2-[Bis(5-chloro-2-pyridylamino)methyl]pyridine monohydrate

Davar M Boghaei; Mohammad Mahdi Najafpour; Vickie McKee

doi:10.1107/S1600536808035940

. 2008 Nov 22;64(Pt 12):o2428. doi: 10.1107/S1600536808035940

2-[Bis(5-chloro-2-pyridylamino)methyl]pyridine monohydrate

Davar M Boghaei ^a,^*, Mohammad Mahdi Najafpour ^a, Vickie McKee ^b

PMCID: PMC2960150 PMID: 21581396

Abstract

In the title compound, the dihedral angles between the 2-amino-5-chloropyridyl rings and the pyridine ring are 56.26 (6)° and 78.83 (5)°; the angle between the 2-amino-5-chloropyridyl rings is 72.42 (5)°. The solvent water molecules are linked to the organic compound by N—H⋯O, O—H⋯O, N—H⋯N and O—H⋯N hydrogen bonds. π⋯π Stacking interactions are also observed between the 2-amino-5-chloropyridyl rings (centroid⋯centroid distance = 3.243 Å).

Related literature

For related crystallographic studies, see: Makowska-Grzyska et al. (2003 ▶); Li et al. (2008 ▶); Peori et al. (2008 ▶).

Experimental

Crystal data

C₁₆H₁₃Cl₂N₅·H₂O
M _r = 364.23
Monoclinic,
a = 34.414 (3) Å
b = 4.4337 (3) Å
c = 26.236 (2) Å
β = 124.778 (1)°
V = 3288.0 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 150 (2) K
0.35 × 0.10 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.870, T _max = 0.980
14914 measured reflections
3778 independent reflections
2830 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.101
S = 1.04
3778 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808035940/wn2287sup1.cif

e-64-o2428-sup1.cif^{(15.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035940/wn2287Isup2.hkl

e-64-o2428-Isup2.hkl^{(185.3KB, 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
N2—H2N⋯N5ⁱ	0.87	2.15	2.994 (2)	165
N4—H4N⋯O1ⁱⁱ	0.87	2.18	2.993 (2)	156
O1—H1O⋯N1	0.82	1.98	2.773 (2)	164
O1—H2O⋯O1ⁱⁱⁱ	0.82	1.96	2.758 (2)	163

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

Acknowledgments

We are grateful to the Research Council of Sharif University of Technology, and Loughborough University for their financial support.

supplementary crystallographic information

Comment

Primary amines add to imines to form aminal compounds; these are not stable (Peori et al., 2008). The title compound, C₁₆H₁₃Cl₂N₅.H₂O, was synthesized by the reaction of 2-amino-5-chloropyridine with 2-pyridinecarbaldehyde in ethanol. Tris(pyridyl)amines are very common ligands and many complexes containing such ligands have been reported (Makowska-Grzyska et al., 2003; Li et al., 2008).

In the title compound, intermolecular N—H···O and N—H···N hydrogen bonds involving amine NH and pyridyl groups form a two dimensional network (Table 1 and Fig. 3). π–π stacking interactions are also observed between the 2-amino-5-chloropyridyl rings [centroid···centroid distance = 3.243 Å]. The dihedral angles between the 2-amino-5-chloropyridyl rings and the pyridine ring are 56.26 (6)° and 78.83 (5)°; the angle between the 2-amino-5-chloropyridyl rings is 72.42 (5)°.

Experimental

The title compound was synthesized by adding 2-pyridinecarbaldehyde (1 mmol, 107 mg) to a solution of 2-amino-5-chloropyridine (3 mmol, 386 mg) and manganese acetate (0.02 mmol, 4.90 mg) in ethanol (20 ml). The mixture was refluxed with stirring for 7 h. The resultant yellow solution was filtered. Colourless single crystals of the title compound suitable for X-ray structure determination were recrystallized from a mixture of ethanol / water (5/1) by slow evaporation of the solvents at room temperature over several days.