Poly[[μ2-(1Z,N′E)-2-(1,3-benzothia­zol-2-ylsulfan­yl)-N′-(2-oxidobenzyl­idene-κ2 O:O)acetohydrazidato-κ2 O,N′](pyridine-κN)copper(II)]

Vladimir V Bon; Svitlana I Orysyk; Vasily I Pekhnyo

doi:10.1107/S160053681004986X

. 2010 Dec 4;67(Pt 1):m11. doi: 10.1107/S160053681004986X

Poly[[μ₂-(1Z,N′E)-2-(1,3-benzothiazol-2-ylsulfanyl)-N′-(2-oxidobenzylidene-κ² O:O)acetohydrazidato-κ² O,N′](pyridine-κN)copper(II)]

Vladimir V Bon ^a, Svitlana I Orysyk ^a,^*, Vasily I Pekhnyo ^a

PMCID: PMC3050211 PMID: 21522523

Abstract

In the title compound, [Cu(C₁₆H₁₁N₃O₂S₂)(C₅H₅N)]_n, the Cu^II atom displays a square-pyramidal CuN₂O₃ coordination geometry with strong elongation in the vertex direction. The hydrazone molecule is coordinated to the Cu^II atom in a tridentate manner in the enolic form, creating five- and six-membered chelate metallarings. The pyridine molecule completes the square-planar base of the copper coordination environment. The crystal structure displays zigzag polymeric Cu—O—Cu chains along [001]. Several weak π–π interactions between benzothiazole rings were found in the same direction [centroid–centroid distances = 3.7484 (16), 3.7483 (16), 3.6731 (17) and 3.7649 (17) Å].

Related literature

For general background to the biological activity of hydrazones and their metal complexes, see: Belkheiri et al. (2010 ▶); Pavan et al. (2010 ▶). For related structures, see: Luo et al. (2009 ▶).

Experimental

Crystal data

[Cu(C₁₆H₁₁N₃O₂S₂)(C₅H₅N)]
M _r = 484.04
Orthorhombic,
a = 21.6256 (5) Å
b = 25.3751 (7) Å
c = 7.1230 (2) Å
V = 3908.76 (18) Å³
Z = 8
Mo Kα radiation
μ = 1.36 mm⁻¹
T = 173 K
0.50 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.550, T _max = 0.923
18118 measured reflections
4003 independent reflections
2903 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.089
S = 1.02
4003 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.33 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: DIAMOND (Brandenburg & Putz, 2010 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681004986X/rk2250sup1.cif

e-67-00m11-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004986X/rk2250Isup2.hkl

e-67-00m11-Isup2.hkl^{(196.3KB, hkl)}

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

Acknowledgments

The authors thank the Ukrainian National Academy of Sciences for support of this study (project No 20–10).

supplementary crystallographic information

Comment

Structure investigation of hydrazones and their metal complexes attract an interest due to their antioxidant, antimycobacterium, antituberculosis activity and cytotoxicity (Belkheiri et al., 2010; Pavan et al., 2010). In the current paper we report the structure investigation of copper(II) one–dimensional coordination polymer obtained at room temperature.

The asymmetric unit of title compound contains one monomeric chain of the polymer. Copper atom displays square–pyramidal CuN₂O₃ coordination geometry, which is strongly elongated in vertex direction (Fig. 1). Hydrazone molecule is coordinated tridentantly in double deprotonated enolic form creating five– and six–membered chelate metalla rings. The square–planar base of copper coordination polyhedron is complemented by coordinated pyridine molecule. The values of Cu—O and Cu—N bond lengths corresponds to related structures (Luo et al., 2009). The geometry of coordination polyhedron is slightly distorted with adjacent angles in the range 80.71 (9)–99.22 (8)°. The Cu–Cu distance between two copper atoms in the polymeric chain is 3.5640 (5)Å. The valence angles O1–Cu1–O1ⁱ and Cu1–O1–Cu1ⁱⁱ have a same value of 99.22 (8)°. Symmetry codes: (i) 3/2-x, y, -1/2+z; (ii) 3/2-x, y, 1/2+z. The five–membered metalla ring Cu1/O2/C4/N2/N1 has a planar geometry with mean deviation from plane 0.0327Å. Contrariwise, the six–membered ring has an envelope conformation with dihedral angle 22.60 (15)° between Cu1/O1/N1 and O1/C1/C2/C3/N1 planes. The pyridine ring is nearly coplanar to square–planar base of copper coordination environment. The dihedral angle between planes Cu1/O1/O2/N1/N2 and N2/C17—C21 creates 11.02 (14)°. Crystal structure of title compound displays 1D zigzag chains (Cu–O–Cu) along [001] direction (Fig. 2). The adjacent polymeric chains in the crystal structure are connected by weak π–π stacking interactions between benzthiazol and phenyl rings: Cg1···Cg1ⁱⁱⁱ = 3.7484 (16)Å, α = 3°; Cg1···Cg1^iv = 3.7483 (16)Å, α = 3°; Cg1···Cg2ⁱⁱⁱ = 3.6731 (17)Å, α = 2.18 (14)°; Cg1···Cg2^iv = 3.7649 (17)Å, α = 2.18 (14)°; (Cg1 - centroid of the ring S2/N3/C6/C7/C8, Cg2 – centroid of the ring C7–C12, α - dihedral angle between rings. Symmetry codes: (iii) x, 1/2-y, -1/2+z; (iv) x, 1/2-y, 1/2+z.

Experimental

Mixture of 20 ml (10 ^-2 mol/L) aqueous solution of copper(II) acetate with 2 ml of pyridine was stirred with 20 ml (10 ^-2 mol/L) ethanolic solution of (E)-2-(benzo[d]thiazol-2-ylthio)-N'-(2-\ hydroxybenzylidene)acetohydrazide for 1 h. The resulted solution was leaved in dark place for evaporation. After 1 week of stating violet needle–like shape crystals were grown.