Poly[[diaqua­bis­{μ-4-[6-(4-carb­oxy­phen­yl)-4,4′-bipyridin-2-yl]benzoato-κ2 O:N 1′}copper(II)] dimethyl­formamide tetra­solvate]

Yabin Sun; E Song; Daguang Wang

doi:10.1107/S1600536813006430

. 2013 Mar 13;69(Pt 4):m202–m203. doi: 10.1107/S1600536813006430

Poly[[diaquabis{μ-4-[6-(4-carboxyphenyl)-4,4′-bipyridin-2-yl]benzoato-κ² O:N ^1′}copper(II)] dimethylformamide tetrasolvate]

Yabin Sun ^a, E Song ^a, Daguang Wang ^b,^*

PMCID: PMC3629482 PMID: 23634000

Abstract

In the title compound, {[Cu(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO}_n, the Cu^II ion, lying on an inversion center, is six-coordinated by two N atoms from two 4-[6-(4-carboxyphenyl)-4,4′-bipyridin-2-yl]benzoate (L) ligands, two deprotonated carboxylate O atoms from two other symmetry-related L ligands and two water molecules in a slightly distorted octahedral geometry. The Cu^II atoms are linked by the bridging ligands into a layer parallel to (101). The presence of intralayer O—H⋯O hydrogen bonds and π–π interactions between the pyridine and benzene rings [centroid–centroid distances = 3.808 (2) and 3.927 (2) Å] stabilizes the layer. Further O—H⋯O hydrogen bonds link the layers and the dimethylformamide solvent molecules.

Related literature

For the design of metal-organic coordination polymers, see: Ge & Song (2012 ▶); Herm et al. (2011 ▶); Liu et al. (2010 ▶); Wang et al. (2010 ▶). For a related structure, see: Xia et al. (2012 ▶).

Experimental

Crystal data

[Cu(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO
M _r = 1182.73
Monoclinic,
a = 7.7161 (17) Å
b = 17.550 (4) Å
c = 20.947 (4) Å
β = 96.800 (4)°
V = 2816.6 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 293 K
0.27 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.885, T _max = 0.913
14622 measured reflections
5226 independent reflections
3371 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.185
S = 1.04
5226 reflections
376 parameters
H-atom parameters constrained
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Click here for additional data file.^{(26KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813006430/hy2619sup1.cif

e-69-0m202-sup1.cif^{(26KB, cif)}

Click here for additional data file.^{(255.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006430/hy2619Isup2.hkl

e-69-0m202-Isup2.hkl^{(255.9KB, 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—H4A⋯O2ⁱ	0.82	1.86	2.584 (4)	146
O1W—H1A⋯O5ⁱⁱ	0.85	1.98	2.808 (5)	165
O1W—H1B⋯O2ⁱⁱⁱ	0.85	1.95	2.758 (4)	159

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

Acknowledgments

The authors are grateful for financial aid from The First Hospital of Jilin University.

supplementary crystallographic information

Comment

Metal-organic coordination polymers (MOCPs) with infinite one-, two- or three-dimensional structures are assembled with metal ions or polynuclear clusters as nodes and organic ligands as linkers (Herm et al., 2011; Liu et al., 2010). Recently, the chemists have devoted themselves to design and synthesize MOCPs, not only due to their potential applications in the realm of gas adsorption and separation, catalysis, magnetism, luminescence, host–guest chemistry and etc, but also for their aesthetic and often complicated architectures and topologies (Ge & Song, 2012; Wang et al., 2010). In order to extend the investigations in this field, we used a multifunctional ligand, 4,4'-(4,4'-bipyridine-2,6-diyl)dibenzoic acid (bpydbH₂) to design and synthesize the title copper(II) complex and report its structure here.

The asymmetric unit of the title compound contains one Cu^II ion lying on an inversion center, one anionic bpydbH ligand, one aqua ligand and two lattice DMF molecules. As shown in Fig. 1, the Cu^II ion is six-coordinated by two N atoms from two bpydbH ligands, two deprotonated carboxylate O atoms from two other symmetry-related bpydbH ligands and two aqua ligands, furnishing a slightly distorted octahedral geometry. The bond distances and angles are in a normal range (Xia et al., 2012). The Cu nodes are extended by the bridging bpydbH linkers into a layer parallel to (101) (Fig. 2). The presence of intralayer O—H···O hydrogen bonds and π–π interactions between the pyridine and benzene rings [centroid–centroid diatances = 3.808 (2) and 3.927 (2) Å] stabilizes the single layer.

Experimental

Cu(NO₃)₂.3H₂O (0.0063 g, 0.025 mmol) and bpydbH₂ (0.0099 g, 0.025 mmol) were suspended in a mixed solvent of dimethylformamide (DMF) (4 ml) and H₂O (0.5 ml), and heated in a 15 ml Teflon-lined stainless-steel autoclave at 80°C for 3 days. After the autoclave was cooled to room temperature slowly, green crystals were collected by filtration and washed with DMF, and dried in air (yield: 65% based on Cu).