2,2′,2′′-[Nitrilo­tris(methyl­ene-p-phenyl­ene)]tribenzonitrile

Li-Zhuang Chen

doi:10.1107/S1600536808029784

. 2008 Sep 20;64(Pt 10):o1980. doi: 10.1107/S1600536808029784

2,2′,2′′-[Nitrilotris(methylene-p-phenylene)]tribenzonitrile

Li-Zhuang Chen ^a,^*

PMCID: PMC2959437 PMID: 21201180

Abstract

In the title compound, C₄₂H₃₀N₄, the conformations of the three wings of the molecule are not similar to each other as the torsion angles between the planes of the benzene rings are significantly different. In addition to van der Waals interactions, the crystal structure is stabilized only by intramolecular C—H⋯N hydrogen bonds.

Related literature

For related structures, see: Fox et al. (1996 ▶); Menage et al. (1992 ▶); Murthy & Karlin (1993 ▶); Schrock (1997 ▶); Foces-Foces et al. (1999 ▶); Chen et al. (2005 ▶); Iwasaki & Iwasaki (1972 ▶).

Experimental

Crystal data

C₄₂H₃₀N₄
M _r = 590.70
Monoclinic,
a = 21.257 (4) Å
b = 15.085 (3) Å
c = 10.294 (2) Å
β = 94.73 (3)°
V = 3289.5 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 298 (2) K
0.27 × 0.18 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.985, T _max = 0.989
32746 measured reflections
7524 independent reflections
4007 reflections with I > 2σ(I)
R _int = 0.081

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.187
S = 1.02
7524 reflections
415 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808029784/pv2103sup1.cif

e-64-o1980-sup1.cif^{(23.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029784/pv2103Isup2.hkl

e-64-o1980-Isup2.hkl^{(368.1KB, 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
C4—H4A⋯N3ⁱ	0.93	2.55	3.446 (5)	162
C24—H24A⋯N2ⁱⁱ	0.93	2.59	3.350 (4)	139

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

Acknowledgments

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

Tripodal ligands have shown tremendous scope in the synthesis of transition-metal complexes. Perhaps the most extensively studied examples are those comprising tris-(2-pyridylmethyl)amine, which has been widely exploited in complexes (Fox et al. 1996; Menage et al. 1992; Murthy & Karlin 1993), tris(2-aminobenzyl)amine (Foces-Foces et al. 1999), tris(2-chlorobenzl)amine and tris(2-bromobenzyl)amine (Chen et al. 2005) and tribenzylamine (Iwasaki & Iwasaki 1972). The construction of new members of this family of ligands is an important direction in the development of modern coordination chemistry (Schrock 1997). We report here the crystal structure of the title compound tris[4-(2-cyano-phenyl)benzyl]amine, (I).

In the title compound (Fig.1), the conformations of the three wings of the molecule do not appear to be similar as the torsion angles between the planes of benzene rings are significantly different from each other. The pairs of benzene rings in the three wings form dihedral angle of 47.70 (10)°, 54.36 (7)° and 87.89 (9)°, respectively. In addition to van der Waals interactions, the crystal structure is stabilized only by intramolecular C—H···N hydrogen bonds: C4—H4A···N3 and C24—H24A···N2 (Table 1).

Experimental

The title compount was obtained from the combination of 2-cyano-4'-(bromomethyl)biphenyl (8.13 g, 30.0 mmol) with 29% aqueous ammonia (2.64 g, 45.0 mmol) in ethanol (50 ml) at room temperature. A white solid precipitated during stirring over 24 h. The precipitate was collected by filtration, washed with ethanol, and allowed to air-dry to yield 2.67 g (43%) of colorless microcrystals. Recrystallization was effected from hot acetonitrile to yield colorless blocks suitable for X-ray analysis.