Tetra­kis[μ3-4-nitro-N-(5-phenyl-1,3,4-oxadiazol-2-yl)benzamidato]tetra­kis­[methano­lsodium(I)]

Guo-Jie Yin; Qing Zhang; Dong Li

doi:10.1107/S1600536812014791

. 2012 Apr 13;68(Pt 5):m570. doi: 10.1107/S1600536812014791

Tetrakis[μ₃-4-nitro-N-(5-phenyl-1,3,4-oxadiazol-2-yl)benzamidato]tetrakis[methanolsodium(I)]

Guo-Jie Yin ^a,^*, Qing Zhang ^a, Dong Li ^a

PMCID: PMC3344320 PMID: 22590086

Abstract

In the title compound, [Na₄(C₁₅H₉N₄O₄)₄(CH₃OH)₄], the N₃O₃ environment around the Na⁺ ion is distorted octahedral. In the unit cell, four Na⁺ ions are bridged by four Schiff base anions, leading to a tetranuclear complex with -4 symmetry. O—H⋯N hydrogen bonds between the methanol molecule and the Schiff base anion stabilize the structural set-up.

Related literature

For the preparation of 2-amino-5-phenyl-1,3,4-oxadiazole, see: Gibson (1962 ▶) and of N-(5-phenyl-1,3,4-oxadiazol-2-yl)-p-nitrobenzamide, see: Zhang et al. (2009 ▶). Organic ligands based on oxadiazole or carboxylate groups have both good coordination ability and diverse coordination modes, see: Hu et al. (2008 ▶).

Experimental

Crystal data

[Na₄(C₁₅H₉N₄O₄)₄(CH₄O)₄]
M _r = 1457.18
Tetragonal,
a = 15.6635 (2) Å
c = 27.1833 (6) Å
V = 6669.29 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.934, T _max = 1.000
15582 measured reflections
3413 independent reflections
2653 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.106
S = 1.02
3413 reflections
239 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812014791/hp2035sup1.cif

e-68-0m570-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014791/hp2035Isup2.hkl

e-68-0m570-Isup2.hkl^{(167.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Na1—O5	2.3413 (14)
Na1—N1	2.3828 (15)
Na1—O1	2.3848 (13)
Na1—O1ⁱ	2.3972 (13)
Na1—N2ⁱⁱ	2.4127 (15)
Na1—N1ⁱⁱ	2.9859 (15)

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

Acknowledgments

This work was supported by a start-up grant from Luoyang Institute of Science and Technology.

supplementary crystallographic information

Comment

As we all know, the organic ligands based on oxadiazole or carboxylate groups which containing N and O donors have both good coordination ability and diverse coordination modes (Hu et al., 2008). Therefore, the ligand N-(5-phenyl-1,3,4-oxadiazol-2-yl)- p-nitrobenzamide was chosen to create coordination architectures.

In the title compound, each Na^I atom is six-coordinated by one O atom from a methyl alcohol, two O atoms and three N atoms from the ligands, forming a distorted octahedral geometry. In the asymmetric unit, the four Na^I ions are bridged by four Schiff base anions, leading to a tetranuclear complex (Fig. 1 and Fig. 2), the coordination geometry of sodium ions can be described as distorted quadrilateral.

Experimental

Reagents and solvents were of commercially available quality. The preparation of 2-Amino-5-phenyl-1,3,4-oxadiazole is based on a published method (Gibson, 1962). Bromine (0.66 ml) in glacial acetic acid (1.34 ml) was added to a stirred slurry of benzaldehyde semicarbazone (2.0 g) and powdered, anhydrous sodium acetate (4.0 g) in acetic acid (12 ml). The solids were dissolved giving a red solution, which suddenly grew warm and rapidly faded with white precipitate formed (sodium bromide). After 15 minutes, the mixture was poured into water (100 ml), and the precipitated solid (1.8 g) collected, washed and dried. Crystallization from ethanol gave stout needles.

The ligand of N-(5-phenyl-1,3,4-oxadiazol-2-yl)-p-nitrobenzamide was synthesized according to the method of literature (Zhang et al., 2009). 4-Nitrobenzoyl chloride (5.94 g, 0.032 mol) was dropped slowly into the stirred slurry of 2-Amino-5-phenyl-1,3,4-oxadiazole (5.64 g, 0.035 mol) in 50 ml pyridine. 2-Amino-5-phenyl-1,3,4-oxadiazole dissolved gradually and gave a buff solution. After 2 h, the solution was poured into water. Then the sodium hydroxide (2.80 g, 0.07 mol) was added to give a alkaline solution, the precipitate was collected and dried under vacuum. The title compound was obtained by re-crystallization from ethanol. Yield: 5.7 g, 60%.