(Cyanato-κN){1-[(E)-phen­yl(pyridin-2-yl-κN)methyl­idene]semicarbazidato-κ2 N 1,O}copper(II)

Roji J Kunnath; MR Prathapachandra Kurup; Seik Weng Ng

doi:10.1107/S1600536812035386

. 2012 Aug 23;68(Pt 9):m1180. doi: 10.1107/S1600536812035386

(Cyanato-κN){1-[(E)-phenyl(pyridin-2-yl-κN)methylidene]semicarbazidato-κ² N ¹,O}copper(II)

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

PMCID: PMC3435602 PMID: 22969475

Abstract

The Cu^II atom in the title compound, [Cu(C₁₃H₁₁N₄O)(NCO)], is N,N′,O-chelated by the mono-deprotonated Schiff base ligand and it is also covalently bonded to the nitrogen end of the cyanate ion. The Cu^II atom shows a square-planar coordination that is distorted towards square-pyramidal owing to an intermolecular Cu⋯N_cyanate interaction [2.623 (2) Å], which gives a centrosymmetric dimer. In the square-planar description, the Cu^II atom is displaced out of the square plane [r.m.s. deviation = 0.048 Å] by 0.084 (1) Å in the direction of the apical occupant. In the crystal, adjacent complex dimers are linked by an amine N—H⋯N hydrogen-bond pair, also giving a centrosymmetric cyclic association [graph set R ₂ ²(8)], generating a linear chain parallel to [110].

Related literature

For the synthesis of the Schiff base, see: de Lima et al. (2008 ▶). For a related copper(II) derivative, see: Peŕez-Rebolledo et al. (2006 ▶). For graph-set notation, see: Etter et al. (1990 ▶).

Experimental

Crystal data

[Cu(C₁₃H₁₁N₄O)(NCO)]
M _r = 344.82
Monoclinic,
a = 8.7601 (1) Å
b = 7.6732 (1) Å
c = 20.0819 (3) Å
β = 96.7467 (7)°
V = 1340.52 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.64 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.638, T _max = 0.735
11886 measured reflections
3069 independent reflections
2728 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.093
S = 1.03
3069 reflections
208 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.47 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/S1600536812035386/zs2226sup1.cif

e-68-m1180-sup1.cif^{(18KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035386/zs2226Isup2.hkl

e-68-m1180-Isup2.hkl^{(150.6KB, 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
N4—H41⋯N3ⁱ	0.88 (1)	2.27 (1)	3.139 (2)	173 (3)

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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 Science and Technology, 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 semicarbazone (de Lima et al., 2008) is a Schiff base that is capable of N,N',O-chelation to transition metal ions. This feature has been documented in a copper(II) dichloride adduct in which the Schiff base exists as a neutral molecule (Peŕez-Rebolledo et al., 2006). However, the Cu^II atom in the title compound [Cu(NCO)(C₁₃H₁₁N₄O)] (Scheme I) is N,N',O-chelated by the mono-deprotonated Schiff base ligand and it is also covalently bonded to the nitrogen end of the cyanate ion. The metal center shows square-planar coordination that is distorted towards square-pyramidal coordination owing to an intermolecular Cu···N_cyanate interaction [2.623 (2) Å], which generates a centrosymmetric dimer (Fig. 1). The geometry is better interpreted as square planar as the Cu···N_cyanate···Cu angle is too acute [93.0 (1)°].

Adjacent dimers are linked by an amine N—H···N hydrogen-bond pair (Table 1), also giving a centrosymmetric cyclic association [graph set R²₂(8) (Etter et al., 1990], generating a linear chain parallel to [1 1 0].

Experimental

A methanol solution (20 ml) of 2-benzoylpyridine semicarbazone (0.240 g, 1 mmol) (de Lima et al., 2008), copper sulfate pentahydrate (0.249 g, 1 mmol) and sodium cyanate (0.065 g, 1 mmol) was heated for 5 h. The dark green solid was collected and recrystallized from methanol.