4-Methyl-6-(piperidin-1-yl)pyrimidin-2-amine

S Sreenivasa; K E ManojKumar; T Srinivasan; P A Suchetan; B S Palakshamurthy; D Velumurgan

doi:10.1107/S1600536812050982

. 2013 Jan 9;69(Pt 2):o197. doi: 10.1107/S1600536812050982

4-Methyl-6-(piperidin-1-yl)pyrimidin-2-amine

S Sreenivasa ^a,^*, K E ManojKumar ^a, T Srinivasan ^b, P A Suchetan ^c, B S Palakshamurthy ^d, D Velumurgan ^b

PMCID: PMC3569258 PMID: 23424481

Abstract

The title compound, C₁₀H₁₆N₄, crystalizes with two molecules (A and B) in the asymmetric unit in which the dihedral angles between the piperidine and pyrimidine rings are 47.5 (1) and 10.3 (1)°. The four C atoms of the pyrimidine ring in one of the molecules are disordered over two sets of sites with occupancy factors 0.508 (11):0.492 (11). In the crystal, the A molecules are linked to one another through N—H⋯N hydrogen bonds, generating R ₂ ²(8) ring patterns and forming inversion dimers. These dimers are further connected on either side to a B molecule through pairs of N—H⋯N hydrogen bonds, resulting in a tetrameric unit.

Related literature

For background to pyrimidine derivatives and their biological activity, see: Patel et al. (2003 ▶) and for a related structure see: Sreenivasa et al. (2012 ▶). For hydrogen bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₁₆N₄
M _r = 192.27
Monoclinic,
a = 13.9605 (4) Å
b = 8.7564 (3) Å
c = 17.7055 (6) Å
β = 104.381 (2)°
V = 2096.57 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.972, T _max = 0.985
15644 measured reflections
3708 independent reflections
2657 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.171
S = 1.10
3708 reflections
308 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(34.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812050982/sj5288sup1.cif

e-69-0o197-sup1.cif^{(34.3KB, cif)}

Click here for additional data file.^{(181.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050982/sj5288Isup2.hkl

e-69-0o197-Isup2.hkl^{(181.8KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812050982/sj5288Isup3.cml

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
N3—HN3B⋯N1ⁱ	0.86 (2)	2.19 (2)	3.043 (2)	173.3 (19)
N3—HN3A⋯N5	0.90 (2)	2.34 (2)	3.210 (2)	162.1 (17)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Dr S. C. Sharma, Vice Chancellor, Tumkur University, for his constant encouragement. BSP thanks Dr H. C. Devarajegowda, Department of Physics, Yuvarajas College (constituent), University of Mysore, for his support and guidence.

supplementary crystallographic information

Comment

Compounds with a nitrogen-containing heterocyclic ring, such as pyrimidine, are promising candidates for drug design. Pyrimidine derivatives form a component in a number of useful drugs and are associated with many biological and therapeutic activities (Patel et al., 2003). With this in mind, we synthesized the title compound to study its crystal structure.

The title compound crystallizes with two molecules in the asymmetric unit with the piperidine rings in each molecule adopting chair conformations. The dihedral angles between the piperidine ring and pyrimidine rings in the two molecules are 47.5 (1)^o and 10.3 (1)^o respectively, compared to 14.00 (1)° observed in 1-(2-amino-6-methylpyrimidin-4-yl)-N,N-dimethylpiperidin-4-aminium chloride (Sreenivasa et al., 2012).

In the crystal structure, the molecules are linked to one another through N—H···N hydrogen bonds generating R₂²(8) ring patterns (Bernstein et al., 1995) forming inversion related dimers. These dimers are further connected to one another through a second N—H···N hydrogen bonds resulting in a tetrameric unit.

Experimental

2-Amino-4-chloro-6-methylpyrimidine(1.39 mmol) was dissolved in acetonirile (3 ml). To this solution, piperidine (1.66 mmol) Xantphos (4,5-bis-diphenylphosphino-9,9-dimethylxanthene), Pd(OAc)₂ and Cs₂CO₃ (0.0695, 0.139 and 2.78 mmole respectively) were added. The reaction mixture was irradiated in a microwave at 60° C for 1.5 hrs. The reaction was monitored by TLC. Acetonitrile was removed under vacuum and the crude product was purified by column chromatography using CH₂Cl₂/methanol as eluents. The single-crystal required for the X-ray diffraction was grown by the slow evaporation technique from CH₂Cl₂ and MeOH (1:4).