[N,N′-Bis(4-chlorobenzylidene)-2,2-dimethylpropane-1,3-diamine-κ2 N,N′]iodidocopper(I)

Reza Kia; Hoong-Kun Fun; Hadi Kargar

doi:10.1107/S160053680900107X

. 2009 Jan 17;65(Pt 2):m197. doi: 10.1107/S160053680900107X

[N,N′-Bis(4-chlorobenzylidene)-2,2-dimethylpropane-1,3-diamine-κ² N,N′]iodidocopper(I)

Reza Kia ^a, Hoong-Kun Fun ^a,^*, Hadi Kargar ^b

PMCID: PMC2968316 PMID: 21581796

Abstract

The molecule of the title compound, [CuI(C₁₉H₂₀Cl₂N₂)], lies across a crystallographic mirror plane. The coordination around the copper centre is distorted trigonal planar, with a bite angle of 94.40 (7)°. A six-membered chelate ring is formed by the coordination of iminic N atoms of the bidentate ligand to the Cu^I atom, adopting a chair conformation. This conformation is required if the local symmetry of the metal coordination site is in accordance with a mirror plane that passes through the metal atom normal to the line connecting the N atoms. The dihedral angle between the benzene rings is 78.66 (5)°. The crystal structure is stabilized by weak intermolecular C—H⋯π interactions, which link the molecules into chains along the b axis.

Related literature

For puckering parameters, see: Cremer & Pople (1975 ▶). For related literature and the catalytic applications, see, for example: Killian et al. (1996 ▶); Jung et al. (1996 ▶); Small et al. (1998 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[CuI(C₁₉H₂₀Cl₂N₂)]
M _r = 537.71
Monoclinic,
a = 16.2770 (1) Å
b = 12.2983 (1) Å
c = 10.6255 (1) Å
β = 92.249 (1)°
V = 2125.37 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.74 mm⁻¹
T = 296 (2) K
0.44 × 0.31 × 0.28 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.334, T _max = 0.463
39802 measured reflections
4869 independent reflections
4157 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.067
S = 1.02
4869 reflections
122 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900107X/hk2609sup1.cif

e-65-0m197-sup1.cif^{(15.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900107X/hk2609Isup2.hkl

e-65-0m197-Isup2.hkl^{(238.6KB, 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
C8—H8A⋯Cg1ⁱ	0.97	2.92	3.7220 (19)	141

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Symmetry code: (i) Inline graphic . Cg1 is the centroid of the C1–C6 benzene ring.

Acknowledgments

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant (No. 305/PFIZIK/613312). RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship. HK thanks PNU for financial support.

supplementary crystallographic information

Comment

In recent years, an increasing amount of research has been focused on the design and preparation of mono- or di-nuclear mixed ligand transition metal complexes containing neutral, chelating nitrogen ligands. Early and late transition metal complexes of this type have extensively been used as catalysts for a wide categories of reactions, including olefin polymerization (Killian et al., 1996) and oxygen activation (Jung et al., 1996). In this context, diverse chelating Schiff base type ligands, amines and pyridine derivatives (Small et al., 1998) have successfully been applied in the preparation of these homogeneous catalysts. Here we report the crystal structure of an aldimine Schiff base ligand with copper(I) iodide. To the best of our knowledge, the title compound is the first tricoordinate complex of an aldimine bis-Schiff base ligand with copper(I) iodide adopting triginal planar geometry.

The title compound, I, Fig. 1, lies across a crystallographic mirror plane. Atoms I1, Cu1, C9, C10 and C11 lies on this mirror plane. The asymmetric unit of (I) is composed of one-half of the molecule. The coordination geometry around copper has a distorted trigonal planar geometry. The deviation of the Cu atom from the N1/N1A/I1 plane is -0.1213 (8) Å. A six-membered chelate ring is formed in this case by the coordination of iminic nitrogen atoms of the bidentate ligand which adopts the chair conformation with the ring puckering paremeters (Cremer & Pople 1975) of Q = 0.7001 (14) Å, Θ = 7.72 (11)°, Φ = 0.0 (9)°. This conformation is required if the local symmetry of the metal coordination site is in accordance with a mirror plane that passed through the metal atom normal to the line connecting the nitrogen atoms. The dihedral angle between the phenyl rings is 78.66 (5)°. The crystal structure is stabilized by weak intermolecular C—H···π interactions (Cg1 is the centroid of the C1–C6 benzene ring) which link the molecules into chains along the b-axis (Fig. 2 and Table 1).

Experimental

N,N'-Bis(4-chlorobenzylidene)-2,2-dimethylpropane (694 mg, 2 mmol) was added dropwise to a suspension of CuI (380 mg, 2.0 mmol) in 50 ml of THF. After 15 minutes a clear yellowish solution was obtained. The volume of the reaction mixture was reduced until the formation of a yellow precipitate occurred. Single crystals suitable for X-ray diffraction were grown from the acetonitrile solution.