14-(2,3-Dichloro­phen­yl)-9,10-dimethyl­benzimidazo[1,2-a]benzo[f][1,8]naphthyridine-6-carbonitrile

Andrii V Tarasov; Tatyana A Volovnenko; Roman I Zubatyuk; Oleg V Shishkin; Yulian M Volovenko

doi:10.1107/S1600536809008447

. 2009 Mar 19;65(Pt 4):o792. doi: 10.1107/S1600536809008447

14-(2,3-Dichlorophenyl)-9,10-dimethylbenzimidazo[1,2-a]benzo[f][1,8]naphthyridine-6-carbonitrile

Andrii V Tarasov ^a,^*, Tatyana A Volovnenko ^a, Roman I Zubatyuk ^b, Oleg V Shishkin ^b, Yulian M Volovenko ^a

PMCID: PMC2969033 PMID: 21582516

Abstract

In the title compound, C₂₇H₁₆Cl₂N₄, the benzimidazo[1,2-a]benzo[f][1,8]naphthyridine system is nearly planar (r.m.s. deviation for all non-H atoms = 0.033 Å). The dichlorophenyl substituent is rotated by −67.5 (2)° from this plane. In the crystal structure, molecules form stacks along the crystallographic (100) direction due to π–π stacking interactions with a centroid–centroid distance of 3.4283 (9) Å.

Related literature

For the synthesis of the title compound and a series of similar compounds, see: Volovnenko et al. (2006 ▶). For 1,2-fused benzimidazo heterocycles and their fluorescence properties, see: Gokhale & Seshadri (1987 ▶); Rajagopal & Seshadri (1991 ▶). For the biological properties of isoquinoline derivatives, see: Shamma (1972 ▶); Kametami & Fukomoto (1981 ▶); Bijan & Basu (1965 ▶); Neumeyer & Weinhard (1970 ▶).

Experimental

Crystal data

C₂₇H₁₆Cl₂N₄
M _r = 467.34
Triclinic,
a = 8.5588 (8) Å
b = 11.0751 (13) Å
c = 12.2332 (11) Å
α = 76.985 (9)°
β = 75.986 (8)°
γ = 85.438 (9)°
V = 1095.77 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.6 × 0.1 × 0.1 mm

Data collection

Oxford-Diffraction Xcalibur-3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.82, T _max = 0.97
20237 measured reflections
4290 independent reflections
2405 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.072
S = 1.01
4290 reflections
300 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008447/sj2589sup1.cif

e-65-0o792-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008447/sj2589Isup2.hkl

e-65-0o792-Isup2.hkl^{(210.2KB, hkl)}

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

supplementary crystallographic information

Comment

In the past few decades 1,2-fused benzimidazo heterocycles have attracted attention because of their fluorescent properties (Gokhale & Seshadri, 1987; Rajagopal & Seshadri 1991). On the other hand isoquinoline derivatives exhibit a wide range of biological effects and are of great interest to synthetic as well as pharmaceutical organic chemists (Shamma, 1972; Kametami & Fukomoto, 1981; Bijan & Basu, 1965; Neumeyer & Weinhard, 1970).

In a previous paper (Volovnenko et al., 2006) we have described the synthesis of a series of 14-arylbenzimidazo[1,2-a]benzo[f]-1,8-naphthyridine-6-carbonitriles. We report herein the crystal structure of the title compound, which is the derivative of the new heterocyclic system, benzimidazo[1,2-a]benzo[f]-1,8-naphthyridine.

The molecular structure of the title compound is illustrated in Fig. 1. The benzimidazo[1,2-a]benzo[f]-1,8-naphthyridine system is nearly planar (RMS deviation of the non-hydrogen atoms from mean plane is 0.033 Å). Benzene ring is rotated with respect to this plane (the C5—C6—C7—C23 torsion angle is -67.5 (2)°). This rotation results in the loss of conjugation between π systems of the heterocycle and benzene ring. In crystal molecules form stacked chains along the a axis (Fig. 2) due to stacking interactions between the π systems of the pentacyclic fragments. The distance between the parallel planes is 3.4186 (8) Å.

Experimental

The title compound was synthesized by the reaction of 3-chloro-1-(2,3-dichlorophenyl)isoquinoline-4-carbaldehyde (1 mmol) with (5,6-dimethyl-1H-benzimidazol-2-yl)acetonitrile (1 mmol) in dimethylformamide (3–4 ml). After refluxing for 3 h, the reaction mixture was left to stand for overnight. The resulting crude solid was filtered, washed twice with acetone (10 ml) and dried. Yield: 65%. Crystals suitable for X-ray analysis were obtained by slow crystallization from hot dimethylformamide.