Aqua­[6-carboxyl­ato-N′-(pyridin-2-yl­methyl­idene)pyridine-2-carbohydrazidato]copper(II) trihydrate

Yu-Min Huang; Wen-Shi Wu; Xin-Yu Wang

doi:10.1107/S1600536812021447

. 2012 May 19;68(Pt 6):m783. doi: 10.1107/S1600536812021447

Aqua[6-carboxylato-N′-(pyridin-2-ylmethylidene)pyridine-2-carbohydrazidato]copper(II) trihydrate

Yu-Min Huang ^a, Wen-Shi Wu ^a,^*, Xin-Yu Wang ^a

PMCID: PMC3379113 PMID: 22719334

Abstract

In the title compound, [Cu(C₁₃H₈N₄O₃)(H₂O)]·3H₂O, the complex molecule, except for the aqua ligand, is essentially planar [r.m.s. deviation = 0.034 (2) Å]. The coordination polyhedron of the Cu²⁺ cation is a square-pyramid, with the aqua ligand at the apex. The compound exhibits a three-dimensional structure, which is is stabilized by O—H⋯O and O—-H⋯N hydrogen bonds and π–π interactions [centroid–centroid distance = 2.987 (3) Å].

Related literature

For the synthesis, see: Wu et al. (2007 ▶). For a related structure, see: Cheng et al. (2007 ▶). graphic file with name e-68-0m783-scheme1.jpg

Experimental

Crystal data

[Cu(C₁₃H₈N₄O₃)(H₂O)]·3H₂O
M _r = 403.85
Triclinic,
a = 7.1646 (16) Å
b = 9.369 (2) Å
c = 12.647 (3) Å
α = 75.313 (4)°
β = 78.864 (4)°
γ = 74.155 (4)°
V = 783.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 173 K
0.46 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.655, T _max = 0.749
4689 measured reflections
3903 independent reflections
3270 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.097
S = 1.09
3903 reflections
259 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536812021447/hg5211sup1.cif

e-68-0m783-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021447/hg5211Isup2.hkl

e-68-0m783-Isup2.hkl^{(168.1KB, 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
O4—H4B⋯O1ⁱ	0.70 (3)	2.04 (3)	2.718 (2)	165 (3)
O7—H7B⋯O6ⁱⁱ	0.72 (3)	2.09 (3)	2.796 (3)	167 (3)
O6—H6A⋯O3ⁱⁱⁱ	0.74 (3)	1.94 (3)	2.675 (3)	176 (3)
O5—H5B⋯O4	0.72 (3)	2.07 (3)	2.788 (3)	173 (3)
O4—H4A⋯N3^iv	0.70 (4)	2.20 (4)	2.878 (2)	163 (3)
O4—H4A⋯O1^iv	0.70 (4)	2.56 (3)	3.053 (2)	129 (3)
O5—H5A⋯O7	0.65 (3)	2.10 (4)	2.742 (3)	168 (4)
O7—H7A⋯O6^v	0.86 (4)	1.95 (4)	2.803 (3)	175 (3)
O6—H6B⋯O5	0.78 (4)	1.94 (4)	2.718 (3)	178 (3)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

We are grateful for financial support from the National Science Foundation of Fujian Province of China (No. 2010J01288) and the Fundamental Research Funds for the Central Universities (No. JB-JC1003). We also thank Dr Zhan-bin Wei (Department of Chemistry, Xiamen University) for the data collection.

supplementary crystallographic information

Comment

In the title compound, [(C₁₃H₈N₄O₃)(H₂O)Cu].3H₂O (I), the Cu(II) ion is 5-coordinated by two nitrogen from two pyridine rings of the same molecule, one nitrogen from the hydrazine, one carboxyl oxygen, and an oxygen atom from H₂O. They form a rectangular pyramid. N1, N2, N4, O2 from the bottom side (Rms=0.0039 (7) Å), The distances of Cu and O4 to the plane are 0.1446 (8)Å and 2.477 (2)Å. The Cu—O bond lengths Cu—O2 and Cu—O4 are 2.008 (2) Å and 2.338 (2) Å , the bond lengths of two pyridine ring nitrogens with Cu are 1.940 (2) Å and 1.932 (2) Å, which are a little shorter then the normal value(1.99 Å). The distance of Cu—N2 is 1.942 (2) Å. The structure of the title compound shown in Fig 1. Except for the H₂O molecules and the Cu atom , the complex molecule is essentially planar, the r.m.s. deviation from planarity being 0.034 (2) Å. It exhibits a three-dimensional structure which is stabilized by hydrogen bonds, van der Waals forces and π–π interactions [the distance between the layers is 0.987 (3) Å]. The O—H···N, O—H···O hydrogen bonds are detailed in Fig 2 and Table 1.

Experimental

Concentrated H₂SO₄ (2 mL)was added slowly with stirring to a solution of pyridine-2,6-dicarboxylic acid in ethanol. The solution was left to reflux for 24 h, yielding a white precipitate of ethylpyridine-2,6-dicarboxylate. This was dissolved in ethanol, then the hydrazine hydrate was slowly added with continuous stirring and the mixture was refluxed over a period of 6 h, yielding awhite crystalline solid of pyridine-2-carbohydrazide-6-carboxyl acid.

The synthesis of N²-(pyridin-2-ylmethylidene)-pyridine-2-carbohydrazide methylformamide -6-carboxylic acid was carried out in accord with the method of Cheng et al. , (2007). To a suspension of pyridine-2-carbohydrazide-6-carboxyl acid (5.43 g, 30 mmol) in absolute ethanol(50 ml), a solution of pyridine-2-aldehyde (6.43 g, 60 mmol) in the same solvent(20 ml) was added at 353 K. The mixture was left to react at refluxing for 8 h. The yellowish product was filtered, washed with hot ethanol(20 ml) three times and dried in vacuo.

The title compound (I) was synthesized according to the method of Wu et al., (2004). The N²-(pyridin-2-ylmethylidene)-pyridine-2-carbohydrazide methylformamide -6-carboxylic acid (0.03 g,0.1 mmol) dissolved in DMF(10 ml), then CuBr₂(0.02 g, 0.1 mmol) in DMF(10 ml) was added slowly. Black crystals of the title complex precipitated after a few weeks of slow evaporation of the DMF solution at room temperature. Elemental analysis: caculated for C₁₃H₁₀CuN₄O₄.3H₂O:C 38.61%, H 3.96%, N 13.86% ; found: C 38.70%, H 3.83%, N 13.95%. Mp: 645 K.