Crystal structure of 2,6-bis­[(1H-pyrazol-1-yl)meth­yl]pyridine

Kyung-sun Son; Jeong Oh Woo; Daeyoung Kim; Sung Kwon Kang

doi:10.1107/S1600536814017474

. 2014 Aug 6;70(Pt 9):o973. doi: 10.1107/S1600536814017474

Crystal structure of 2,6-bis[(1H-pyrazol-1-yl)methyl]pyridine

Kyung-sun Son ^a, Jeong Oh Woo ^a, Daeyoung Kim ^a, Sung Kwon Kang ^a,^*

PMCID: PMC4186076 PMID: 25309287

Abstract

In the title compound, C₁₃H₁₃N₅, the planes of the pyrazolyl groups are nearly perpendicular to that of the central pyridine ring, making dihedral angles of 87.77 (8) and 85.73 (7)°. In the crystal, weak C—H⋯N hydrogen bonds link the molecules into layers extending parallel to (10-1).

Keywords: crystal structure, pyridine, purazole, tridentate ligand, catalysis

Related literature

For the synthesis of the title compound, see: Reger et al. (2005 ▶). For metal complexes with similar ligands, see: Sharma et al. (2011 ▶); Ojwach et al. (2007 ▶); Manikandan et al. (2000 ▶, 2001 ▶); Halcrow & Kilner (2002 ▶). For potential applications of the ligand in catalysis, see: Karam et al. (2005 ▶).

Experimental

Crystal data

C₁₃H₁₃N₅
M _r = 239.28
Monoclinic,
a = 7.481 (3) Å
b = 9.076 (4) Å
c = 19.021 (8) Å
β = 95.471 (5)°
V = 1285.7 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.26 × 0.2 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
25319 measured reflections
3136 independent reflections
2260 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.149
S = 1.09
3136 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814017474/is5371sup1.cif

e-70-0o973-sup1.cif^{(759.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017474/is5371Isup2.hkl

e-70-0o973-Isup2.hkl^{(172.2KB, hkl)}

Click here for additional data file.^{(5.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814017474/is5371Isup3.cml

Click here for additional data file.^{(961.8KB, tif)}

. DOI: 10.1107/S1600536814017474/is5371fig1.tif

Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability ellipsoids.

Click here for additional data file.^{(2.7MB, tif)}

. DOI: 10.1107/S1600536814017474/is5371fig2.tif

Part of the crystal structure of the title compound, showing molecules linked by intermolecular C—H⋯N hydrogen bonds (dashed lines).

CCDC reference: 1016859

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N15ⁱ	0.93	2.62	3.550 (3)	178
C6—H6B⋯N12ⁱⁱ	0.97	2.54	3.430 (2)	152

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

Acknowledgments

This work was supported by the research fund of Chungnam National University.

supplementary crystallographic information

S1. Experimental

To a stirred solution of 2,6-pyridinedimethanol (0.28 g, 2 mmol) and NaOH (0.8 g, 20 mmol) in THF/water (7.5/7.5 ml) was added a solution of p-toluenesulfonyl chloride (0.761 g, 4 mmol) in THF (7.5 ml) at 0 °C. After 4 h of stirring, the mixture was poured into 20 ml of water and extracted with methylene chloride. The organic phase was washed with saturated aqueous NaCl solution and distilled water and dried over Na₂SO₄, and the solvent was removed in vacuo to afford 2,6-pyridine-dimethylene-ditosylate (0.788 g, 88%) as a white powder. In a separate flask under a nitrogen atmosphere, a solution of pyrazole (0.22 g, 3.2 mmol) in dry THF (5 ml) was added dropwise to a suspension of NaH (0.08 g, 3.2 mmol) in dry THF (5 ml) at 0 °C. After 15 min of stirring, a clear solution of NaPz was obtained. A solution of 2,6-pyridine-dimethylene-ditosylate (0.73 g, 1.6 mmol) in dry THF (7.5 ml) was added to this solution; the mixture was stirred overnight and filtered, and the solvent was removed. The crude product was purified by column chromatography on silica gel with ethyl acetate as eluent to afford 0.30 g (76%) of pure ligand as a white solid. Single crystals of the title compound were obtained by slow diffusion of hexane into a concentrated solution of the white solid in THF at room temperature within 1–2 days.