8)0.0414 (9)−0.0081 (7)−0.0061 (8)−0.0084 (7)
N60.0498 (10)0.0580 (11)0.0529 (10)−0.0117 (8)−0.0121 (8)0.0037 (8)
C10.0515 (11)0.0438 (10)0.0470 (11)−0.0161 (8)−0.0045 (8)−0.0085 (8)
C170.0528 (12)0.0509 (12)0.0489 (11)−0.0052 (9)−0.0055 (9)−0.0087 (9)
C110.0554 (11)0.0548 (12)0.0429 (10)−0.0236 (9)−0.0148 (9)−0.0085 (9)
C70.0694 (13)0.0378 (10)0.0502 (11)−0.0189 (9)−0.0198 (10)0.0054 (8)
C120.0541 (11)0.0462 (11)0.0367 (9)−0.0179 (8)−0.0092 (8)−0.0101 (8)
C160.0558 (12)0.0634 (13)0.0444 (11)−0.0225 (10)−0.0180 (9)0.0042 (9)
C40.0924 (17)0.0458 (12)0.0475 (12)−0.0306 (11)−0.0207 (11)−0.0032 (9)
N10.0925 (16)0.0651 (13)0.0639 (13)−0.0318 (11)−0.0235 (12)−0.0193 (10)
C80.0737 (14)0.0501 (12)0.0465 (11)−0.0202 (10)−0.0255 (11)0.0069 (9)
C20.0635 (14)0.0516 (13)0.0656 (15)−0.0244 (10)−0.0103 (11)−0.0161 (11)
C30.120 (2)0.0663 (16)0.0496 (13)−0.0387 (16)−0.0302 (15)−0.0036 (11)

Geometric parameters (Å, °)

S1—C91.7867 (19)C5—C41.374 (3)
S1—S22.0238 (7)C5—C11.388 (3)
S2—C101.7734 (19)N6—C171.339 (3)
N5—C101.321 (2)N6—C161.331 (3)
N5—C131.352 (2)C1—C21.385 (3)
N3—C91.335 (2)C1—H1A0.9300
N3—C61.342 (2)C17—H17A0.9300
C13—C121.392 (2)C11—C121.384 (3)
C13—C141.486 (3)C11—H11A0.9300
C10—N41.336 (2)C7—C81.382 (3)
C14—C181.393 (3)C7—H7A0.9300
C14—C151.395 (3)C12—H12A0.9300
N4—C111.332 (3)C16—H16A0.9300
N2—C81.333 (3)C4—C31.389 (3)
N2—C91.323 (2)C4—H4B0.9300
C18—C171.377 (3)N1—C21.323 (3)
C18—H18A0.9300N1—C31.335 (3)
C15—C161.380 (3)C8—H8A0.9300
C15—H15A0.9300C2—H2B0.9300
C6—C71.386 (3)C3—H3B0.9300
C6—C51.491 (2)
Cg1···Cg2i3.888 (2)Cg3···Cg4ii3.572 (1)
C9—S1—S2104.02 (6)C2—C1—C5118.5 (2)
C10—S2—S1106.81 (6)C2—C1—H1A120.8
C10—N5—C13115.68 (14)C5—C1—H1A120.8
C9—N3—C6115.86 (16)N6—C17—C18123.76 (19)
N5—C13—C12120.70 (17)N6—C17—H17A118.1
N5—C13—C14116.75 (15)C18—C17—H17A118.1
C12—C13—C14122.55 (16)N4—C11—C12122.50 (16)
N5—C10—N4128.71 (17)N4—C11—H11A118.8
N5—C10—S2122.14 (13)C12—C11—H11A118.7
N4—C10—S2109.10 (13)C8—C7—C6117.84 (19)
C18—C14—C15116.68 (17)C8—C7—H7A121.1
C18—C14—C13121.97 (16)C6—C7—H7A121.1
C15—C14—C13121.33 (16)C11—C12—C13117.66 (17)
C10—N4—C11114.73 (16)C11—C12—H12A121.2
C8—N2—C9114.58 (16)C13—C12—H12A121.2
C17—C18—C14119.77 (18)N6—C16—C15124.43 (18)
C17—C18—H18A120.1N6—C16—H16A117.8
C14—C18—H18A120.1C15—C16—H16A117.8
N3—C9—N2128.50 (18)C5—C4—C3119.3 (2)
N3—C9—S1111.00 (14)C5—C4—H4B120.4
N2—C9—S1120.50 (14)C3—C4—H4B120.4
C16—C15—C14119.14 (18)C2—N1—C3116.0 (2)
C16—C15—H15A120.4N2—C8—C7122.63 (19)
C14—C15—H15A120.4N2—C8—H8A118.7
N3—C6—C7120.54 (17)C7—C8—H8A118.7
N3—C6—C5116.60 (16)N1—C2—C1124.7 (2)
C7—C6—C5122.84 (17)N1—C2—H2B117.6
C4—C5—C1117.73 (18)C1—C2—H2B117.6
C4—C5—C6120.55 (18)N1—C3—C4123.8 (2)
C1—C5—C6121.71 (18)N1—C3—H3B118.1
C17—N6—C16116.21 (18)C4—C3—H3B118.1

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2571).

References

  • Bruker (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT-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.
  • Ji, J.-F., Li, L. & Zhu, H.-B. (2009). Acta Cryst. E65, o1253. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tabellion, F. M., Seidel, S. R., Arif, A. M. & Stang, P. J. (2001). J. Am Chem. Soc.123, 7740–7741. [PubMed]

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