Tris{2-[4-(2-pyrid­yl)pyrimidin-2-ylsulfan­yl]eth­yl}amine

Jian-Quan Wang; Ya-Wen Zhang; Lin Cheng

doi:10.1107/S160053680902741X

. 2009 Jul 18;65(Pt 8):o1889–o1890. doi: 10.1107/S160053680902741X

Tris{2-[4-(2-pyridyl)pyrimidin-2-ylsulfanyl]ethyl}amine

Jian-Quan Wang ^a, Ya-Wen Zhang ^a, Lin Cheng ^a,^*

PMCID: PMC2977494 PMID: 21583580

Abstract

The tripodal character of the title compound, C₃₃H₃₀N₁₀S₃, arises from the three thioether arms surrounding a central amine N atom. The three arms have approximately the same conformation but distinct geometries in a trans–trans–cis conformation, resulting in a short pyridine–sulfanyl N⋯S distance of 4.320 (7) Å. The distances of the central N atom to the N atoms of three pyridine rings in the arms are 8.305 (7), 8.032 (7) and 5.076 (9)Å. In the crystal, molecules are joined into a three-dimensional supramolecular network via effective π–π stacking between adjacent heterocycles [centroid–centroid distances of 3.700 (3)–4.118 (4) Å between adjacent interlayer pyrimidine rings and 3.676 (4) Å between the pyridine rings].

Related literature

For the use of tripodal ligands in crystal engineering, see: Hammes et al. (1998 ▶); Hiraoka et al. (2005 ▶). For the use of thioether ligands in crystal engineering, see: Dong et al. (2008a ▶,b ▶); Zhang et al. (2008 ▶).

Experimental

Crystal data

C₃₃H₃₀N₁₀S₃
M _r = 662.85
Orthorhombic,
a = 16.169 (3) Å
b = 25.670 (5) Å
c = 7.6166 (14) Å
V = 3161.3 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 295 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.922, T _max = 0.947
16502 measured reflections
6104 independent reflections
3099 reflections with I > 2σ(I)
R _int = 0.105

Refinement

R[F ² > 2σ(F ²)] = 0.070
wR(F ²) = 0.123
S = 1.06
6104 reflections
415 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ▶), 2750 Friedel pairs
Flack parameter: −0.33 (12)

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902741X/si2186sup1.cif

e-65-o1889-sup1.cif^{(23.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902741X/si2186Isup2.hkl

e-65-o1889-Isup2.hkl^{(298.8KB, hkl)}

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

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

Recently, tripodal ligands have attracted much attention because they can be used to construct interesting topologies such as moleular cages and boxes (Hammes et al. 1998, Hiraoka et al. 2005). Meanwhile, flexible thioethers have been well established ligands in coordination and metallosupramolecular chemistry because of their rich structural information (Dong et al. 2008a, b; Zhang et al. 2008). Herein, we report the crystal structure of the title compound, C₃₃H₃₀N₁₀S₃, based on a tripodal dithioether ligand -tris(2-(4-(pyridin-3-yl)pyrimidin-2-ylthio)ethyl)amine.

The tripodal character of the title compound arises from the three thioether arms surrounding a central amine nitrogen. The three arms have approximately the same conformation but distinct geometries, in a trans-trans-cis conformation (Fig. 1). The distances of the central nitrogen atom to the nitrogen atoms of three pyridine rings in the arms are 8.305 (7), 8.032 (7) and 5.076 (9)°, respectively. Two different heterocyclic rings in each arm are not coplanar with the angle of 18.0 (3), 11.9 (3) and 26.4 (2)°, respectively. The discrete molecules are joined into a three-dimensional supramolecular network via effective π—π stacking (Fig. 2) between the interlayer adjacent pyrimidine rings with the Cg3···Cg5ⁱ separation of 3.700 (3) to 4.118 (4) Å, with a torsion angle of 7.24°, and a Cg4···Cg6ⁱⁱ distance between pyridine rings of 3.676 (4) Å, with a torsion angle of 4.64°. Cg3 and Cg5 are the centroids of the pyrimidine rings (N5 C11 C12 C13 N4 C10) and (N8 C20 C21 C22 N7 C19), and Cg4 and Cg6 are the centroids of the pyridine rings (C14 C15 C16 C17 N6 C18) and (C23 C24 N9 C25 C26 C27). Symmetry codes: (i = 1 - x, 1 - y, 1/2 + z; ii = 1 - x, 1 - y, -1/2 + z).

Experimental

An ethanol solution (50 ml) of tris(2-bromoethyl)amine (3.35 g, 10 mmol) was added to a dry ethanol solution (300 ml) containing 4-(pyridin-3-yl)pyrimidine-2-thiol (5.67 g, 30 mmol) and sodium hydroxide (1.20 g, 30 mmol). The solution was stirred and refluxed for 8 h. Yellow precipitates were filtered out, washed by water and ethanol, and dried in vacuum. Yield (3.24 g) 48.9%. The yellow crystals were obtained after the filter slowly evaporated.