Bis{N-ethyl-2-[3-(hy­droxy­imino-κN)butan-2-yl­idene]hydrazinecarbothio­amide-κ2 N 2,S}nickel(II) dichloride

Halema Shaban Abduelftah; Amna Qasem Ali; Naser Eltaher Eltayeb; Siang Guan Teoh; Hoong-Kun Fun

doi:10.1107/S1600536811055383

. 2012 Jan 21;68(Pt 2):m183–m184. doi: 10.1107/S1600536811055383

Bis{N-ethyl-2-[3-(hydroxyimino-κN)butan-2-ylidene]hydrazinecarbothioamide-κ² N ²,S}nickel(II) dichloride

Halema Shaban Abduelftah ^a,^b, Amna Qasem Ali ^a,^b, Naser Eltaher Eltayeb ^a,^c,^‡, Siang Guan Teoh ^a,^*, Hoong-Kun Fun ^d,^§

PMCID: PMC3274909 PMID: 22346856

Abstract

In the title complex, [Ni(C₇H₁₄N₄OS)₂]Cl₂, the Ni^II ion is six-coordinated in a distorted octahedral geometry by four N atoms from the two imine and two oxime groups, and two S atoms from the thione groups. Two chloride ions complete the asymmetric unit. In the crystal, molecules are linked through N—H⋯Cl and O—H⋯Cl hydrogen bonds into an infinite chain propagating along [101].

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For a related structure, see: Choi et al. (2008 ▶). For the biological activity, pharmacological properties and analytical applications of thiosemicarbazones and their metal complexes, see: Cowley et al. (2002 ▶); Ming (2003 ▶); Lobana et al. (2004 ▶, 2007 ▶).

Experimental

Crystal data

[Ni(C₇H₁₄N₄OS)₂]Cl₂
M _r = 534.17
Monoclinic,
a = 18.4990 (11) Å
b = 14.2097 (9) Å
c = 9.2422 (6) Å
β = 98.542 (1)°
V = 2402.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 293 K
0.42 × 0.20 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.625, T _max = 0.869
30693 measured reflections
8190 independent reflections
6071 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.089
S = 1.03
8190 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811055383/is5020sup1.cif

e-68-0m183-sup1.cif^{(24.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811055383/is5020Isup2.hkl

e-68-0m183-Isup2.hkl^{(400.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ni1—N1	2.1247 (14)
Ni1—N2	2.0120 (12)
Ni1—N5	2.1258 (13)
Ni1—N6	2.0086 (12)
Ni1—S1	2.4089 (5)
Ni1—S2	2.4126 (5)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯Cl1ⁱ	0.730 (19)	2.47 (2)	3.1689 (17)	161 (2)
O2—H1O2⋯Cl1	0.84 (3)	2.20 (3)	3.0062 (14)	161 (2)
N7—H1N7⋯Cl2ⁱⁱ	0.87 (2)	2.34 (2)	3.1488 (16)	153.9 (17)
N3—H1N3⋯Cl1ⁱ	0.76 (2)	2.50 (2)	3.2015 (16)	154 (2)
O1—H1O1⋯Cl2	0.79 (3)	2.20 (3)	2.9396 (16)	157 (2)
N8—H1N8⋯Cl2ⁱⁱ	0.85 (2)	2.349 (19)	3.1567 (19)	159 (2)

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia for the RU research grant (1001/PKIMIA/815067). NEE thanks Universiti Sains Malaysia for a post-doctoral fellowship and the International University of Africa (Sudan) for providing research leave. HAF and AQA each thank the Ministry of Higher Education and the University of Sabha (Libya) for a scholarship.

supplementary crystallographic information

Comment

Thiosemicarbazones and their metal complexes have attracted significant attention because of their wide-ranging biological and pharmacological properties, analytical applications, specific structures, and chemical properties (Cowley et al., 2002; Ming, 2003; Lobana et al., 2007; Lobana et al., 2004). In this paper we report the crystal structure of bis{N-ethyl-2-[2-(hydroxyimino-κN)butan-2-ylidene]hydrazinecarbothioamide-κ²N²,S}nickle(II)dichloride.

In the mononuclear title complex (Fig. 1), [Ni(C₇H₁₄N₄OS)₂]Cl₂, the nickel(II) ion is six-coordinated in a distorted octahedral geometry by four N atoms from two imine groups and two oxime groups and two S atoms from two thione groups. The Ni—N and Ni—S bond distances (Table 1) and the bond angles around Ni1 are in agreement with the values found for related Ni(II) complex (Choi et al., 2008). Bond lengths and angles observed in the structure are normal (Allen et al., 1987). Ni1 is a meeting-point of four five-membered rings, namely: A (Ni1/S1/N2/N3/C9), B ((Ni1/S2/N6/N7/C12), C ((Ni1/N1/N2/C1/C2) and D ((Ni1/N5/N6/C5/C6).The dihedral angles between these four rings as follows: A/B = 87.11 (5)°, A/C = 4.37 (6)°, A/D = 88.83 (6)°, B/C = 88.55 (6)°, B/D = 4.26 (6)° and C/D = 86.88 (7)°. In the crystal, molecules are linked through intermolecular N4—H1N4···Cl1, O2—H1O2···Cl1, N7—H1N7···Cl2, N3—H1N3···Cl1, O1—H1O1···Cl2 and N8—H1N8···Cl2 hydrogen bonds (Table 2) into infinite chains propagating along [101] (Fig. 2).

Experimental

The ligand was prepared by the mixing of 2,3-butanedione monoxime (1.01 g) dissolved in 20 ml of EtOH with 4-ethyl-3-thiosemicarbazide (1.19 g) dissolved in 20 ml of EtOH and a few drops of acetic acid. The mixture was boiled under reflux with stirring for 3 h. The mixture was filtered and left to cool and evaporate the solvent at room temperature and the resulting white solid formed was collected by suction filtration and washed with cold EtOH (yield 66%, m.p. 475.2 - 477.2 K). To a solution of the ligand (0.2021 g) in EtOH (20 ml) was added a solution of (NiCl₂.6H₂O) (0.2377 g) in EtOH (20 ml). The mixture was boiled under reflux for 2 h with stirring. The mixture was filtered and left to cool accompanied by slow evaporation of the solvent at room temperature. The brown crystals were grown in DMF-acetone (1:4) mixture by slow evaporation at room temperature for 2 weeks (yield 45%, m.p. 513.9 K).