[2-(1-{2-[Aza­nid­yl(ethyl­sulfan­yl)methyl­idene-κN]hydrazin-1-yl­idene-κN 1}eth­yl)phenolato-κO](pyridine-κN)nickel(II)

Reza Takjoo; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812026177

. 2012 Jun 16;68(Pt 7):m911. doi: 10.1107/S1600536812026177

[2-(1-{2-[Azanidyl(ethylsulfanyl)methylidene-κN]hydrazin-1-ylidene-κN ¹}ethyl)phenolato-κO](pyridine-κN)nickel(II)

Reza Takjoo ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3393181 PMID: 22807749

Abstract

The Ni^II atom in the title complex, [Ni(C₁₁H₁₃N₃OS)(C₅H₅N)], exists within a square-planar N₃O donor set provided by N,N′,O atoms of the dianionic tridentate ligand and a pyridine N atom. The maximum deviation from the ideal geometry is seen in the N—Ni—N five-membered chelate bite angle of 83.28 (12)°. The pyridine molecule forms a dihedral angle of 44.43 (6)° with the N₃O donor set. Supramolecular stacks along the a axis mediated by alternating π–π interactions between the pyridine and five- [centroid–centroid distance = 3.4784 (16) Å] and six-membered [3.4633 (17) Å] chelate rings, feature in the crystal packing.

Related literature

For the complexing ability of S-alkyl esters of thiosemicarbazone derivatives, see: Ahmadi et al. (2012 ▶). For medicinal applications of thiosemicarbazone, see: Dilworth & Hueting (2012 ▶). For a related structure, see: Guveli & Ulkuseven (2011 ▶).

Experimental

Crystal data

[Ni(C₁₁H₁₃N₃OS)(C₅H₅N)]
M _r = 373.11
Orthorhombic,
a = 7.2956 (4) Å
b = 9.8463 (5) Å
c = 21.7489 (11) Å
V = 1562.33 (14) Å³
Z = 4
Mo Kα radiation
μ = 1.39 mm⁻¹
T = 100 K
0.35 × 0.10 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.790, T _max = 1.000
6002 measured reflections
3584 independent reflections
3130 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.075
S = 1.00
3584 reflections
213 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.39 e Å⁻³
Absolute structure: Flack (1983 ▶), 1501 Friedel pairs
Flack parameter: −0.028 (16)

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812026177/hb6842sup1.cif

e-68-0m911-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026177/hb6842Isup2.hkl

e-68-0m911-Isup2.hkl^{(175.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ni—O1	1.828 (2)
Ni—N1	1.861 (2)
Ni—N3	1.845 (3)
Ni—N4	1.918 (2)

Open in a new tab

Acknowledgments

The authors are grateful to the Ferdowsi University of Mashhad for financial support, and thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM·C/HIR/MOHE/SC/3).

supplementary crystallographic information

Comment

Schiff bases derived from S-alkyl esters of thiosemicarbazone comprise an important class of ligands containing sulfur-nitrogen donor atoms for metals. Thus, they are capable of reacting with both transition and some main group metals (Ahmadi et al., 2012) and may be used as therapeutic and imaging agents (Dilworth & Hueting, 2012). Herein, the crystal and molecular structure of the title complex, (I), is described.

The Ni^II atom in (I), Fig. 1, exists within a square planar N₃O donor set defined by the N,N,O atoms of the dinegative tridentate ligand and a pyridine-N atom, Table 1. The donor set is planar with a r.m.s. deviation = 0.0323 Å and maximum deviations of 0.0336 (13) and -0.0331 (13) Å for the N3 and N1 atoms, respectively. The Ni atom lies 0.0056 (13) Å out of the plane. The maximum deviations from the ideal geometry are manifested in the N1—Ni—N3 chelate angle of 83.28 (12)°. The pyridine molecule is inclined to the N₃O donor set, forming a dihedral angle of 44.43 (6)°. The molecular structure resembles that of the S-methyl ester where the Ni atom is coordinated by Ph₃P rather than pyridine (Guveli & Ulkuseven, 2011).

The most notable feature of the crystal packing is the formation of π—π interactions whereby the pyridine links alternating five- [inter-centroid distance = 3.4784 (16) Å, angle of inclination = 4.67 (14)° for symmetry operation: 1/2 + x, 1/2 - y, 2 - z] and six-membered [3.4633 (17) Å and 4.13 (13)° for -1/2 + x, 1/2 - y, 2 - z] chelate rings along the a axis, Fig. 2. Stacks assemble without specific interactions between them, Fig. 3.

Experimental

Nickel acetate tetrahydrate (0.25 g, 1.0 mmol) was added to a solution of 1-(2-hydroxyphenyl)ethanone S-ethylisothiosemicarbazone hydrobromide (0.25 g, 1.0 mmol) in ethanol (10 ml). Three drops of pyridine was added to solution. The red solution was heated under reflux for 1 h. Orange prisms were deposited after 3 days, collected by filtration, washed with ethanol, and dried in air. M. pt: 421 K. Yield: 85%.