[1-(5-Bromo-2-oxidobenzyl­idene)thio­semicarbazidato-κ3 O,N 1,S](pyridine-κN)nickel(II)

Fernanda Rosi Soares Pederzolli; Leandro Bresolin; Johannes Beck; Jörg Daniels; Adriano Bof de Oliveira

doi:10.1107/S1600536812028917

. 2012 Aug 1;68(Pt 9):m1138. doi: 10.1107/S1600536812028917

[1-(5-Bromo-2-oxidobenzylidene)thiosemicarbazidato-κ³ O,N ¹,S](pyridine-κN)nickel(II)

Fernanda Rosi Soares Pederzolli ^a, Leandro Bresolin ^a, Johannes Beck ^b, Jörg Daniels ^b, Adriano Bof de Oliveira ^c,^*

PMCID: PMC3435568 PMID: 22969441

Abstract

The reaction of 5-bromosalicylaldehyde thiosemicarbazone with nickel acetate tetrahydrate and pyridine yielded the title compound, [Ni(C₈H₆BrN₃OS)(C₅H₅N)]. The Ni^II atom is four-coordinated in a square-planar environment by one deprotonated dianionic thiosemicarbazone ligand, acting in a tridentate chelating mode through N, O and S atoms forming two metalla-rings, and by one pyridine molecule. The complex molecules are linked into dimers by pairs of centrosymmetrical N—H⋯N interactions. In addition, molecules are connected through intermolecular Br⋯Br interactions [3.545 (1) Å], forming chains along the b-axis direction.

Related literature

For the synthesis of 5-bromosalicylaldehyde thiosemicarbazones and for the antibacterial activity of their complexes, see: Joseph et al. (2010 ▶). For the crystal structure of 5-bromosalicylaldehyde thiosemicarbazone, see: Kargar et al. (2010 ▶). For the crystal structure of an Ni^II complex with a similar coordination environment, see: Güveli et al. (2009 ▶). For the coordination chemistry of thiosemicarbazone derivatives, see: Lobana et al. (2009 ▶).

Experimental

Crystal data

[Ni(C₈H₆BrN₃OS)(C₅H₅N)]
M _r = 409.94
Monoclinic,
a = 12.2447 (4) Å
b = 4.1135 (1) Å
c = 31.1380 (11) Å
β = 112.646 (1)°
V = 1447.46 (8) Å³
Z = 4
Mo Kα radiation
μ = 4.25 mm⁻¹
T = 293 K
0.93 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.443, T _max = 0.830
13946 measured reflections
3224 independent reflections
2697 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.083
S = 1.05
3224 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812028917/zl2486sup1.cif

e-68-m1138-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028917/zl2486Isup2.hkl

e-68-m1138-Isup2.hkl^{(158.2KB, 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
N3—H1⋯N2ⁱ	0.78	2.31	3.095 (3)	178

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge financial support through the DECIT/SCTIE-MS-CNPq-FAPERGS-Pronem-# 11/2029–1 and PRONEX-CNPq-FAPERGS projects.

supplementary crystallographic information

Comment

Thiosemicarbazone derivatives have a wide range of applications in biological inorganic chemistry and a very interesting coordination chemistry (Lobana et al., 2009). For example, Cu^II and Ni^II complexes with 5-bromosalicylaldehyde thiosemicarbazone show antibacterial activity against Staphylococcus aureus and Escherichia coli (Joseph et al., 2010). As part of our study of thiosemicarbazone derivatives, we report herein the synthesis and the crystal structure of a new Ni^II complex with 5-bromosalicylaldehyde thiosemicarbazone. In the title compound, in which the molecular structure unit matches the asymmetric unit, the Ni^II ion is coordinated in a square planar environment by one deprotonated dianionic 5-bromosalicylaldehyde thiosemicarbazone and one pyridine ligand (Fig. 1). The selected bond angles formed between donor atoms trough the Ni atom are N1—Ni1—N4 = 177.00 (10)° and O1—Ni1—S1 = 176.46 (6)°, and show a slightly distorted coordination environment. The thiosemicarbazone ligand is coordinated to the Ni^II ion in a tridentate chelating mode, forming five- and six-membered rings, as a "NOS" donor with the O/S atoms trans to each other, while the N1 azomethine atom is trans to the N4 atom from the pyridine ligand.

The acidic hydrogen of the hydrazine fragment is lost by the reaction with KOH, which is in agreement with thiosemicarbazone derivatives prepared from aldehydes or ketones. The negative charge is delocalized over the C—N—N—C—S fragment as indicated by their intermediate bond distances. The imine and thioamide C—N distances indicate considerable double bond character, while the C—S distance is consistent with increased single bond character. These distances are C7—N1 = 1.295 (3) Å, N1—N2 = 1.403 (3) Å, N2—C8 = 1.289 (4) Å and C8—S1 = 1.735 (3) Å. The hydrogen of the hydroxyl group is also deprotonated with KOH, resulting in the dianionic form of the ligand.

The ligand shows a Z—E—E—Z conformation for the donor atoms about the C1—C7/C7—N1/N1—N2/N2—C8 bonds and the mean deviations from the least squares planes for the chelated fragments Ni1/N1/C7/C1/C2/O1 and Ni1/N1/N2/C8/S1 amount to 0.0286 (15) Å for N1 and 0.0170 (12) Å for N1, respectively, and the dihedral angle between the two planes is 2.97 (11)°. The Z—E—E—Z conformation is also observed for the free ligand (Kargar et al., 2010) as well as for a complex with similar coordination environment (Güveli et al., 2009).

Both ligands are almost planar (Fig. 1 and Fig. 2) and the maximum deviation from the least squares plane through all non-hydrogen atoms for the deprotonated thiosemicarbazone fragment C1/C2/C3/C4/C5/C6/C7/C8/Br1/N1/N2/N3/O1/S1 and for the pyridine molecule C9/C10/C11/C12/C13/N4 amount to 0.0668 (25) Å for C7 and 0.0059 (21) Å for C9, respectively, and the dihedral angle between the two planes is 61.15 (6)°.

The molecules are linked by pairs of centrosymmetrical N—H···N interactions (Fig. 2 and Table 1; N3—H5···N2ⁱ) forming a dimeric molecular structure, which stabilizes the crystal packing. Symmetry codes: (i) -x, -y + 1, -z.

The crystal structure shows that molecules are additionally connected through intermolecular Br···Br interactions into chains along the crystallographic b direction (Fig. 3). The Br···Br distances amount to 3.545 (1) Å, which are shorter than the sum of the van der Waals radii for Br atoms (3.70 Å).

Experimental

Starting materials were commercially available and were used without further purification. The synthesis of 5-bromosalicylaldehyde thiosemicarbazone was adapted from a procedure reported previously (Joseph et al., 2010). 5-Bromosalicylaldehyde thiosemicarbazone (0.5 mmol) was dissolved in tetrahydrofurane (50 ml) and treated with one KOH pellet. After 30 min stirring under slight warming to 333 K, the solution was filtered and added to a nickel acetate tetrahydrate (0.5 mmol) solution in pyridine (10 ml). The reaction mixture was refluxed for 4 h under continuous stirring and showed a brown-red colour. Brown-red crystals of the complex, suitable for X-ray analysis, were obtained after six weeks by adding a 3:1 mixture of dimethylformamide and toluene (80 ml) to the reaction solution.