1,3-Dibenzyl-2-(2-chloro­phen­yl)-4-methyl­imidazolidine

Augusto Rivera; Lorena Cardenas; Jaime Ríos-Motta; Václav Eigner; Michal Dušek

doi:10.1107/S1600536812047575

. 2012 Nov 24;68(Pt 12):o3427–o3428. doi: 10.1107/S1600536812047575

1,3-Dibenzyl-2-(2-chlorophenyl)-4-methylimidazolidine

Augusto Rivera ^a,^*, Lorena Cardenas ^a, Jaime Ríos-Motta ^a, Václav Eigner ^b,^c, Michal Dušek ^c

PMCID: PMC3589010 PMID: 23476246

Abstract

In the title compound, C₂₄H₂₅ClN₂, the methine, methylene and methyl C atoms of the methyl-substituted imidazolidine ring are disordered over two sets of sites with a refined occupancy ratio of 0.834 (4):0.166 (4). Each disordered ring assumes an envelope conformation with an N atom as the flap. The pendant benzyl rings are oriented equatorially with respect to the imidazolidine ring. The chlorophenyl ring is inclined to the mean plane of the four planar atoms of the major component of the imidazolidine ring by 76.27 (12)°. The dihedral angles between the chlorophenyl ring and the two benzyl rings are 55.31 (9) and 57.50 (8)°; the dihedral angle between these latter rings is 71.59 (9)°. In the crystal, molecules are linked by C—H⋯Cl interactions and a number of weak C—H⋯π interactions, involving all three aromatic rings, forming a three-dimensional structure.

Related literature

For uses of imidazolidine-bridged bis(phenol) derivatives in coordination chemistry, see: Xu et al. (2007 ▶). For related structures, see: Yang et al. (2009 ▶); Xia et al. (2007 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₄H₂₅ClN₂
M _r = 376.9
Monoclinic,
a = 7.1858 (1) Å
b = 9.8577 (2) Å
c = 29.3310 (5) Å
β = 96.8591 (15)°
V = 2062.80 (6) Å³
Z = 4
Cu Kα radiation
μ = 1.70 mm⁻¹
T = 120 K
0.44 × 0.32 × 0.21 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.62, T _max = 0.751
39415 measured reflections
3665 independent reflections
3464 reflections with I > 3σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.144
S = 2.91
3665 reflections
260 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: JANA2006.

Supplementary Material

Click here for additional data file.^{(21.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812047575/su2527sup1.cif

e-68-o3427-sup1.cif^{(21.6KB, cif)}

Click here for additional data file.^{(151.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047575/su2527Isup2.hkl

e-68-o3427-Isup2.hkl^{(151.2KB, hkl)}

Click here for additional data file.^{(7.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812047575/su2527Isup3.cml

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

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

Cg1, Cg2 and Cg3 are the centroids of the C1–C6, C12–C17 and C18–C23 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H1C9⋯Cl24	0.96	2.58	3.1596 (16)	119
C21—H1c21⋯Cg2ⁱ	0.96	2.87	3.6324 (19)	137
C11—H2c11⋯Cg2ⁱⁱ	0.96	2.82	3.6192 (19)	142
C4—H1c4⋯Cg3ⁱⁱⁱ	0.96	2.79	3.695 (2)	157
C26—H1c26⋯Cg1ⁱⁱⁱ	0.96	2.91	3.688 (2)	139

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

Acknowledgments

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia, for financial support of this work, as well as the Institutional research plan (No. AVOZ10100521) of the Institute of Physics. VE and MD acknowledge the suport provided by the project Praemium Academiae of the Academy of Sciences (ASCR), Czech Republic.

supplementary crystallographic information

Comment

As part of our studies on the synthesis of new imidazolidine derivatives we have prepared the title compound. It is an imidazolidine-bridged bis(phenol) which can serve as a useful precursor for the synthesis of lanthanide complexes of great potential application in homogeneous catalysis (Xu et al., 2007), and herein we report on its crystal structure.

In the title compound, Fig. 1, the methyl substituted imidazolidine ring exhibits molecular disorder over two orientations, with a refined occupancy ratio of 0.834 (4):0.166 (4) for atoms (C25,C26,C27):(C25',C26',C27'). The bond lengths (Allen et al., 1987) and angles are close to normal. In the imidazolidine ring, the bond lengths and angles are similar to those reported for closely related structures (Yang et al., 2009; Xia et al., 2007).

Each disordered component of the imidazolidine ring [N8/C9/N10/C25(25')/C26(26')] adopts an envelope conformation on N10 (major component) and N8 (minor component), respectively, with puckering parameters of Q2 = 0.427 (2) Å and φ2 = 252.5 (3)° for the major component, and Q2 = 0.555 (6) Å and φ2 = 178.7 (8)° for the minor component [Cremer & Pople, 1975].

The chlorophenyl ring attached to C9 (C18—C23) is inclined to the mean plane of the four planar atoms of the major component of the imidazolidine ring by 76.27 (12) °. The dihedral angles between the chlorophenyl ring (C18–C23) and the two benzyl rings (C1-C6) and (C12-C17) are 55.31 (9) and 57.50 (8)°, respectively. The pendant phenyl rings of the benzyl groups are oriented equatorially to the imidazolidine ring. The dihedral angle between these rings is 71.59 (9)°.

In the crystal, molecules are linked by C-H···Cl interactions and a number of weak C—H···π interactions, involving all three aromatic rings (Table 1), forming a three-dimensional structure.

Experimental

A toluene solution of N¹,N²-dibenzylpropane-1,2-diamine was refluxed for 8 h with 4-chlorobenzaldehyde in a molar ratio of 1.1:1.0. The mixture was evaporated on a rotary evaporator. The residue was cooled, and the precipitate was filtered off. It was then washed with cold ethanol, dried in air, and recrystallized from ethanol [Yield 81%; M.p. 352-353 K].