N-[2,6-Bis(1-methyl­eth­yl)phen­yl]pyridine-4-carboxamide

Baptiste Laramée; Mihaela Cibian; Garry S Hanan

doi:10.1107/S1600536812038846

. 2012 Sep 22;68(Pt 10):o2975–o2976. doi: 10.1107/S1600536812038846

N-[2,6-Bis(1-methylethyl)phenyl]pyridine-4-carboxamide

Baptiste Laramée ^a,^*, Mihaela Cibian ^a, Garry S Hanan ^a

PMCID: PMC3470342 PMID: 23125755

Abstract

In the title compound, C₁₈H₂₂N₂O, the dihedral angle between the benzene ring and the pyridine ring is 80.0 (1)°. In the crystal, N—H⋯O hydrogen bonds connect the molecules into chains along the b axis. The packing also features C—H⋯O and C—H⋯N hydrogen bonds and C—H⋯π interactions, one directed to the benzene ring and the other to the center of the pyridine ring.

Related literature

For general review and synthetic details about amide bond generation and application, see: Pattabiraman & Bode (2011 ▶). The title compound has not been reported in coordination chemistry, but complexes of similar ligands are known. For the use of such ligands in coordination chemistry, see: Baytekin et al. (2009 ▶); Hasegawa et al. (2007 ▶); Kumar et al. (2004 ▶). For related benzamide crystal structures, see: Saeed et al. (2010 ▶); Zhang & Zhao (2010 ▶); Roopan et al. (2009 ▶); Gowda et al. (2008 ▶). For background to the synthetic route, see: Boeré et al. (1998 ▶); Krajete et al. (2004 ▶); Schafer et al. (2011 ▶); Wallace et al. (1990 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₈H₂₂N₂O
M _r = 282.38
Monoclinic,
a = 9.0994 (1) Å
b = 9.8039 (1) Å
c = 18.1882 (2) Å
β = 96.8650 (4)°
V = 1610.93 (3) Å³
Z = 4
Cu Kα radiation
μ = 0.57 mm⁻¹
T = 150 K
0.20 × 0.12 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.895, T _max = 0.935
81057 measured reflections
3126 independent reflections
3000 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.097
S = 1.04
3126 reflections
198 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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: UdMX (Maris, 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812038846/nk2182sup1.cif

e-68-o2975-sup1.cif^{(26KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038846/nk2182Isup2.hkl

e-68-o2975-Isup2.hkl^{(153.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812038846/nk2182Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

Cg1 and Cg2 are the centroids of the phenyl and pyridyl rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H20⋯O1ⁱ	0.872 (16)	1.970 (16)	2.7985 (11)	158.3 (13)
C3—H3⋯O1ⁱ	0.95	2.54	3.4500 (12)	161
C5—H5⋯N2ⁱⁱ	0.95	2.61	3.4983 (13)	155
C6—H6⋯Cg1ⁱⁱⁱ	0.95	2.81	3.6467	150
C15—H15B⋯Cg2^iv	0.98	2.97	3.7858	143

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

Acknowledgments

The authors thank the Department of Chemistry of the Université de Montréal for access to the CCD facility. They thank Thierry Maris for useful crystallographic discussions and are grateful to the Université de Montréal for financial assistance.

supplementary crystallographic information

Comment

In the present work, N-[2,6-bis(1-methylethyl)phenyl]-4-pyridinecarboxamide has been synthesized as a potential ligand in coordination chemistry. The metal complexes of similar precursors are already known to catalyse hydroamination of aminoalkenes (Schafer et al. (2011)).

The molecular structure of the title compound is illustrated in Fig. 1. The bond distances are normal (Allen (2002)). The pyridyl ring is slightly tilted with respect to the central amide group at the angle of 5.7 (1)°, while the substituted phenyl ring is tilted by 79.8 (1)°.

Fig. 2 illustrates conventional intermolecular N—H···O hydrogen bonding, forming chains along b axis.

Experimental

N-[2,6-bis(1-methylethyl)phenyl]-4-pyridinecarboxamide was prepared by combining and modifying reported methods (Wallace et al. (1990); Boeré et al. (1998); Krajete et al. (2004)). Isonicotinic acid (8.00 g, 65.0 mmol) is refluxed in thionyl chloride (30.0 ml), under nitrogen atmosphere, for 3 h. The excess thionyl chloride is distilled off, to afford the corresponding isonicotinoyl chloride (HCl salt) as pale-yellow solid (not isolated). Dry dichloromethane (20.0 ml), dry pyridine (70.0 ml), and 2,6-diisopropylaniline (12.9 ml, 68.2 mmol) are added at 0°C (ice bath). The reaction mixture is left to heat to room temperature, and is subsequently refluxed for 2 h. The green-yellow suspension obtained is reduced to around 70 ml by evaporation under vacuum, and water (150 ml) is added. The green-yellow precipitate formed is recuperated as solid by filtration. Recrystallization from hot methanol at 4°C affords the desired N-(2,6-diisopropylphenyl)isonicotinamide as X-ray quality off-white needles, air dried (14.9 g, 52.7 mmol). Yield 81% 1H NMR (300 MHz, DMSO-d6) delta p.p.m. 10.05 (s, 1 H, NH) 8.80 (d, J=6 Hz, 2 H, H-py) 7.89 (d, J=6 Hz, 2 H, H-py) 7.28 - 7.37 (m, 1 H, p-H—Ph) 7.22 (d, J=8 Hz, 2 H, m-H—Ph) 3.05 (spt, J=7 Hz, 2 H, –CH-(CH3)2) 1.14 (dd, J=18, 7 Hz, 12 H, –CH-(CH3)2)