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

Nura Suleiman Gwaram; Siti Munirah Saharin; Hamid Khaledi; Hapipah Mohd Ali

doi:10.1107/S1600536811011512

. 2011 Mar 31;67(Pt 4):m513. doi: 10.1107/S1600536811011512

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

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

PMCID: PMC3099768 PMID: 21754017

Abstract

In the title compound, [Ni(NCS)₂(C₁₁H₁₇N₃)(H₂O)], the Ni^II ion is six-coordinated by the N,N′,N"-tridentate Schiff base N atoms, two cis-positioned N-bound isothiocyanate groups and one water molecule. In the crystal, O—H⋯S hydrogen bonds link adjacent molecules into infinite layers parallel to the ac plane. The layers are further connected into a three-dimensional network via C—H⋯π interactions. The –CH₂–N(CH₃)₂ fragment is disordered over two sets of sites in a 0.556 (5):0.444 (5) ratio.

Related literature

For the structure of a similar mononuclear nickel(II) thiocyanate complex, see: Suleiman Gwaram et al. (2011 ▶). For dimeric nickel(II) thiocyanate complexes with similar Schiff bases, see: Diao (2007 ▶); Bhowmik et al. (2010 ▶).

Experimental

Crystal data

[Ni(NCS)₂(C₁₁H₁₇N₃)(H₂O)]
M _r = 384.16
Monoclinic,
a = 12.8404 (2) Å
b = 14.2623 (3) Å
c = 9.5868 (2) Å
β = 99.467 (1)°
V = 1731.75 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.37 mm⁻¹
T = 100 K
0.22 × 0.19 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.753, T _max = 0.864
7792 measured reflections
3698 independent reflections
3451 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.070
S = 1.02
3698 reflections
234 parameters
16 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ▶), 1798 Friedel pairs
Flack parameter: 0.020 (11)

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 datablocks I, global. DOI: 10.1107/S1600536811011512/go2008sup1.cif

e-67-0m513-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011512/go2008Isup2.hkl

e-67-0m513-Isup2.hkl^{(181.3KB, hkl)}

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

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

Cg1 is the centroid of the N1,C1–C5 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯S1ⁱ	0.82 (2)	2.38 (2)	3.181 (3)	164 (4)
O1—H1A⋯S2ⁱⁱ	0.84 (2)	2.35 (2)	3.190 (3)	178 (4)
C7—H7C⋯Cg1ⁱⁱⁱ	0.98	2.88	3.531 (3)	125

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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 mixed-ligand complex was obtained via the treatment of nickel(II) ion with the Schiff base N,N-dimethyl-N'-[methyl(2-pyridyl)methylene]ethane-1,2-diamine, prepared in situ, and the thiocyanate salt. The Schiff base acts as an N,N',N"-tridentate chelate and the two thiocyanate ions behave in an N-donor fashion towards the Ni^II ion. The geometry around the metal center is completed by one water O atom. This arrangement is similar to what was observed in the nickel(II) thiocyanate complex of a similar Schiff base (Suleiman Gwaram et al., 2011). In contrast, the metal ions in the nickel(II) thiocyanate complex of N,N-dimethyl-N'-(2-pyridylmethylene)ethane-1,2-diamine (Diao, 2007) and N,N-diethyl-N'-[methyl(2-pyridyl)methylene]ethane-1,2-diamine (Bhowmik et al., 2010) are doubly bridged into dimers by N:S-bridging thiocyanate ligands. In the present structure, the adjacent molecules are connected into 2-D arrays in ac plane via O—H···S interactions (Table 1, Fig. 2). A C—H···π interaction (Table 1) connects the layers into a three-dimensional structure.

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 for 2 h followed by addition of a solution of nickel(II) acetate tetrahydrate (0.41 g, 1.65 mmol) and sodium thiocyanate (0.27 g, 3.3 mmol) in a minimum amount of water. The resulting solution was refluxed for 30 min, then set aside at room temperature. Brown crystals of the title compound were obtained by slow evaporation of the resulting reaction mixture.