4,6-Bis[4-(benzyl­sulfan­yl)styr­yl]-2-(methyl­sulfan­yl)pyrimidine

Min Wang; Le-Hua Cheng; Xian-Ping Chu; Shi-You Xu

doi:10.1107/S1600536807065063

. 2007 Dec 12;64(Pt 1):o257. doi: 10.1107/S1600536807065063

4,6-Bis[4-(benzylsulfanyl)styryl]-2-(methylsulfanyl)pyrimidine

Min Wang ^a, Le-Hua Cheng ^a,^*, Xian-Ping Chu ^a, Shi-You Xu ^a

PMCID: PMC2915314 PMID: 21200822

Abstract

The title compound, C₃₅H₃₀N₂S₃, has been synthesized by a solvent-free reaction. The molecule exhibits an E,E configuration, the benzene rings and pyrimidine rings being located on the opposite sides of the C=C bonds. The centroid–centroid separation of 3.5808 (17) Å indicates the existence of π–π stacking between nearly parallel pyrimidine and benzene rings of adjacent molecules.

Related literature

For details of the applications of conjugated organic molecules, see: Frederiksen et al. (2001 ▶); Zhao et al. (1995 ▶). For heterocycle-based two-photon absorbing chromophores exhibiting large TPA cross-sections, see: Huang et al. (2003 ▶).

Experimental

Crystal data

C₃₅H₃₀N₂S₃
M _r = 574.79
Triclinic,
a = 7.199 (1) Å
b = 10.1694 (15) Å
c = 21.161 (2) Å
α = 77.412 (1)°
β = 88.425 (3)°
γ = 81.129 (2)°
V = 1493.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 298 (2) K
0.50 × 0.38 × 0.31 mm

Data collection

Bruker SMART CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.875, T _max = 0.920
7820 measured reflections
5185 independent reflections
3229 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.129
S = 1.04
5185 reflections
361 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807065063/xu2372sup1.cif

e-64-0o257-sup1.cif^{(24.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065063/xu2372Isup2.hkl

e-64-0o257-Isup2.hkl^{(253.9KB, hkl)}

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

Acknowledgments

This work was supported by the Education Committee of Anhui Province, China (KJ2007B089). We thank Professor D.-Q. Wang of Liao Cheng University for assistance with the crystal structure determination.

supplementary crystallographic information

Comment

Two-photon absorption (TPA) processes in conjugated organic molecules have aroused considerable attention due to their potential applications in optical data storage, three-dimension fluorescence imaging, photodynamic therapy, two-photon upconversion lasing and three-dimension lithographic microfabrication (Frederiksen et al., 2001; Zhao et al., 1995). A sustained level of fundamental research over the past ten years has left organic nonlinear optical (NLO) well positioned to make a technological impact in a variety of disciplines. Some studies showed that the heterocycle-based two-photon absorbing chromophores exhibit large TPA cross-sections (Huang et al., 2003). As part of our ongoing investigtion on heterocycle-based two-photon absorbing chromophores, the title compound has been prepared and its crystal structure is presented here.

The molecule structure is shown in Fig. 1. Bond lengths and angles are normal. The C7-containing and C22-containing benzene rings are nearly coplanar with the pyrimidine ring, dihedral angles being 8.59 (2)° and 8.40 (2)°, respectively. In the crystal structure, π-π stacking is observed between nearly parallel pyrimidine and C10ⁱ-containing benzene rings as shown in Fig. 2 [symmetry code: (i) 1 + x,y,z]; the dihedral angle and centroid-to-centroid separation being 8.69 (13)° and 3.5808 (17) Å, respectively.

Experimental

At room temperature, t-BuOK (5.6 g, 50 mmol) was placed into a dry mortar and milled to very small, then 2-thiomethyl-4,6-dimethylpyrimidine (1.54 g, 10 mmol) and 4-benzylthiobenzalaldehyde (4.56 g, 20 mmol) were added and mixed. The mixture was milled vigorously for about 20 min. The mixture became sticky and then continuously milled for 10 min. After completion of the reaction (monitored by TLC), the mixture was dispersed in 100 ml me thanol. The residual solid was filtered and recrystallized from anhydrous dichloromethane/methanol solution, to give microcrystals (2.87 g, yield 50%). Single crystals suitable for X-ray analysis were obtained by slow evaporation from a dichloromethane/2-propanol (3:1) solution.