2-Amino-6-(dimethyl­amino)pyridine-3,5-dicarbonitrile

Shaaban K Mohamed; Ahmed M Soliman; Eman M M Abdel-Raheem; Sohail Saeed; Wing-Tak Wong

doi:10.1107/S1600536812017278

. 2012 Apr 25;68(Pt 5):o1532. doi: 10.1107/S1600536812017278

2-Amino-6-(dimethylamino)pyridine-3,5-dicarbonitrile

Shaaban K Mohamed ^a, Ahmed M Soliman ^b, Eman M M Abdel-Raheem ^b, Sohail Saeed ^c,^*, Wing-Tak Wong ^d

PMCID: PMC3344634 PMID: 22590396

Abstract

The title compound, C₉H₉N₅, is slightly twisted from planarity, with a maximum deviation of 0.0285 (13) Å from the pyridine plane for the C atom bearing the amino group. The cyano groups are on different sides of the pyridine plane, with C- and N-atom deviations of 0.072 (3)/0.124 (4) and −0.228 (4)/−0.409 (5) Å from the pyridine plane. In the crystal, N—H⋯N and C—H⋯N hydrogen bonds connect the molecules into zigzag chains running along the c axis.

Related literature

For the synthesis of similar structures, see: Horton et al. (2012a ▶,b ▶); Soliman et al. (2012 ▶). For the biological significance of cyanoamino pyridines, see: Al-Haiza et al. (2003 ▶); Bhalerao & Krishnaiah (1995 ▶); Deo et al. (1990 ▶); Murata et al. (2003 ▶); Konda et al. (2010 ▶); Altomare et al. (2000 ▶); Hosni & Abdulla (2008 ▶); Shishoo et al. (1983 ▶).

Experimental

Crystal data

C₉H₉N₅
M _r = 187.21
Monoclinic,
a = 28.667 (7) Å
b = 3.9702 (10) Å
c = 17.950 (4) Å
β = 112.920 (3)°
V = 1881.7 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.32 × 0.21 × 0.03 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.972, T _max = 0.997
4846 measured reflections
1658 independent reflections
1173 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.147
S = 1.03
1658 reflections
138 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017278/im2369sup1.cif

e-68-o1532-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017278/im2369Isup2.hkl

e-68-o1532-Isup2.hkl^{(81.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812017278/im2369Isup3.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
N2—H1⋯N3ⁱ	0.88 (3)	2.25 (3)	3.119 (3)	167 (2)
N2—H2⋯N1ⁱⁱ	0.88 (3)	2.43 (3)	3.260 (3)	158 (3)
C3—H3⋯N4ⁱⁱⁱ	0.93	2.55	3.471 (4)	170

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors are thankful to the University of Hong Kong for providing the single-crystal X-ray crystallography facility.

supplementary crystallographic information

Comment

In continuation of our research interest in the synthesis of potential biologically active molecules (Soliman et al., 2012; Horton et al., 2012a,b), we got prompted to study the chemical and pharmacological characterization of new cyano-amino pyridine derivatives due to their vibrant chemical activities. Hence cyano-amino pyridines have been considered as convenient synthons due to their diverse applications particularly in organic synthesis (Shishoo et al., 1983; Deo et al., 1990; Bhalerao & Krishnaiah, 1995; Al-Haiza et al., 2003) and medicinal chemistry (Altomare et al., 2000; Hosni & Abdulla, 2008; Murata et al., 2003; Konda et al., 2010).

The title compound, 2-amino-6-(dimethylamino)-pyridine-3,5-dicarbonitrile, is slightly twisted. The maximum deviation from the mean plane of the pyridyl ring, N1/C1—C5 (marked with asterisk) is 0.0285 (13) Angstrom. The cyano groups are flipped to different sides of the pyridine plane with atoms C6 & N3 showing deviations of +0.072 (3) Å and +0.124 (4) Å, while atoms C7 & N4 are bent out of the pyridine plane by -0.228 (4) Å and -0.409 (5) Å, respectively.

Hydrogen bonding interactions are observed in the crystal lattice connecting the molecules into zigzag chains running along the c-axis. As it is expected, N—H···N interactions are shorter as the observed N4···H3(–C3) distance.

Experimental

The title compound (1) was obtained as a by-product from the reaction of 2-amino-6-chloropyridine-3,5-dicarbonitrile (1 mmol; 179 mg) with amino guanidine (1 mmol; 74 mg) in dimethylformamide. The reaction mixture was refluxed for 4 h at 426 K and then poured on cold water. A solid product was filtered off, dried and recrystallized from ethanol to afford cupric needles which were suitable for X-Ray diffraction without further recrystallization. Yield 45% and m.p. 453 K.