6-Chloro-N-methyl-5-nitro-N-phenyl­pyrimidin-4-amine

Fuqiang Shi; Li-Hong Zhu; Li Mu; Long Zhang; Ya-Feng Li

doi:10.1107/S1600536811037664

. 2011 Sep 20;67(Pt 10):o2689. doi: 10.1107/S1600536811037664

6-Chloro-N-methyl-5-nitro-N-phenylpyrimidin-4-amine

Fuqiang Shi ^a, Li-Hong Zhu ^a, Li Mu ^b, Long Zhang ^a, Ya-Feng Li ^a,^*

PMCID: PMC3201521 PMID: 22064444

Abstract

In the title compound, C₁₁H₉ClN₄O₂, the dihedral angle between the aromatic rings is 79.67 (8)°. π–π stacking between centrosymmetrically related pairs of pyrimidine rings occurs along [100] [centroid–centroid separations = 3.4572 (8) and 3.5433 (7) Å].

Related literature

For a related structure, see: Shi et al. (2011 ▶).

Experimental

Crystal data

C₁₁H₉ClN₄O₂
M _r = 264.67
Triclinic,
a = 6.8980 (14) Å
b = 8.9282 (18) Å
c = 11.427 (2) Å
α = 73.76 (3)°
β = 86.80 (3)°
γ = 84.21 (3)°
V = 672.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.44 × 0.38 × 0.13 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.885, T _max = 0.964
5925 measured reflections
2730 independent reflections
1742 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.154
S = 1.07
2730 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2000 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811037664/ng5229sup1.cif

e-67-o2689-sup1.cif^{(14.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037664/ng5229Isup2.hkl

e-67-o2689-Isup2.hkl^{(134KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037664/ng5229Isup3.cml

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

Acknowledgments

This project is sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (grant No. 20071108) and the Scientific Research Foundation for the Returned Overseas Team, Chinese Education Ministry.

supplementary crystallographic information

Comment

Here, the crystal structure of 6-chloro-N-methyl-5-nitro-N-phenylpyrimidin-4-amine, the precursor of 6-chloro-N-methyl-N-phenylpyrimidine-4,5-diamine (Shi et al., 2011) is determined by X-ray single crystal diffraction.

In the structure of (I) (Fig. 1), the dihedral angle between the aromatic rings is 79.667 (81)°. Uninterrupted aromatic π-π stacking between centrosymmetrically related pairs of pyrimidine rings occurs along with [100] direction [centroid – centroid separation = 3.4572 (8)Å or 3.5433 (7)Å].

Experimental

To a solution of 4,6-dichloro-5-nitro-pyrimidine (2.08 g, 10.8 mmol), and triethylamine (13.0 mL, 0.55 mmol) in anhydrous THF (25 mL) was added a solution of N-methylbenzylamine (0.85 mL, 10.8 mmol) in anhydrous THF (15 mL) slowly. The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo, diluted with water, and extracted with EtOAc. The organic phase was washed with 1N HCl, brine, dried over anhydrous MgSO₄, and concentrated in vacuo to yield the crude product as a solid. Purification by recrystallization from methanol provided the desired pure product, 6-chloro-N-methyl-5-nitro-N-phenylpyrimidin-4-amine (yellow solid, 1.85g, 64.7%, 130.3-131.4 °C). ¹H NMR (CDCl₃, 400 Hz), δ: 8.51 (s, 1H), 7.393-7.37(m, 3H), 7.17-7.15(m, 2H), 3.57 (s, 3H); ¹³C NMR (CDCl₃, 100 Hz), δ: 156.6, 153.9, 152.4, 142.2, 129.8, 128.6, 126.3, 41.7. ES-MS: 265.0 [(M + H⁺)].