2-(4-Methyl­phen­yl)-1H-imidazo[4,5-f][1,10]phenanthroline

Ling Ma; Liping Lu; Miaoli Zhu

doi:10.1107/S1600536811008853

. 2011 Mar 12;67(Pt 4):o864–o865. doi: 10.1107/S1600536811008853

2-(4-Methylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline

Ling Ma ^a, Liping Lu ^a, Miaoli Zhu ^a,^*

PMCID: PMC3099870 PMID: 21754145

Abstract

In the title compound, C₂₀H₁₄N₄, all the non-H atoms are roughly coplanar with an r.m.s. deviation of 0.0776 Å. In the crystal, molecules are linked by N—H⋯N hydrogen bonds, forming chains along the ( Inline graphic ). The chains are connected by intermolecular C—H⋯N hydrogen bonds and π–π stacking interactions between inversion-related phenanthroline, imidazole and phenyl rings with centroid–centroid distances in the range 3.777 (1)–3.905 (1) Å.

Related literature

For the biological activity of complexes of metal ions with 1,10-phenanthroline and its derivatives, see: Gao et al. (2009 ▶); Lu et al. (2003 ▶); Yuan et al. (2009 ▶, 2010 ▶); Chen et al. (2010 ▶). For aromatic π–π stacking interactions in related structures, see: Lu et al. (2004a ▶,b ▶,c ▶,d ▶); Ma et al. (2010 ▶); Ye et al. (2005 ▶); Zhang et al. (2005 ▶).

Experimental

Crystal data

C₂₀H₁₄N₄
M _r = 310.35
Monoclinic,
a = 9.1609 (8) Å
b = 15.5398 (13) Å
c = 11.725 (1) Å
β = 108.892 (1)°
V = 1579.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.976, T _max = 0.984
10917 measured reflections
2790 independent reflections
2182 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.107
S = 1.05
2790 reflections
222 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811008853/lw2058sup1.cif

e-67-0o864-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008853/lw2058Isup2.hkl

e-67-0o864-Isup2.hkl^{(137KB, 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
N4—H4⋯N1ⁱ	0.908 (19)	2.106 (19)	3.0131 (19)	176.0 (17)
C1—H1⋯N3ⁱⁱ	0.93	2.57	3.479 (2)	165

Open in a new tab

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

Acknowledgments

The authors acknowledge the National Natural Science Foundation of China (grant No. 20471033), the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry (20093602), the Provincial Natural Science Foundation of Shanxi Province (grant No. 2010011011–2) and the Overseas Returned Scholar Foundation of Shanxi Province (200808) for financial support.

supplementary crystallographic information

Comment

We have been interested in the bioactivity research of the complexes of metal ions with 1,10-phenanthroline and its derivatives, such as nuclease activity of mono (1,10-phenanthroline) copper complex (Lu et al., 2003), protein tyrosine phosphatases inhibition activities of oxovanadium complexes with polypyridyl derivatives (Yuan et al., 2009,2010; Gao et al., 2009), selective OFF-ON fluorescent sensor for zinc in aqueous solution and living cells (Chen et al., 2010). As we know, 1,10-phenanthroline and its derivatives, 2,2'-bipyridyl-like, are good planar ligands in metal-organic compounds, in which there are strong π–π stacking interactions (Ye et al., 2005; Lu et al., 2004a, 2004b, 2004c; 2004d; Zhang et al., 2005; Ma et al., 2010). We report here the structure of (I) (Fig. 1), which was synthesized from 1,10-Phenanthroline-5,6-dione and 4-methylbenzaldehyde. All non-hydrogen atoms of (I) are coplanar with a 0.0776 value of r.m.s. deviation of fitted atoms. The molecules are linked by N—H···N hydrogen bonds to form one-dimensional chains (Fig. 2), and the chains are connected by intermolecular C—H···N hydrogen bonds and π–π stacking interactions between inversion related phenanthroline and phenyl rings to complete the hydrogen bonding network in the crystal structure. The stacking distance π–π is in the range of 3.777 (1) to 3.905 (1) Å, namely Cg1···Cg3ⁱ 3.905 (1), Cg2···Cg3ⁱ 3.867 (1), Cg3···Cg3ⁱⁱ 3.777 (1) Å. Cg1, Cg2, and Cg3 for the centroids of rings N1/C1—C5, C4—C7/C11/C12, C14—C19, respectively, symmetry codes i 1 - x,-y,1 - z; ii 2 - x,-y,1 - z.

Experimental

1,10-Phenanthroline-5,6-dione (1.2 mmol), 4-methylbenzaldehyde (1.0 mmol), and ammonium acetate (4 mmol) were added in 20 ml of glacial acetic acid with a constant of stirring, and the mixture was refluxed for 2 h. When the reaction was cooled to room temperature, poured in 20 ml of water. The solution was neutralized with ammonia to pH 7. The precipitate was filtered off and recrystallized from methanol solution to give (I) for X-ray diffraction at room temperature.