catena-Poly[[tris­(pyridine-κN)copper(II)]-μ-tetra­fluoro­terephthalato-κ2 O 1:O 4]

Chang-Ge Zheng; Jie Zhang; Jian-Quan Hong; Song Li

doi:10.1107/S1600536808018977

. 2008 Jun 28;64(Pt 7):m965. doi: 10.1107/S1600536808018977

catena-Poly[[tris(pyridine-κN)copper(II)]-μ-tetrafluoroterephthalato-κ² O ¹:O ⁴]

Chang-Ge Zheng ^a,^*, Jie Zhang ^a, Jian-Quan Hong ^a, Song Li ^a

PMCID: PMC2961727 PMID: 21202811

Abstract

In the title compound, [Cu(C₈F₄O₄)(C₅H₅N)₃]_n, the Cu^II atom, lying on a twofold rotation axis, is five-coordinated by two O atoms from two tetrafluoroterephthalate ligands and three N atoms from three pyridine ligands in a distorted trigonal-bipyramidal geometry. Adjacent Cu^II atoms are connected via the bridging tetrafluoroterephthalate ligands into a one-dimensional chain running along the [101] direction.

Related literature

For related literature, see: Baeg & Lee (2003 ▶); Baruah et al. (2007 ▶); Bastin et al. (2008 ▶); Cheng et al. (2007 ▶); Eddaoudi et al. (2000 ▶); Gould et al. (2008 ▶); Reineke et al. (1999 ▶); Stephenson & Hardie (2006 ▶); Yuan et al. (2004 ▶); Zhang et al. (2007 ▶); Zheng et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₈F₄O₄)(C₅H₅N)₃]
M _r = 536.92
Monoclinic,
a = 15.3579 (8) Å
b = 8.7652 (5) Å
c = 16.6050 (9) Å
β = 100.241 (3)°
V = 2199.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 273 (2) K
0.15 × 0.10 × 0.06 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.857, T _max = 0.939
10049 measured reflections
1950 independent reflections
1857 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.071
S = 1.09
1950 reflections
160 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018977/hy2139sup1.cif

e-64-0m965-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018977/hy2139Isup2.hkl

e-64-0m965-Isup2.hkl^{(96.1KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—N1	2.0236 (16)
Cu1—O1	2.0609 (12)
Cu1—N2	2.073 (2)

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N1—Cu1—N1ⁱ	174.71 (9)
N1—Cu1—O1	91.84 (6)
N1—Cu1—O1ⁱ	85.17 (6)
O1—Cu1—O1ⁱ	111.11 (8)
N1—Cu1—N2	92.64 (4)
O1—Cu1—N2	124.45 (4)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Center for Analysis and Testing of Jiangnan University and the Research Institute of Elemento–Organic Chemistry of Taishan College.

supplementary crystallographic information

Comment

Recently, organically directed metal–terephthalates have attracted much attention due to their novel structures and desirable physical properties, and a lot of research work has been done on this type of complexes (Bastin et al., 2008; Eddaoudi et al., 2000; Gould et al., 2008). However, there are rare reports about halogen substituted terephthalate metal complexes till now. Some research work in computational study suggests that adsorption property in gas storage can be improved with electronegative atoms (e.g. halogen atoms) in the organic linkers or frameworks (Zhang et al., 2007). New topologies with favorable properties will be achieved by introducing some strong electronegative atoms to the phenyl ring.

The title compound consists of one-dimensional neutral zig-zag chains (Fig. 1 and Fig. 2). The tetrafluoroterephthalate ligand is coordinated to Cu^II ion in a bridging bis-monodentate fashion. In the trigonal bipyramidal coordination unit, two O atoms from two tetrafluoroterephthalate ligands and one N atom from a pyridine molecule form the equatorial plane. The axial positions are occupied by N atoms from two pyridine molecules with an N—Cu—N angle of 174.71 (9)° (Table 1). The Cu—N bond lengths lie in the range of 2.0236 (16) to 2.073 (2) Å and agree well with the reported values (Baruah et al., 2007; Cheng et al., 2007). The Cu—O bond lengths are 2.0609 (12) Å, which are comparable with the reported values in the similar complexes (Baeg & Lee, 2003; Stephenson & Hardie, 2006; Yuan et al., 2004). In the aromatic ring systems, the values of bond lengths and angles coincide with those previously reported (Zheng et al., 2008).

Experimental

All the reagents and solvents employed were commercially available. Tetrafluoroterephthalic acid was purified by recrystallization. According to the literature procedure (Reineke et al., 1999), the title compound was synthesized by slow vapor diffusion at room temperature of pyridine (3 ml) into an N,N-dimethylformamide solution (2 ml) containing a mixture of tetrafluoroterephthalic acid (0.071 g, 0.30 mmol) and Cu(NO₃)₂.3H₂O (0.036 g, 0.15 mmol) diluted with CH₃OH (6 ml). After two weeks, blue block-shaped crystals were obtained (yield 55% based on Cu). Analysis, calculated for C₂₃H₁₅CuF₄N₃O₄: C 51.45, H 2.82, N 7.82%; found: C 51.50, H 2.86, N 7.76%.