catena-Poly[[bis­(nitrato-κO)copper(II)]-bis­[μ-1,4-bis­(pyridin-3-ylmeth­oxy)benzene-κ2 N:N′]]

Ping Zou; Ying Liu; Guang-Feng Hou; Jin-Sheng Gao

doi:10.1107/S1600536811016096

. 2011 May 7;67(Pt 6):m692. doi: 10.1107/S1600536811016096

catena-Poly[[bis(nitrato-κO)copper(II)]-bis[μ-1,4-bis(pyridin-3-ylmethoxy)benzene-κ² N:N′]]

Ping Zou ^a, Ying Liu ^b,^c, Guang-Feng Hou ^b, Jin-Sheng Gao ^b,^*

PMCID: PMC3120522 PMID: 21754597

Abstract

In the title compound, [Cu(NO₃)₂(C₁₈H₁₆N₂O₂)₂]_n, the Cu^II ion lies on an inversion center and is six-coordinated in a Jahn–Teller-distored octahedral geometry defined by four N atoms of the pyridine derivative forming a square plane, above and below which are the O atoms of the nitrate anion. The ligand links the metal atoms linto a linear chain running along the a axis. One of the nitrate O atoms is equally disordered over two sets of sites.

Related literature

For the synthesis and background to network structures built up from flexible pyridyl-based aromatic ligands and transition metals, see Liu et al. (2010a ▶,b ▶).

Experimental

Crystal data

[Cu(NO₃)₂(C₁₈H₁₆N₂O₂)₂]
M _r = 772.22
Monoclinic,
a = 8.4859 (17) Å
b = 17.030 (3) Å
c = 12.986 (4) Å
β = 116.22 (2)°
V = 1683.6 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 291 K
0.20 × 0.18 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.867, T _max = 0.889
16256 measured reflections
3831 independent reflections
3067 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.097
S = 1.07
3831 reflections
251 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536811016096/ng5152sup1.cif

e-67-0m692-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016096/ng5152Isup2.hkl

e-67-0m692-Isup2.hkl^{(187.8KB, hkl)}

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

Acknowledgments

The authors thank the Youth Fundation of the Education Department of Sichuan Province, China (No. 08ZB031), Sichuan Agriculture University, Heilongjiang University and Heilongjiang Institute of Technology for supporting this work.

supplementary crystallographic information

Comment

The bridging pyridyl ligands can be used to construct interesting 0D to three-dimensional supramolecular architectures. Our group has reported some isolated molecule, chain, plane and three-dimensional network structures built up by flexible pyridyl-based aromatic ligands and transition metals. (Liu et al., 2010a; Liu et al., 2010b). As our continuing work for pyridyl ligands, we report here the synthesis and crystal structure of the title compound.

An asymmetric unit of the title compound consists of a 1,4-bis(pyridin-3-ylmethoxy)benzene molecule, a nitrate anion and a Cu^II cation (Figure 1). The Cu^II cations lie on the inversion centers and are six-coordinated in the Jahn-Teller distored octahedral geometry environments defined by four N atoms forming the square planes and two O atoms locating the polar axis.

In the crystal, ribbon structures along [2 0 1] direction are built up by heterocyclic ligands bridging Cu^II cations (Figure 2, Table 1).

Experimental

The 1,4-bis(pyridin-3-ylmethoxy)benzene ligand was synthesized as the reference method (Liu et al., 2010a): A mixture of 1,4-dihydroxybenzene (1.1 g, 10 mmol), 3-chloromethylpyridine hydrochloride (3.28 g, 20 mmol) and NaOH (1.6 g, 40 mmol) in acetonitrile (50 ml) was refluxed under nitrogen with stirring for 24 h. After cooling to room temperature, the solution was filtered and the residue was washed with acetonitrile for several times. The mixed filtrate was droped into 300 ml water solution to get the powder crude product. A total of 2.51 g (yield 86%) pure product was obtained by recrystallizing from the mixed solution of 10 ml water and 10 ml me thanol. The title compound was synthesized by reaction of 1,4-bis(pyridin-3-ylmethoxy)benzene ligand (0.29 g, 1.0 mmol) and Cu(NO₃)₂^.3H₂O (0.22 g, 1.0 mmol) in 5 ml water and 5 ml me thanol mixed solution. After filtration, blue block crystals suitable for X-ray diffraction were obtained by slow evaporation at room temperature for several days in 46% yield.