Bis[μ-N′-isobutyryl-1-oxidonaphtha­lene-2-carbohydrazidato(3-)]dipyridine­tricopper(II)

Xue-Feng Shi; Dacheng Li; Pi-Yong Li; Da-Qi Wang

doi:10.1107/S1600536809009003

. 2009 Mar 25;65(Pt 4):m435. doi: 10.1107/S1600536809009003

Bis[μ-N′-isobutyryl-1-oxidonaphthalene-2-carbohydrazidato(3-)]dipyridinetricopper(II)

Xue-Feng Shi ^a, Dacheng Li ^a,^*, Pi-Yong Li ^a, Da-Qi Wang ^a

PMCID: PMC2968934 PMID: 21582373

Abstract

The complete molecule of the title complex, [Cu₃(C₁₅H₁₃N₂O₃)₂(C₅H₅N)₂], is generated by crystallographic twofold symmetry, with the central Cu atom lying on the rotation axis: it is coordinated by two N,O-bidentate ligands in a trans-CuN₂O₂ distorted square-planar arrangement. The other Cu atom is coordinated by an N,O,O′-tridentate ligand and a pyridine molecule in a distorted trans-CuN₂O₂ arrangement. In the crystal structure, a C—H⋯π interaction occurs.

Related literature

For related structures, see: Patole et al. (2003 ▶); Pouralimardan et al. (2007 ▶). For background on C—H⋯π interactions, see: Nishio (2004 ▶); Saalfrank & Bernt (1998 ▶).

Experimental

Crystal data

[Cu₃(C₁₅H₁₃N₂O₃)₂(C₅H₅N)₂]
M _r = 887.37
Monoclinic,
a = 23.661 (2) Å
b = 13.0521 (18) Å
c = 13.3142 (15) Å
β = 113.684 (2)°
V = 3765.5 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.74 mm⁻¹
T = 298 K
0.37 × 0.35 × 0.31 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ▶) T _min = 0.566, T _max = 0.615 (expected range = 0.537–0.584)
9477 measured reflections
3310 independent reflections
2319 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.135
S = 1.00
3310 reflections
251 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009003/hb2917sup1.cif

e-65-0m435-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009003/hb2917Isup2.hkl

e-65-0m435-Isup2.hkl^{(162.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—O1	1.920 (3)
Cu1—O1ⁱ	1.920 (3)
Cu1—N2	1.946 (3)
Cu1—N2ⁱ	1.946 (3)
Cu2—N1	1.884 (3)
Cu2—O2	1.890 (3)
Cu2—O3	1.953 (3)
Cu2—N3	1.975 (3)

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Symmetry code: (i) Inline graphic .

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

Cg1 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯Cg1ⁱⁱ	0.93	2.53	3.362 (4)	150

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Symmetry code: (ii) Inline graphic .

Acknowledgments

We acknowledge financial support from the National Natural Science Foundation of China (grant No. 20671048).

supplementary crystallographic information

Comment

A large number of aroylhydrazine complexes have been prepared and studied due to their diverse molecular architectures and quite interesting chemical properties (Patole et al., 2003; Pouralimardan et al., 2007). However, researches on the copper(II) complexes with N-isobutyryl-1-hydroxy-2-naphthalenecarbohydrazide have not reported. So we have synthesized a new complex, (I), (Fig. 1), which has been characterized by X-ray diffraction and elemental analysis. The molecule of (I) contains three copper(II), two ligand molecules, and two pyridine molecules. Both copper centres adopt distorted square planar trans-CuN₂O₂ arrangements. The triple-deprotonated N-isobutyryl-1-hydroxy-2-naphthalenecarbohydrazide bridges the metal ions using a hydrazide N—N group and formed the trinuclear copper complex. In the crystal packing, the complex molecules are linked into two-dimensional network by intermolecular C—H···π interactions (Fig. 2) (Saalfrank & Bernt, 1998; Nishio, 2004).

Experimental

Isobutyric anhydride (0.632 g, 4 mmol) and 1-hydroxy-2-naphthalenecarbohydrazide (0.808 g, 4 mmol) were added to 40 ml of chloroform at ice-water bath. The reaction mixture was slowly warmed to room temperature and stirred for 24 h. After overnight refrigeration, the resulting white precipitate was filtered and rinsed with chloroform and diethyl ether (1.02 g, 93.57% yield). A solution of CuNO₃(0.04 g,0.2 mmol) in methanol (10 ml) was added to a mixture of N-isobutyryl-1-hydroxy-2-naphthalenecarbohydrazide (0.055 g, 0.2 mmol) and sodium methylate (0.0324 g, 0.6 mmol) in pyridine (10 ml). A green solution was obtained after refluxing for 3 h. After being filtrated, dimethyl ether was slowly diffused into the filtrate, and green blocks of (I) were obtained after two weeks. Elemental analysis calculated for C₄₀H₃₆N₆O₆Cu₃: C, 54.09; H, 4.05; O, 10.78; N, 9.43. Found (%): C, 54.12; H, 4.06; O, 10.82; N, 9.47