4-{4-Methyl-2-[(meth­yl)(2-methyl­phen­yl)amino]-1,3-thia­zol-5-yl}-N-(3-methyl­phen­yl)pyrimidin-2-amine

Hai-Bo Shi; Feng Xu; Hai-Bo Li; Wei-Xiao Hu

doi:10.1107/S1600536810053560

. 2011 Jan 8;67(Pt 2):o259. doi: 10.1107/S1600536810053560

4-{4-Methyl-2-[(methyl)(2-methylphenyl)amino]-1,3-thiazol-5-yl}-N-(3-methylphenyl)pyrimidin-2-amine

Hai-Bo Shi ^a,^b, Feng Xu ^c, Hai-Bo Li ^d, Wei-Xiao Hu ^b

PMCID: PMC3051713 PMID: 21522952

Abstract

In the title compound, C₂₃H₂₃N₅S, the thiazole ring and pyrimidine ring are almost coplanar, making a dihedral angle of 4.02 (9)°. in the crystal, weak intermolecular N—H⋯N interactions link pairs of molecules into centrosymmetric dimers.

Related literature

For general background to the biological activity of thiazole derivatives, see: Narayana et al. (2004 ▶). For the synthesis of the title compound, see: Bredereck et al. (1964 ▶).

Experimental

Crystal data

C₂₃H₂₃N₅S
M _r = 401.52
Triclinic,
a = 7.886 (2) Å
b = 9.576 (3) Å
c = 13.531 (4) Å
α = 86.590 (9)°
β = 81.657 (7)°
γ = 85.926 (8)°
V = 1007.2 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 103 K
0.53 × 0.37 × 0.15 mm

Data collection

Rigaku FC10/Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2008 ▶) T _min = 0.910, T _max = 0.973
9716 measured reflections
4535 independent reflections
3652 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.145
S = 1.04
4535 reflections
267 parameters
H-atom parameters constrained
Δρ_max = 0.88 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053560/ng5078sup1.cif

e-67-0o259-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053560/ng5078Isup2.hkl

e-67-0o259-Isup2.hkl^{(217.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5N⋯N3ⁱ	0.88	2.22	3.097 (2)	173

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are very thankful to the Natural Science Foundation of Ningbo City (grant No. 2009 A610185) for financial support. We are also grateful to the Beijing Institute of Technology for the X-ray diffraction measurements.

supplementary crystallographic information

Comment

Thiazole derivatives are found to be associated with various biological activities (Narayana et al., 2004). In order to further study the structure-activity relationship (SAR) of the thiazolyl-pyrimidine derivatives, we introduced arylamino group into 2-position of thiazole ring of thiazolyl-pyrimidine according to the general pyrimidine condensation method of Bredereck (Bredereck et al., 1964). But, it was found that the obtained compound was not desired compound that confirmed by ¹H NMR, MS. So, the structure of (I) was further determined using single-crystal X-ray diffraction.

The molecular structure of (I) is illustrated in Fig. 1. The thiazole ring (S1/C7/N2/C8/C9) and the pyrimidine ring (C10/C11/C12/N3/C13/N4) are almost planar, with a dihedral angle of 4.02 (9)°. The aniline rings (C1/C2/C3/C4/C5/C6/N1) and (C14/C15/C16/C17/C18/C19/N5) make dihedral angles of 80.96 (11) Å and 14.15 (9) Å with the thiazole ring, respectively. In the thiazole ring, the bond lengths S1—C7 [1.739 (2) Å], S1—C9 [1.748 (18) Å] and N2—C8 [1.372 (2) Å] correspond to typical single bond, and the C7—N2 [1.312 (2) Å], C8—C9 [1.373 (3) Å] belong to typical for double bonds. The crystal structure is stabilized by intermolecular weak N—H···N interactions (Fig. 2). Furthermore, every two molecules containing two N—H···N hydrogen bondings consists a dimer as octagon.

Experimental

A mixture of 3-dimethylamino-1-[4-methyl-2-(methyl-o-tolyl-amino)-thiazol-5-yl]-propenone (1.575 g, 5 mmol) and NaOH (0.2 g, 5 mmol) in 2-methoxylethanol (20 ml) was treated with N-m-tolyl-guanidine carbonate (1.58 g, 7.5 mmol). The reaction mixture was heated at 383 K under N₂ for 11 h. After concentration, the residue was filtered and washed liberally with ethanol and water. Recrystallization from acetone affored the title compound as dark yellow crystals, 1.17 g, m.p.455–458 K, yield 58.5%. Since the crystal product was not found to be suitable for X-ray diffraction studies,a few crystals were dissolved in 2-butanone, which was allowed to evaporate slowly to give yellow crystals of (I) suitable for X-ray diffraction studies. ¹H NMR(CDCl₃, TMS, 400 MHz, δp.p.m.): 8.24 (d, 1H, J = 5.2 Hz, py—H), 7.65 (s, 1H, Ar—H), 7.36–7.27 (m, 4H, Ar—H), 7.13–7.09 (m, 2H, Ar—H), 6.92 (s, 1H, Ar—H), 6.79 (d, 1H, J = 5.6 Hz, py—H), 3.49 (s, 3H, CH₃), 2.61 (s, 3H, CH₃), 2.29 (s, 3H, CH₃), 2.15 (s, 3H, CH₃). EIMS m/z (%): 401 (M⁺, 100), 386 (28), 368 (17), 283 (9), 222 (8), 129 (10), 118 (8), 98 (11), 91 (15), 83 (12), 73 (21), 65 (10), 57 (28).