{N,N-Dimethyl-N′-[1-(2-pyrid­yl)ethyl­idene]ethane-1,2-diamine-κ3 N,N′,N′′}bis­(thio­cyanato-κN)copper(II)

Nura Suleiman Gwaram; Hamid Khaledi; Hapipah Mohd Ali

doi:10.1107/S1600536811022057

. 2011 Jun 18;67(Pt 7):m930. doi: 10.1107/S1600536811022057

{N,N-Dimethyl-N′-[1-(2-pyridyl)ethylidene]ethane-1,2-diamine-κ³ N,N′,N′′}bis(thiocyanato-κN)copper(II)

Nura Suleiman Gwaram ^a, Hamid Khaledi ^a,^*, Hapipah Mohd Ali ^a

PMCID: PMC3151817 PMID: 21836914

Abstract

The asymmetric unit of the title compound, [Cu(NCS)₂(C₁₁H₁₇N₃)], consists of two crystallographically independent molecules. In each molecule, the Cu^II ion is five-coordinated in a distorted square-pyramidal geometry wherein the basal plane is defined by the N,N′,N"-tridentate Schiff base and one N-bound thiocyanate ligand. The second N-donor thiocyanate group, located at the apical site, completes the coordination environment. In the crystal, intermolecular C—H⋯S and C—H⋯N hydrogen bonds link adjacent molecules into infinite layers parallel to the ac plane. Intramolecular C—H⋯N interactions are also observed.

Related literature

For the structures of similar copper(II) isothiocyanate complexes, see: Xue et al. (2010 ▶); Yue et al. (2005 ▶). For the structure of the polymeric cadmium thiocyanate complex of the same Schiff base, see: Suleiman Gwaram et al. (2011 ▶). For a description of the geometry of complexes with five-coordinate metal atoms, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Cu(NCS)₂(C₁₁H₁₇N₃)]
M _r = 370.98
Triclinic,
a = 10.9895 (4) Å
b = 11.2172 (4) Å
c = 13.7549 (5) Å
α = 81.222 (2)°
β = 87.121 (2)°
γ = 79.702 (2)°
V = 1648.27 (10) Å³
Z = 4
Mo Kα radiation
μ = 1.58 mm⁻¹
T = 100 K
0.44 × 0.31 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.544, T _max = 0.821
14403 measured reflections
7159 independent reflections
5182 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.128
S = 1.00
7159 reflections
385 parameters
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022057/is2717sup1.cif

e-67-0m930-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022057/is2717Isup2.hkl

e-67-0m930-Isup2.hkl^{(350.3KB, 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—H4⋯N5ⁱ	0.95	2.58	3.429 (5)	149
C8—H8B⋯S4ⁱⁱ	0.99	2.82	3.788 (4)	167
C9—H9A⋯S4ⁱⁱⁱ	0.99	2.84	3.735 (4)	150
C22—H22A⋯S2ⁱⁱⁱ	0.99	2.81	3.749 (4)	159
C11—H11B⋯N5	0.98	2.60	3.156 (5)	116
C21—H21A⋯S1	0.99	2.84	3.727 (4)	150
C21—H21B⋯S2	0.99	2.82	3.793 (4)	167
C24—H24B⋯N10	0.98	2.60	3.193 (5)	119

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

Acknowledgments

The authors thank the University of Malaya for funding this study (FRGS grant No. FP004/2010B).

supplementary crystallographic information

Comment

The title compound was obtained upon the reaction of the Schiff base, N,N-dimethyl-N'-[methyl(2-pyridyl)methylene]ethane-1,2-diamine, with Cu^II ion in the presence of thiocyanate anion. There are two geometrically slightly different molecules in crystal structure. The weighted r.m.s. fit for the superposition of the non-H atoms in both molecules is 0.296 Å. Each metal ion is five-coordinated by the three N atoms from the Schiff base and two N-donor thiocyanate ligands. Similar arrangements are observed in the structures of related mixed-ligand copper(II) complexes (Xue et al., 2010; Yue et al., 2005). Different from those, in the cadmium(II) thiocyanate complex of the same Schiff base (Suleiman Gwaram et al., 2011), N:S bridging thiocyanates connect the metal ions into an octahedral polymeric structure. The Addison τ values (Addison et al., 1984) of 0.13 for Cu1 complex and 0.14 for Cu2 complex (τ = 0 for an ideal square pyramid and τ = 1 for an ideal trigonal bipyramid) imply distorted square-pyramidal geometries of the molecules. In the crystal, the adjacent molecules are bonded via C—H···S and C—H···N interactions (Table 1) into layers parallel to the ac plane. Moreover, intramolecular C—H···N hydrogen bonding occurs (Table 1).

Experimental

A mixture of 2-acetylpyridine (0.2 g, 1.65 mmol) and N,N-dimethylethyldiamine (0.15 g, 1.65 mmol) in ethanol (20 ml) was refluxed. After 2 hr a solution of copper(II) chloride dihydrate (0.28 g, 1.65 mmol) and sodium thiocyanate (0.27 g, 3.3 mmol) in a minimum amount of water was added. The resulting solution was refluxed for an hour, then left at room temperature. The green crystals of the title compound were obtained in a few days.