5-Phenyl-2-(4-pyrid­yl)pyrimidine

Marie-Pierre C Santoni; Siu Hong Yu; Garry S Hanan; Anna Proust; Bernold Hasenknopf

doi:10.1107/S160053680800398X

. 2008 Feb 13;64(Pt 3):o584. doi: 10.1107/S160053680800398X

5-Phenyl-2-(4-pyridyl)pyrimidine

Marie-Pierre C Santoni ^a,^*, Siu Hong Yu ^a, Garry S Hanan ^a, Anna Proust ^b, Bernold Hasenknopf ^b

PMCID: PMC2960877 PMID: 21201923

Abstract

The title compound, C₁₅H₁₁N₃, crystallizes with two independent molecules in the asymmetric unit. The dihedral angles between the phenyl and pyridine rings in each molecule are 53.48 (5) and 50.80 (5)°. In the crystal structure, weak intermolecular C—H⋯N hydrogen bonds connect molecules into one-dimensional chains. In addition, the crystal structure is stabilized by weak C—H⋯π(arene) interactions.

Related literature

For related literature, see: Fang et al. (2002 ▶, 2007 ▶); Medlycott & Hanan (2005 ▶, 2006 ▶); Spek (2003 ▶). graphic file with name e-64-0o584-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₁N₃
M _r = 233.27
Triclinic,
a = 9.2813 (5) Å
b = 9.3609 (5) Å
c = 13.9001 (7) Å
α = 71.462 (2)°
β = 86.957 (2)°
γ = 75.788 (3)°
V = 1109.54 (10) Å³
Z = 4
Cu Kα radiation
μ = 0.68 mm⁻¹
T = 100 (2) K
0.40 × 0.38 × 0.08 mm

Data collection

Bruker SMART 6000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.734, T _max = 0.947
15167 measured reflections
3967 independent reflections
3226 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.139
S = 1.00
3967 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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 (local program).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800398X/lh2593sup1.cif

e-64-0o584-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800398X/lh2593Isup2.hkl

e-64-0o584-Isup2.hkl^{(194.4KB, 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
C7—H7⋯N5ⁱ	0.95	2.55	3.3818 (18)	147
C9—H9⋯N6ⁱⁱ	0.95	2.56	3.4027 (18)	148
C22—H22⋯N2ⁱ	0.95	2.54	3.3784 (18)	147
C24—H24⋯N3ⁱⁱ	0.95	2.56	3.4049 (19)	149
C1—H1⋯Cg3ⁱⁱⁱ	0.95	2.91	3.5925 (15)	129
C4—H4⋯Cg3	0.95	2.72	3.4163 (15)	130
C12—H12⋯Cg1ⁱ	0.95	2.89	3.5844 (15)	131
C15—H15⋯Cg1^iv	0.95	2.92	3.5202 (15)	122
C17—H17⋯Cg6^v	0.95	2.84	3.5561 (16)	133
C20—H20⋯Cg6ⁱⁱ	0.95	2.85	3.5251 (15)	129
C26—H26⋯Cg5	0.95	2.86	3.5242 (15)	128
C29—H29⋯Cg5^vi	0.95	2.77	3.4451 (15)	129

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg1 is the centroid of the N1/C1-C5 ring, Cg3 is the centroid of the N4/C16–C20 ring, Cg5 is the centroid of the C10–C15 ring and Cg6 is the centroid of the C25–C30 ring.

Acknowledgments

The authors are grateful to the Natural Sciences and Engineering Research Council of Canada, the Ministère de l’Education du Québec and the Université de Montréal for financial support. The authors gratefully acknowledge Mme Françine Bélanger-Gariépy (Laboratoire de diffraction des rayons X, Université de Montréal, Canada) for the teaching of crystallography to MPS. Yuan-Qing Fang is acknowledged for help and guidance with the synthesis.

supplementary crystallographic information

Comment

Ruthenium polypyridyl complexes have long attracted attention due to their exceptional photophysical properties which makes them suitable as chromophores in light-harvesting devices (Medlycott & Hanan, 2005, 2006). Recently, we have reported new pyrimidine-substituted terpyridine ligands and their Ru(II) polypyridyl complexes (Fang et al., 2002, 2007). Introduction of the pyrimidine motif on a terpyridine unit leads to planarization of the system through hydrogen bonds, thus extending pi-delocalization in the acceptor ligand of the metal-to-ligand charge transfer (MLCT) emitting excited-states, which improves the photophysical properties of the complexes. The title compound C₁₅H₁₁N₃ (3) [see Fig. 3] was designed for the enhanced π-acceptor character of pyridyl-type ligands for coordination and supramolecular chemistry.

The title compound crystallizes with two molecules per asymmetric unit. The assignment of the nitrogen atoms was confirmed by comparing the observed and expected torsion angles and bond lengths. Ligand (3) is less planar than the terpyridyl analogue (Fang et al., 2007) despite weak intramolecular C—H···lone pair (N) interactions. All non-bonded N···H distances are shorter than 2.75 Å [N2···H2 = 2.57 Å, N3···H4 = 2.57 Å, N5···H17 = 2.62 Å, N6···H19 = 2.51 Å]. The dihedral angles between the phenyl and pyridine rings in each molecule are 53.48 (5)° and 50.80 (5)°. These deviations from planarity, in part, may be influenced by weak intermolecular C—H···N hydrogen bonds connecting molecules into one-dimensional chains and in addition, by the crystal structure being stabilized by weak C—H···π stacking interactions between "head-to-tail" molecules.

Experimental

4-Pyridylamidine hydrochloride (1) (10,0 g, 63.5 mmol), 2-phenyl-1,3-bis(dimethylamino)trimethinium hexafluorophosphate (2) (1 eq, 22.1 g, 63.5 mmol) and NaOMe (1.2 eq, 4.13 g, 76.5 mmol) were dissolved in anhydrous MeOH (500 ml). The resulting yellow solution was refluxed for 15 h under N₂. The white solid was isolated by filtration and dried under vacuum to give white shiny micro-crystals (11.0 g, 74%) of pure title compound (3). These crystals were suitable for X-ray diffraction measurements, m.p. 477.8–478.5 K. Anal Calcd for C₁₅H₁₁N₃ (233.3): C, 77.23; H, 4.75; N, 18.01. Found: C, 77.04; H, 4.69; N, 17.86.