Bis{2-hydroxy­imino-N′-[1-(2-pyrid­yl)ethyl­idene]propanohydrazidato}zinc(II) dihydrate

Yurii S Moroz; Kateryna O Znovjyak; Iryna O Golenya; Svetlana V Pavlova; Matti Haukka

doi:10.1107/S1600536810003351

. 2010 Jan 30;66(Pt 2):m242–m243. doi: 10.1107/S1600536810003351

Bis{2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazidato}zinc(II) dihydrate

Yurii S Moroz ^a,^*, Kateryna O Znovjyak ^a, Iryna O Golenya ^a, Svetlana V Pavlova ^a, Matti Haukka ^b

PMCID: PMC2979945 PMID: 21579695

Abstract

The title compound, [Zn(C₁₀H₁₁N₄O₂)₂]·2H₂O, was prepared by the reaction between Zn(CH₃COO)₂·2H₂O and 2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazide (Hpop). The central Zn^II atom has a distorted tetragonal-bipyramidal coordination geometry formed by two amide O atoms and four N atoms of two azomethine and two pyridine groups. In the crystal, complex molecules form layers parallel to the crystallographic b direction. The layers are connected by O—H⋯N and O—H⋯O hydrogen bonds involving the solvent water molecules.

Related literature

For zinc(II)-containing complexes with similiar ligands, see: Petrusenko et al. (1997 ▶); Comba et al. (2002 ▶); Kasuga et al. (2003 ▶). For the structural parameters of amide derivatives of 2-hydroxyiminopropanoic acid, see: Onindo et al. (1995 ▶); Sliva et al. (1997a ▶,b ▶); Mokhir et al. (2002 ▶); Moroz et al. (2009a ▶,b ▶). For the preparation and characterization of 3d-metal complexes with 2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazone, see: Moroz et al. (2008a ▶,b ▶).

Experimental

Crystal data

[Zn(C₁₀H₁₁N₄O₂)₂]·2H₂O
M _r = 539.86
Triclinic,
a = 8.3241 (3) Å
b = 10.6299 (4) Å
c = 13.9006 (5) Å
α = 94.184 (2)°
β = 101.389 (2)°
γ = 108.052 (2)°
V = 1134.48 (7) Å³
Z = 2
Mo Kα radiation
μ = 1.14 mm⁻¹
T = 100 K
0.28 × 0.07 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.743, T _max = 0.977
21551 measured reflections
5171 independent reflections
4253 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.092
S = 1.05
5171 reflections
320 parameters
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: COLLECT (Bruker, 2004 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810003351/jh2129sup1.cif

e-66-0m242-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003351/jh2129Isup2.hkl

e-66-0m242-Isup2.hkl^{(253.2KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Zn1—N2	2.061 (2)
Zn1—N6	2.085 (2)
Zn1—O1	2.0880 (15)
Zn1—O3	2.1470 (15)
Zn1—N5	2.1955 (19)
Zn1—N1	2.2877 (19)

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N2—Zn1—O1	76.10 (7)
N6—Zn1—O3	74.17 (6)
N6—Zn1—N5	75.07 (7)
N2—Zn1—N1	73.97 (7)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯N7ⁱ	0.92	1.89	2.801 (3)	170
O4—H4O⋯O5ⁱⁱ	0.93	1.77	2.675 (3)	164
O5—H5P⋯O3	0.91	1.93	2.811 (3)	161
O5—H5O⋯O6	0.86	2.08	2.889 (3)	157
O6—H6O⋯N4ⁱⁱⁱ	0.92	2.12	2.934 (3)	148
O6—H6P⋯N8ⁱⁱ	0.93	2.10	2.971 (3)	154

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

Acknowledgments

The authors thank the Ministry of Education and Science of Ukraine for financial support (grant No. F28/241–2009).

supplementary crystallographic information

Comment

As a part of our study of coordination compounds based on oxime-containing Schiff bases we would like to present the structure of the title compound 1, Fig. 1, which is based on polynucleative strand-type ligand 2-hydroxyimino-N'-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop) (Fig. 1). It has been shown previously that Hpop is able to form mono- and tetranuclear [2 x 2] grid-like assemblies with 3d-metal ions (Moroz et al., 2008a,b).

The title compound consists of neutral complex molecules and solvating water molecules. Zinc ion has a distorted tetragonal bipyramidal geometry. The coordination polyhedron is formed by two oxygen atoms from the amide groups and four nitrogen atoms belonging to two azomethine and two pyridine groups. The Zn—N and Zn—O bond lengths are comparable to previously reported zinc complexes with thiosemicarbasone and semicarbasone derivatives (Kasuga et al., (2003)), ligands with pyridine groups complexed to the metal ion (Petrusenko et al. (1997), Comba et al., (2002)) and the zinc-containing complex based on Hpop (Moroz et al., 2008b) (Table 1). The bite angles around the central atom deviate from an ideal square-planar configuration, that is a consequence of the formation of four almost flat five-membered chelate rings (Table 1). The ligands exist in complex molecule in singly charged form due to deprotonation of the amide group, C–N, C–O and N–N' bond distances are typical for deprotonated functions. In Hpop the oxime group is situated in anti- position to the amide group which was early shown in the structures of the free ligand and similiar compounds - amide derivatives of 2-hydroxyiminopropanoic acid (Onindo et al. (1995); Sliva et al. (1997a,b); Mokhir et al. (2002); Moroz et al., 2009a,b).

In the crystal packing the molecules of 1 form columns along a crystallographic direction due to hydrogen bonds and π-stacking interaction (Fig. 2). The columns are connected in 3D structure by a variety of hydrogen bonds where solvated water molecules act as donors and O and N atoms of the oxime group and O atom of the amide group of the ligand act as acceptors (Table 2).

Experimental

Zinc(II) acetate (0.011 g, 0.05 mmol) in 5 ml H₂O was added to 10 ml of hot methanol solution of Hpop (0.022 g, 0.1 mmol) and followed by 1 ml of alkali solution (0.1 M KOH). The mixture was left for slow evaporation at room temperature. After 5 days cubic yellowish crystals of 1 suitable for X-ray analysis were obtained.