1-(2-Amino-6-methyl­pyrimidin-4-yl)-N,N-dimethyl­piperidin-4-aminium chloride

S Sreenivasa; KE ManojKumar; PA Suchetan; T Srinivasan; B S Palakshamurthy; D Velmurgan

doi:10.1107/S1600536812046533

. 2012 Nov 17;68(Pt 12):o3371. doi: 10.1107/S1600536812046533

1-(2-Amino-6-methylpyrimidin-4-yl)-N,N-dimethylpiperidin-4-aminium chloride

S Sreenivasa ^a,^*, KE ManojKumar ^a, PA Suchetan ^b, T Srinivasan ^c, B S Palakshamurthy ^d, D Velmurgan ^c

PMCID: PMC3588967 PMID: 23476203

Abstract

In the title molecular salt, C₁₂H₂₂N₅ ⁺·Cl⁻, the cation is protonated at the dimethyl-substituted tertiary N atom. The piperidine ring adopts a chair conformation with the exocyclic N—C bond in an equatorial orientation. The dihedral angle between the piperidine ring (all atoms) and the pyrimidine ring is 14.00 (1)°. In the crystal, the ions are connected by N—H⋯N hydrogen bonds, forming inversion dimers, which are further connected by N—H⋯Cl hydrogen bonds. Aromatic π–π stacking interactions [centroid–centroid separation = 3.4790 (9) Å] are also observed in the structure.

Related literature

For background to pyrimidine derivatives and their biological activity, see: Patel et al. (2003 ▶).

Experimental

Crystal data

C₁₂H₂₂N₅ ⁺·Cl⁻
M _r = 271.80
Monoclinic,
a = 24.7908 (12) Å
b = 8.2419 (4) Å
c = 13.8764 (6) Å
β = 91.968 (2)°
V = 2833.6 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 K
0.21 × 0.18 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) ▶ T _min = 0.947, T _max = 0.994
10807 measured reflections
2502 independent reflections
2266 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.107
S = 1.08
2502 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; 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.^{(21.8KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046533/hb6988sup1.cif

e-68-o3371-sup1.cif^{(21.8KB, cif)}

Click here for additional data file.^{(123KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046533/hb6988Isup2.hkl

e-68-o3371-Isup2.hkl^{(123KB, hkl)}

Click here for additional data file.^{(5.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812046533/hb6988Isup3.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—H3NB⋯Cl1	0.84 (2)	2.60 (2)	3.4284 (17)	167.2 (17)
N5—H5N⋯Cl1ⁱ	0.878 (19)	2.20 (2)	3.0785 (14)	177.1 (17)
N3—H3NA⋯N2	0.86 (2)	2.26 (2)	3.114 (2)	175.5 (18)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

Nitrogen-containing heterocyclic ring such as pyrimidine is a promising structural moiety for drug design. Pyrimidine derivatives form a component in a number of useful drugs and are associated with many biological and therapeutical activities (Patel et al., 2003). In this view, we synthesized the title compound to study its crystal structure. The title compound crystallizes in monoclinic C2/c space group with the piperidine ring in the molecule adopting chair conformation. The dihedral angle between the piperidine ring and the pyrimidine ring in the molecule is 14.00 (1)°. In the crystal structure, the molecules are linked to one another through N—H···N hydrogen bonds generating R₂²(8) ring patterns forming inversion related dimers. These dimers are further connected to one another through N—H···Cl hydrogen bonds and weak π-π interactions.

Experimental

To a solution of 2-amino-4-chloro-6-methylpyrimidine (1.39 mmol) in acetonitrile (3 ml) was added 4-(dimethylamino)piperidine (1.66 mmol), xantphos (0.0695 mmol), Pd(OAc)₂ (0.139 mmol) and Cs₂CO₃ (2.78 mmol). The reaction mixture was irradiated with microwave radiation at 60° C for 1.5 hrs. The reaction was monitored by TLC. The solvent was removed under reduced pressure and the crude product was purified by column chromatography using MDC/methanol as eluent. Colourless prisms were obtained from slow evaporation of the solution of the compound in dilute alcohol.