Di-μ-azido-κ4 N 1:N 1′-bis­({1-[(E)-phen­yl(pyridin-2-yl-κN)methyl­idene]thio­semi­carbazidato-κ2 N 1,S}copper(II))

Roji J Kunnath; M R Prathapachandra Kurup; Seik Weng Ng

doi:10.1107/S1600536812035751

. 2012 Aug 23;68(Pt 9):m1195. doi: 10.1107/S1600536812035751

Di-μ-azido-κ⁴ N ¹:N ^1′-bis({1-[(E)-phenyl(pyridin-2-yl-κN)methylidene]thiosemicarbazidato-κ² N ¹,S}copper(II))

Roji J Kunnath ^a, M R Prathapachandra Kurup ^a, Seik Weng Ng ^b,^c,^*

PMCID: PMC3435612 PMID: 22969485

Abstract

In the title compound, [Cu₂(C₁₃H₁₁N₄S)₂(N₃)₂], the Cu^II cation is N,N′,S-chelated by the deprotonated Schiff base ligand and is coordinated by the azide anion, while an N atom from an adjacent azide anion bridges the Cu^II cation at the apical position with a longer Cu—N distance of 2.533 (3) Å, completing the distorted N₄S square-pyramidal coordination geometry. A pair of azide anions bridge the two Cu^II cations, forming a centrosymmetric binuclear molecule. In the crystal, the binuclear molecules are linked by an N—H⋯N hydrogen bond into a ribbon running along the a axis.

Related literature

For the structure of the parent Schiff base, see: Casas et al. (2003 ▶).

Experimental

Crystal data

[Cu₂(C₁₃H₁₁N₄S)₂(N₃)₂]
M _r = 721.78
Monoclinic,
a = 11.2462 (12) Å
b = 7.2344 (10) Å
c = 18.519 (2) Å
β = 96.653 (5)°
V = 1496.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 295 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.604, T _max = 0.690
13614 measured reflections
3747 independent reflections
2973 reflections with I > 2σ(I)
R _int = 0.075

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.134
S = 1.04
3747 reflections
205 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812035751/xu5611sup1.cif

e-68-m1195-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035751/xu5611Isup2.hkl

e-68-m1195-Isup2.hkl^{(183.7KB, 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	0.87 (1)	2.22 (1)	3.075 (3)	168 (4)

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Symmetry code: (i) Inline graphic .

Acknowledgments

RJK thanks the University Grants Commission (India) for a Junior Research Fellowship. We thank the Sophisticated Analytical Instruments Facility, Cochin University of S & T, for the diffraction measurements. We also thank the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

supplementary crystallographic information

Comment

2-Benzoylpyridine thiosemicarbazone (Casas et al., 2003) is a Schiff base that is capable of N,N',S-chelation to metal ions. The Cu^II atom in [Cu(N₃)(C₁₃H₁₁N₄S)]₂ (Scheme I) is N,N',S-chelated by the deprotonated Schiff base, and it exists in a square pyramidal environment (Fig. 1). Two molecules are disposed about a center-of-inversion and the distance between the copper atom and their apical nitrogen atom of the other azide is 2.533 (3) Å. Adjacent inversion-related pairs of molecules are linked by an N–H···N hydrogen bond to form a ribbon running along the a-axis (Table 1).

Experimental

The Schiff base ligand by heating 2-benzoylpyridine (0.183 g,1 mmol) and thiosemicarbazide (0.091 g,1 mmol) for 3 h. Copper acetate hydrate (0.199 g,1 mmol) and sodium azide (0.065 g,1 mmol) was added and the solution heated for another 2 h. Dark green colored crystals were obtained from the cool solution.