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

Zhu, H.-B.; Wang, H.; Li, L.

doi:10.1107/S1600536809022004

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1588

doi:10.1107/S1600536809022004

Open

access

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

Hai-Bin Zhu,^a ^* Hai Wang ^a and Lei Li ^a

^aSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing, People's Republic of China
^*Correspondence e-mail: zhuhaibin@seu.edu.cn

(Received 3 June 2009; accepted 10 June 2009; online 17 June 2009)

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 ); Higashi et al. (1978 ); Tabellion et al. (2001 ). For general background to heterocyclic disulfides, see: Horikoshi & Mochida (2006 ).

Experimental

Crystal data

C₁₈H₁₂N₆S₂
M_r = 376.48
Triclinic, $[P \overline 1]$
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 ) 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[F² > 2σ(F²)] = 0.056
wR(F²) = 0.158
S = 1.12
3982 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ); cell refinement: 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

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

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

checkCIF report

Comment top

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) .

Related literature top

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

Experimental top

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.

Computing details top

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).

Figures top

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

4,4'-Di-4-pyridyl-2,2'-dithiodipyrimidine top

Crystal data top

C₁₈H₁₂N₆S₂	Z = 2
M_r = 376.48	F(000) = 388
Triclinic, P1	D_x = 1.452 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1060 (8) Å	Cell parameters from 3982 reflections
b = 9.3861 (9) Å	θ = 2.3–25.5°
c = 10.9176 (10) Å	µ = 0.32 mm⁻¹
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 top

Bruker APEXII CCD area-detector diffractometer	3982 independent reflections
Radiation source: fine-focus sealed tube	3283 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.093
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→12
T_min = 0.884, T_max = 0.920	k = −10→11
5665 measured reflections	l = −14→13

Refinement top

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.092P)²] where P = (F_o² + 2F_c²)/3
3982 reflections	(Δ/σ)_max = 0.026
235 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₁₈H₁₂N₆S₂	γ = 72.983 (1)°
M_r = 376.48	V = 861.27 (14) Å³
Triclinic, P1	Z = 2
a = 9.1060 (8) Å	Mo Kα radiation
b = 9.3861 (9) Å	µ = 0.32 mm⁻¹
c = 10.9176 (10) Å	T = 298 K
α = 84.228 (1)°	0.14 × 0.12 × 0.10 mm
β = 74.926 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3982 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3283 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.920	R_int = 0.093
5665 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.12	Δρ_max = 0.63 e Å⁻³
3982 reflections	Δρ_min = −0.50 e Å⁻³
235 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
S1	0.17317 (7)	0.15307 (5)	0.45673 (4)	0.04865 (18)
S2	0.04746 (6)	0.10746 (6)	0.34511 (5)	0.05008 (19)
N5	0.33888 (18)	−0.04716 (16)	0.21420 (13)	0.0350 (3)
N3	0.23093 (18)	0.39811 (16)	0.49060 (14)	0.0390 (3)
C13	0.4305 (2)	−0.12822 (18)	0.11230 (16)	0.0350 (4)
C10	0.1865 (2)	0.00258 (19)	0.21737 (17)	0.0372 (4)
C14	0.6028 (2)	−0.18393 (19)	0.10565 (16)	0.0359 (4)
N4	0.1100 (2)	−0.01902 (19)	0.13474 (17)	0.0465 (4)
N2	0.1638 (2)	0.39133 (19)	0.29373 (16)	0.0488 (4)
C18	0.7094 (2)	−0.2658 (2)	0.00391 (19)	0.0450 (4)
H18A	0.6733	−0.2889	−0.0618	0.054*
C9	0.1901 (2)	0.3355 (2)	0.40474 (17)	0.0391 (4)
C15	0.6663 (2)	−0.1528 (2)	0.19982 (18)	0.0445 (4)
H15A	0.6009	−0.0976	0.2695	0.053*
C6	0.2505 (2)	0.53454 (19)	0.45950 (17)	0.0382 (4)
C5	0.2986 (2)	0.6052 (2)	0.55342 (17)	0.0398 (4)
N6	0.9295 (2)	−0.2845 (2)	0.09198 (18)	0.0547 (5)
C1	0.3575 (2)	0.7282 (2)	0.5210 (2)	0.0477 (5)
H1A	0.3689	0.7692	0.4391	0.057*
C17	0.8683 (3)	−0.3123 (3)	0.0009 (2)	0.0537 (5)
H17A	0.9372	−0.3662	−0.0684	0.064*
C11	0.2021 (2)	−0.0998 (2)	0.03537 (19)	0.0481 (5)
H11A	0.1556	−0.1189	−0.0254	0.058*
C7	0.2231 (3)	0.6050 (2)	0.3465 (2)	0.0510 (5)
H7A	0.2337	0.7005	0.3253	0.061*
C12	0.3641 (2)	−0.1563 (2)	0.01909 (19)	0.0445 (4)
H12A	0.4265	−0.2112	−0.0517	0.053*
C16	0.8274 (3)	−0.2050 (3)	0.1883 (2)	0.0525 (5)
H16A	0.8673	−0.1831	0.2522	0.063*
C4	0.2837 (3)	0.5510 (3)	0.6763 (2)	0.0586 (6)
H4B	0.2450	0.4686	0.7018	0.070*
N1	0.3860 (3)	0.7375 (2)	0.7322 (2)	0.0695 (6)
C8	0.1796 (3)	0.5286 (2)	0.2664 (2)	0.0546 (5)
H8A	0.1605	0.5747	0.1904	0.066*
C2	0.3989 (3)	0.7884 (3)	0.6135 (2)	0.0584 (6)
H2B	0.4387	0.8704	0.5905	0.070*
C3	0.3270 (4)	0.6206 (3)	0.7623 (2)	0.0737 (8)
H3B	0.3142	0.5837	0.8455	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0729 (4)	0.0372 (3)	0.0380 (3)	−0.0224 (2)	−0.0072 (2)	−0.0058 (2)
S2	0.0442 (3)	0.0486 (3)	0.0559 (3)	−0.0174 (2)	0.0021 (2)	−0.0188 (2)
N5	0.0447 (8)	0.0311 (7)	0.0309 (7)	−0.0148 (6)	−0.0068 (6)	−0.0009 (6)
N3	0.0498 (9)	0.0321 (7)	0.0342 (7)	−0.0121 (6)	−0.0061 (6)	−0.0053 (6)
C13	0.0472 (9)	0.0291 (8)	0.0291 (8)	−0.0153 (7)	−0.0047 (7)	−0.0005 (6)
C10	0.0462 (10)	0.0306 (8)	0.0372 (9)	−0.0179 (7)	−0.0061 (7)	−0.0008 (7)
C14	0.0467 (10)	0.0302 (8)	0.0311 (8)	−0.0141 (7)	−0.0065 (7)	0.0013 (6)
N4	0.0465 (9)	0.0481 (9)	0.0506 (9)	−0.0194 (7)	−0.0123 (7)	−0.0064 (7)
N2	0.0622 (11)	0.0463 (9)	0.0425 (9)	−0.0183 (8)	−0.0164 (8)	−0.0035 (7)
C18	0.0487 (11)	0.0450 (10)	0.0391 (9)	−0.0091 (8)	−0.0082 (8)	−0.0087 (8)
C9	0.0438 (9)	0.0359 (9)	0.0345 (8)	−0.0099 (7)	−0.0032 (7)	−0.0071 (7)
C15	0.0516 (11)	0.0480 (11)	0.0344 (9)	−0.0162 (8)	−0.0078 (8)	−0.0036 (8)
C6	0.0430 (9)	0.0324 (8)	0.0372 (9)	−0.0090 (7)	−0.0062 (7)	−0.0047 (7)
C5	0.0448 (10)	0.0307 (8)	0.0414 (9)	−0.0081 (7)	−0.0061 (8)	−0.0084 (7)
N6	0.0498 (10)	0.0580 (11)	0.0529 (10)	−0.0117 (8)	−0.0121 (8)	0.0037 (8)
C1	0.0515 (11)	0.0438 (10)	0.0470 (11)	−0.0161 (8)	−0.0045 (8)	−0.0085 (8)
C17	0.0528 (12)	0.0509 (12)	0.0489 (11)	−0.0052 (9)	−0.0055 (9)	−0.0087 (9)
C11	0.0554 (11)	0.0548 (12)	0.0429 (10)	−0.0236 (9)	−0.0148 (9)	−0.0085 (9)
C7	0.0694 (13)	0.0378 (10)	0.0502 (11)	−0.0189 (9)	−0.0198 (10)	0.0054 (8)
C12	0.0541 (11)	0.0462 (11)	0.0367 (9)	−0.0179 (8)	−0.0092 (8)	−0.0101 (8)
C16	0.0558 (12)	0.0634 (13)	0.0444 (11)	−0.0225 (10)	−0.0180 (9)	0.0042 (9)
C4	0.0924 (17)	0.0458 (12)	0.0475 (12)	−0.0306 (11)	−0.0207 (11)	−0.0032 (9)
N1	0.0925 (16)	0.0651 (13)	0.0639 (13)	−0.0318 (11)	−0.0235 (12)	−0.0193 (10)
C8	0.0737 (14)	0.0501 (12)	0.0465 (11)	−0.0202 (10)	−0.0255 (11)	0.0069 (9)
C2	0.0635 (14)	0.0516 (13)	0.0656 (15)	−0.0244 (10)	−0.0103 (11)	−0.0161 (11)
C3	0.120 (2)	0.0663 (16)	0.0496 (13)	−0.0387 (16)	−0.0302 (15)	−0.0036 (11)

Geometric parameters (Å, º) top

S1—C9	1.7867 (19)	C5—C4	1.374 (3)
S1—S2	2.0238 (7)	C5—C1	1.388 (3)
S2—C10	1.7734 (19)	N6—C17	1.339 (3)
N5—C10	1.321 (2)	N6—C16	1.331 (3)
N5—C13	1.352 (2)	C1—C2	1.385 (3)
N3—C9	1.335 (2)	C1—H1A	0.9300
N3—C6	1.342 (2)	C17—H17A	0.9300
C13—C12	1.392 (2)	C11—C12	1.384 (3)
C13—C14	1.486 (3)	C11—H11A	0.9300
C10—N4	1.336 (2)	C7—C8	1.382 (3)
C14—C18	1.393 (3)	C7—H7A	0.9300
C14—C15	1.395 (3)	C12—H12A	0.9300
N4—C11	1.332 (3)	C16—H16A	0.9300
N2—C8	1.333 (3)	C4—C3	1.389 (3)
N2—C9	1.323 (2)	C4—H4B	0.9300
C18—C17	1.377 (3)	N1—C2	1.323 (3)
C18—H18A	0.9300	N1—C3	1.335 (3)
C15—C16	1.380 (3)	C8—H8A	0.9300
C15—H15A	0.9300	C2—H2B	0.9300
C6—C7	1.386 (3)	C3—H3B	0.9300
C6—C5	1.491 (2)

Cg1···Cg2ⁱ	3.888 (2)	Cg3···Cg4ⁱⁱ	3.572 (1)

C9—S1—S2	104.02 (6)	C2—C1—C5	118.5 (2)
C10—S2—S1	106.81 (6)	C2—C1—H1A	120.8
C10—N5—C13	115.68 (14)	C5—C1—H1A	120.8
C9—N3—C6	115.86 (16)	N6—C17—C18	123.76 (19)
N5—C13—C12	120.70 (17)	N6—C17—H17A	118.1
N5—C13—C14	116.75 (15)	C18—C17—H17A	118.1
C12—C13—C14	122.55 (16)	N4—C11—C12	122.50 (16)
N5—C10—N4	128.71 (17)	N4—C11—H11A	118.8
N5—C10—S2	122.14 (13)	C12—C11—H11A	118.7
N4—C10—S2	109.10 (13)	C8—C7—C6	117.84 (19)
C18—C14—C15	116.68 (17)	C8—C7—H7A	121.1
C18—C14—C13	121.97 (16)	C6—C7—H7A	121.1
C15—C14—C13	121.33 (16)	C11—C12—C13	117.66 (17)
C10—N4—C11	114.73 (16)	C11—C12—H12A	121.2
C8—N2—C9	114.58 (16)	C13—C12—H12A	121.2
C17—C18—C14	119.77 (18)	N6—C16—C15	124.43 (18)
C17—C18—H18A	120.1	N6—C16—H16A	117.8
C14—C18—H18A	120.1	C15—C16—H16A	117.8
N3—C9—N2	128.50 (18)	C5—C4—C3	119.3 (2)
N3—C9—S1	111.00 (14)	C5—C4—H4B	120.4
N2—C9—S1	120.50 (14)	C3—C4—H4B	120.4
C16—C15—C14	119.14 (18)	C2—N1—C3	116.0 (2)
C16—C15—H15A	120.4	N2—C8—C7	122.63 (19)
C14—C15—H15A	120.4	N2—C8—H8A	118.7
N3—C6—C7	120.54 (17)	C7—C8—H8A	118.7
N3—C6—C5	116.60 (16)	N1—C2—C1	124.7 (2)
C7—C6—C5	122.84 (17)	N1—C2—H2B	117.6
C4—C5—C1	117.73 (18)	C1—C2—H2B	117.6
C4—C5—C6	120.55 (18)	N1—C3—C4	123.8 (2)
C1—C5—C6	121.71 (18)	N1—C3—H3B	118.1
C17—N6—C16	116.21 (18)	C4—C3—H3B	118.1

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₂N₆S₂
M_r	376.48
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.1060 (8), 9.3861 (9), 10.9176 (10)
α, β, γ (°)	84.228 (1), 74.926 (1), 72.983 (1)
V (Å³)	861.27 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.884, 0.920
No. of measured, independent and observed [I > 2σ(I)] reflections	5665, 3982, 3283
R_int	0.093
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.158, 1.12
No. of reflections	3982
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.50

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

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
Ji, J.-F., Li, L. & Zhu, H.-B. (2009). Acta Cryst. E65, o1253. Web of Science CSD CrossRef IUCr Journals 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