1,2-Diphenyl-1H-imidazo[4,5-f][1,10]phenanthroline

S Rosepriya; A Thiruvalluvar; J Jayabharathi; M Venkatesh Perumal; R J Butcher; J P Jasinski; J A Golen

doi:10.1107/S1600536811010890

. 2011 Mar 26;67(Pt 4):o989. doi: 10.1107/S1600536811010890

1,2-Diphenyl-1H-imidazo[4,5-f][1,10]phenanthroline

S Rosepriya ^a, A Thiruvalluvar ^a,^*, J Jayabharathi ^b, M Venkatesh Perumal ^b, R J Butcher ^c, J P Jasinski ^d, J A Golen ^d

PMCID: PMC3099849 PMID: 21754246

Abstract

In the title compound, C₂₅H₁₆N₄, the fused ring system is essentially planar [maximum deviation = 0.1012 (15) Å]. The imidazole ring makes dihedral angles of 77.41 (8) and 56.26 (8)° with the phenyl rings attached to nitrogen and carbon, respectively. The dihedral angle between the two phenyl rings is 65.50 (8)°. Weak C—H⋯π interactions are found in the crystal structure.

Related literature

For 1,2-diphenyl-1H-imidazo[4,5-f][1,10]phenanthroline derivatives, see: Hadadzadeh et al. (2006 ▶). For metal complexes of the 1,10-phenanthroline-5,6-dione ligand, see: Goss & Abruna (1985 ▶).

Experimental

Crystal data

C₂₅H₁₆N₄
M _r = 372.42
Triclinic,
a = 8.8693 (7) Å
b = 10.0637 (6) Å
c = 11.8960 (9) Å
α = 100.219 (6)°
β = 110.310 (7)°
γ = 102.475 (6)°
V = 934.63 (14) Å³
Z = 2
Cu Kα radiation
μ = 0.63 mm⁻¹
T = 170 K
0.43 × 0.38 × 0.26 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.965, T _max = 1.000
5832 measured reflections
3522 independent reflections
3121 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.117
S = 1.05
3522 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010890/hg5009sup1.cif

e-67-0o989-sup1.cif^{(25.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010890/hg5009Isup2.hkl

e-67-0o989-Isup2.hkl^{(169.2KB, hkl)}

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

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

Cg4 and Cg6 are the centroids of the C4–C6/C11/C12/C17 and C24–C29 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯Cg6ⁱ	0.95	2.86	3.757 (3)	157
C25—H25⋯Cg4ⁱⁱ	0.95	2.75	3.4835 (16)	135

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

Acknowledgments

JPJ acknowledges the NSF-MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

1,2-diphenyl-1H-imidazo[4,5-f][1,10]phenanthroline derivatives play important roles as molecular scaffolding for supramolecular assemblies, building block for the synthesis of metallo-dendrimers, thin films of luminescent complexes and ligands for synthesis of ring opening metathesis polymerization (ROMP) (Hadadzadeh et al., 2006). Metal complexes of phen-dione ligand allow for the variation and control of redox properties over a wide range as well as the fine tuning of potentials through pH changes (Goss & Abruna, 1985). Since our group doing the research in organic light emitting devices, we are interested to use the title compound as ligand for synthesizing Ir(III) complexes.

In the title compound (Fig. 1), C₂₅H₁₆N₄, the fused ring system is essentially planar [maximum deviation of 0.1012 (15) Å for N13]. The imidazole ring makes dihedral angles of 77.41 (8) and 56.26 (8)° with the phenyl ring (C18—C23) attached to N1 and phenyl ring (C24—C29) attached to C2 respectively. The dihedral angle between the two phenyl rings is 65.50 (8)°. Further, weak C15—H15···π interaction involving phenyl (C24—C29) ring and C25—H25···π interaction involving (C4/C5/C6/C11/C12/C17) ring are found in the crystal structure (Table 1).

Experimental

Pure 1,10-Phenanthroline-5,6-dione (2.10 g, 10 mmol) in ethanol (10 ml), aniline (0.91 g, 10 mmol), ammonium acetate (0.77 g, 10 mmol) and benzaldehyde (1.0 g, 10 mmol) was added about 1 h by maintaining the temperature at 333 K. The reaction mixture was refluxed for 7 days and extracted with dichloromethane. The solid separated was purified by column chromatography using Benzene: Ethyl acetate as the eluent. Yield: 1.48 g (40%). Crystals suitable for X-ray diffraction studies were grown by slow solvent evaporation of a solution of the compound in dichloromethane.