1-(4-Methyl­phen­yl)-2-[4-(trifluoro­methyl)phen­yl]-1H-phenanthro[9,10-d]imida­zole

T Mohandas; R Sathishkumar; J Jayabharathi; A Pasupathy; P Sakthivel

doi:10.1107/S1600536813009471

. 2013 Apr 13;69(Pt 5):o710. doi: 10.1107/S1600536813009471

1-(4-Methylphenyl)-2-[4-(trifluoromethyl)phenyl]-1H-phenanthro[9,10-d]imidazole

T Mohandas ^a, R Sathishkumar ^b, J Jayabharathi ^b, A Pasupathy ^c, P Sakthivel ^d,^*

PMCID: PMC3648243 PMID: 23723863

Abstract

In the title compound, C₂₉H₁₉F₃N₂, the tetracyclic ring system is essentially planar [maximum deviation from the best plane = 0.076 (1) Å] and makes dihedral angles of 78.10 (5) and 33.71 (4)° with the methylphenyl and fluorophenyl rings, respectively. An intramolecular C—H⋯π interaction occurs. In the crystal, pairs of C—H⋯π interactions link inversion-related molecules.

Related literature

For background to organic electroluminescent materials and devices, see: Adachi et al. (1995 ▶); Loy et al. (2002 ▶) and for the photophysical, electrochemical and mobility properties of phenanthroimidazole derivatives, see: Yuan et al. (2011 ▶). For applications of imidazole and phenanthrolene derivatives, see: Moylan et al. (1993 ▶); Bu et al. (1996 ▶); Wang et al. (2002 ▶). graphic file with name e-69-0o710-scheme1.jpg

Experimental

Crystal data

C₂₉H₁₉F₃N₂
M _r = 452.46
Triclinic,
a = 8.113 (3) Å
b = 11.733 (5) Å
c = 12.713 (2) Å
α = 76.397 (1)°
β = 73.490 (2)°
γ = 86.185 (5)°
V = 1127.7 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.967, T _max = 0.977
22540 measured reflections
22540 independent reflections
14735 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.236
S = 1.04
22540 reflections
310 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: APEX2 and SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Click here for additional data file.^{(32.5KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813009471/go2084sup1.cif

e-69-0o710-sup1.cif^{(32.5KB, cif)}

Click here for additional data file.^{(1.1MB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009471/go2084Isup2.hkl

e-69-0o710-Isup2.hkl^{(1.1MB, hkl)}

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

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

Cg1 and Cg2 are the centroids of the C15–C20 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Cg1	0.93	2.84	3.698 (2)	155
C26—H26⋯Cg2ⁱ	0.93	2.86	3.487 (2)	125

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Symmetry code: (i) Inline graphic .

Acknowledgments

PS and AP thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

Comment

The optical and conductive properties of the conjugated materials containing imidazole and phenanthroline heterocycles have found in many applications (Moylan et al.,1993, Bu et al.,1996, Wang et al.,2002).

The 1H-phenanthro[9,10 - d]imidazole is a promising building block in the field of molecular materials. It has many desirable properties such as good heat stability, ease of introduction into molecules used as chromophores, fluorescent in nature and readily tunable absorption wavelengths.

The study of organic electroluminescent materials and devices (Loy et al., 2002, Adachi et al., 1995) is therefore of great importance. The photophysical, electrochemical and mobility properties of phenanthroimidazole derivatives have been reported (Yuan et al., 2011).

As our research group deals with organic light emitting devices, we are interested in the title compound (I), Figure 1, as a ligand for inorganic complexes.

The dihedral angle between the phenanthrene moiety and the flourobenzene ring is 33.71 (4)° and to that of the benzene ring of methylphenyl is 78.10 (5)°. The dihedral angle between methylphenyl and benzene ring of trifluorobenzene ring is 72.60 (5)°. The maximum deviation of C12 atom from the mean plane of phenanthrotetracyclic system is 0.076 (1)°. The crystal structure is stabilized by C—H···π interactions. One of these, C12–H12···Cg1 is an intramolecular interaction. The other, C26–H26···Cg2 links the molecules into centrosymmetically related pairs across the centre-of-symmetry at (0.5, 0, 0.5), Figure 2. Cg1 and Cg2 are the centres of gravity of the benzene rings C15–C20 and C8–C13 respectively.

Experimental

A mixture of phenanthrene-9,10-dione (1.0 g, 4.8 mmol), ammonium acetate (1.48 g,19.2 mmol), 4-trifluoromethylbenzaldehyde (0.83 g, 4.8 mmol) and 4-methyl aniline (2.56 g, 24 mmol) were refluxed in ethanol (20 ml) at 80°C. The reaction was monitored by TLC and purified by column chromotography using petroleum ether: ethyl acetate (9:1) as the eluent. Yield: 0.69 g (52%). The compound was dissolved in dimethyl sulfoxide and allowed and slow evaporation produced crystal suitable for X-ray diffraction.