Dichlorido{N-[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine}copper(II)

Qiang Wang; Cai-Feng Bi; Da-Qi Wang; Yu-Hua Fan

doi:10.1107/S1600536809010149

. 2009 Mar 25;65(Pt 4):m439. doi: 10.1107/S1600536809010149

Dichlorido{N-[1-(2-pyridyl)ethylidene]ethane-1,2-diamine}copper(II)

Qiang Wang ^a, Cai-Feng Bi ^a,^*, Da-Qi Wang ^b, Yu-Hua Fan ^a

PMCID: PMC2968900 PMID: 21582376

Abstract

The title complex, [CuCl₂(C₉H₁₃N₃)], is mononuclear and contains a five-coordinate Cu^II atom. The geometry of the Cu^II atom can be described as tetragonal-pyramidal derived from the calculation of the value τ = 0.102. The three N atoms of the pyridine and ethane-1,2-diamine ligands and one Cl atom belong to the basal plane and the other Cl atom represents the axial position of the pyramid. The Cu atom is displaced by 0.2599 (2) Å from the basal plane towards the axial Cl atom. In the crystal, molecules are linked into chains by intermolecular N—H⋯Cl and C—H⋯Cl hydrogen bonds.

Related literature

For general background, see: Coles et al. (1998 ▶). For the calculation of the geometry parameter τ in five-coordinate complexes, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[CuCl₂(C₉H₁₃N₃)]
M _r = 297.66
Triclinic,
a = 7.2701 (10) Å
b = 8.8008 (12) Å
c = 9.5773 (15) Å
α = 82.940 (2)°
β = 76.289 (1)°
γ = 85.751 (2)°
V = 590.16 (15) Å³
Z = 2
Mo Kα radiation
μ = 2.27 mm⁻¹
T = 298 K
0.50 × 0.42 × 0.17 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.396, T _max = 0.699
2903 measured reflections
2021 independent reflections
1549 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.160
S = 1.04
2021 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809010149/si2162sup1.cif

e-65-0m439-sup1.cif^{(15.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809010149/si2162Isup2.hkl

e-65-0m439-Isup2.hkl^{(99.4KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—N2	1.977 (5)
Cu1—N3	2.002 (5)
Cu1—N1	2.050 (5)
Cu1—Cl2	2.2659 (17)
Cu1—Cl1	2.4812 (16)

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N3—Cu1—N1	158.54 (19)
N2—Cu1—Cl2	164.66 (16)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl1ⁱ	0.90	2.47	3.248 (5)	145
N3—H3B⋯Cl2ⁱⁱ	0.90	2.49	3.322 (5)	154
C6—H6⋯Cl2ⁱⁱⁱ	0.93	2.77	3.666 (7)	161
C4—H4⋯Cl1^iv	0.93	2.74	3.612 (7)	156
C1—H1A⋯Cl1^v	0.96	2.80	3.726 (6)	161

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

Acknowledgments

The authors acknowledge financial support by the Shandong Provincial Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University, People’s Republic of China.

supplementary crystallographic information

Comment

Schiff-base ligands have played an integral role in the development of coordination chemistry since the late 19t h century. The finding that metal complexes of these ligands are ubiquitous is a reflection of their facile synthesis, wide application and the accessibility of diverse structural modifications (Coles et al., 1998). We report here the synthesis and crystal structure of the title complex, a new copper(II) complex, with a tridentate Schiff base ligand derived from the condensation of 2-acetylpyridine and diamine.

The molecular structure of the title complex is shown in Fig.1. The Cu^II atom is five-coordinated. The basal plane for a tetragonal-pyramidal geometry is defined by the atoms N1, N2, N3 and Cl2, their mean deviation from this plane is 0.025 Å, and the Cu atom juts out of this plane by 0.2599 (2) Å. The axial position of the pyramid is occupied by atom Cl1. For this point of view, a geometry parameter τ, which is defined τ = (β - α)/60, applicable to five-coordinate structures within the structural continuum between trigonal bipyramidal and tetragonal or rectangular pyramidal. For a perfect tetragonal symmetry τ is zero, and for a perfect trigonal-bipyramidal geometry τ becomes 1.0 (Addison et al. 1984). In the title compound, the largest angles within the four atoms N1, N2, N3, Cl2 are β = 164.66 (16)° for N2–Cu1–Cl2, and α = 158.54 (19)° for N1–Cu1–N3. Thus, τ is (164.66–158.54)/60 = 0.102, indicating a 90% rectangular pyramidal geometry. Selected geometric parameters are presented in Table 1. As seen in Fig. 2, the molecules are linked into chains by intermolecular N—H···Cl and C—H···Cl hydrogen bonds (Table 2).

Experimental

2-acetylpyridine (10 mmol, 1205 mg) was added dropwise to a absolute ethanol (20 ml) of diamine (10 mmol, 611 mg). The mixture was heated under reflux with stirring for 3 h. An absolute ethanol solution (10 ml) of cupric chloride dihydrate (10 mmol, 1700 mg) was then added dropwise, and the mixture was stirred at room temperature for another 13 h. The solution was filtered off, the filterate was kept at room temperature for about three weeks, after which large green block-shaped crystals of the title complex suitable for X-ray diffraction analysis were obtained.