(1R,2R,E,E)-N,N′-Bis(4-chloro­benzyl­idene)cyclo­hexane-1,2-diamine

Hamid Arvinnezhad; Khosrow Jadidi; Behrouz Notash

doi:10.1107/S1600536812000724

. 2012 Jan 14;68(Pt 2):o407–o408. doi: 10.1107/S1600536812000724

(1R,2R,E,E)-N,N′-Bis(4-chlorobenzylidene)cyclohexane-1,2-diamine

Hamid Arvinnezhad ^a, Khosrow Jadidi ^a,^*, Behrouz Notash ^a

PMCID: PMC3275080 PMID: 22347025

Abstract

The title Schiff base ligand, C₂₀H₂₀Cl₂N₂, was prepared by condensation of commercially available p-chlorobenzaldehyde and (R,R)-1,2-diammoniumcyclohexane mono-(+)-tartrate. The cyclohexane ring adopts a chair conformation. The dihedral angle between the two aromatic rings is 62.52 (8)°. The crystal structure is stabilized by an intermolecular C—H⋯Cl hydrogen bond.

Related literature

For the crystal structures of some Schiff bases derived from cyclohexane-1,2-diamine, see: Fan et al. (2011 ▶); Glidewell et al. (2005 ▶); Saleh Salga et al. (2010 ▶). For applications of chiral Schiff base ligands, see: Da Silva et al. (2011 ▶); Przybylski et al. (2009 ▶); Gupta & Sutar (2008 ▶); Dhar & Taploo (1982 ▶); Munslow et al. (2001 ▶); Gillespie et al. (2002 ▶); Kureshy et al. (2001 ▶); Takenaka et al. (2002 ▶). For the synthesis of the title compound, see: Larrow & Jacobsen (1998 ▶); Periasamy et al. (2001 ▶).

Experimental

Crystal data

C₂₀H₂₀Cl₂N₂
M _r = 359.28
Orthorhombic,
a = 5.5058 (11) Å
b = 15.734 (3) Å
c = 21.302 (4) Å
V = 1845.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 120 K
0.5 × 0.23 × 0.15 mm

Data collection

Stoe IPDS 2T diffractometer
12920 measured reflections
4973 independent reflections
4065 reflections with I > 2σ(I)
R _int = 0.088

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.113
S = 1.13
4973 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (1983 ▶), 2099 Friedel pairs
Flack parameter: −0.11 (7)

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2005 ▶); 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812000724/bt5777sup1.cif

e-68-0o407-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812000724/bt5777Isup2.hkl

e-68-0o407-Isup2.hkl^{(243.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812000724/bt5777Isup3.cml

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
C3—H3A⋯Cl1ⁱ	0.97	2.81	3.525 (3)	131

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Vice President of Research Affairs at Shahid Beheshti University, General Campus, for financial support.

supplementary crystallographic information

Comment

The class of chiral chelating Schiff bases are significant compounds in chemistry so that several reviews have been published on these substances (Da Silva et al., 2011; Przybylski et al., 2009; Gupta and Sutar 2008). Because of their stereochemical structures as well as their industrial properties (Dhar & Taploo, 1982) and potent biological activities (Da Silva et al., 2011; Przybylski et al., 2009) they are very attractive synthetic targets. Furthermore, it should be stressed that these useful and recyclable materials have been widely used in various enantioselective reactions, such as cyclopropanation (Munslow et al., 2001), aziridination (Gillespie et al., 2002), epoxidation (Kureshy et al., 2001), Diels-Alder reaction (Takenaka et al., 2002) as ligands or catalysts.

The asymmetric unit of the title compound which contains one molecule of related Schiff base compound is shown in Fig. 1. The reaction scheme for the synthesis of the title Schiff base is presented in Fig. 2. The bond distances and angles in the title compound are in agreement with related structures (Fan et al., 2011; Glidewell et al., 2005; Saleh Salga et al., 2010). The crystal structure is stabilized by an intermolecular C—H···Cl hydrogen bond (Fig. 3 & Table 1).

Experimental

In a 25 ml two-necked round bottom flask with a reflux condenser, (R,R)-1,2-diammoniumcyclohexane mono-(+)-tartrate (2.64 g 10 mmol, 2 eq) and K₂CO₃ (2.76 g 20 mmol, 2 eq) were dissolved in H₂O (3 ml) (Larrow & Jacobsen 1998). The mixture was stirred and heated gently (~50 °C) for 10 min. Then a solution of p-chlorobenzaldehyde (2.8 g 20 mmol, 2 eq) in EtOH (10 ml) was poured in dropping funnel and added dropwise. The reaction mixture was stirred and refluxed for further 2 hrs. The mixture was cooled to room temperature and concentrated in vacuo. The residue was dissolved in CH₂Cl₂ (10 ml) and washed with saturated sodium bicarbonate (5 ml) and dried over Na₂SO₄. The organic layer was evaporated to yield crude product. Recrystallization in hot EtOH (7 ml) afford desired compound as colorless needles. 3.47 g, 97% yield, mp. 150 °C (mp 148–150°C), [α]²⁰_D= -308° (c=1, CHCl₃) ([α]²⁰_D= -136 (c=1, CHCl₃))(Periasamy et al., 2001).