catena-Poly[[(2,2′-bipyridine)copper(II)]-μ-5-tert-butyl­isophthalato]

Xiao-Ling Li; Miao-Ling Huang

doi:10.1107/S1600536808035484

. 2008 Nov 8;64(Pt 12):m1501–m1502. doi: 10.1107/S1600536808035484

catena-Poly[[(2,2′-bipyridine)copper(II)]-μ-5-tert-butylisophthalato]

Xiao-Ling Li ^a,^*, Miao-Ling Huang ^b

PMCID: PMC2960003 PMID: 21581122

Abstract

In the crystal structure of the title polymeric compound, [Cu(C₁₂H₁₂O₄)(C₁₀H₈N₂)]_n, the asymmetric unit consists of one Cu^II ion, one 5-tert-butylisophthalate (tbip) and one 2,2′-bipyridine (bpy) ligand. The copper(II) ion is four-coordinated by two N atoms from bipy and two O atoms from two tbip ligands, leading to a distorted tetrahedral coordination. Each tbip ligand adopts a bis-monodentate coordination mode to connect two symmetry-related copper(II) ions, so forming a zigzag polymer chain parallel to [001]. The tert-butyl methyl groups are disordered over two positions with occupancies of 0.506 (6)/0.494 (6)

Related literature

For related literature on the synthesis of flexible organic ligands, see: Chang et al. (2005 ▶); Ma, Chen et al. (2008 ▶); Xu et al. (2006 ▶). For related literature on coordination polymers, see: Ma, Wang, Huo et al. (2008 ▶); Ma, Wang, Wang et al. (2008 ▶); Pan et al. (2006 ▶); Yang et al. (2002 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Cu(C₁₂H₁₂O₄)(C₁₀H₈N₂)]
M _r = 439.94
Monoclinic,
a = 8.905 (2) Å
b = 20.875 (5) Å
c = 11.564 (3) Å
β = 98.188 (3)°
V = 2127.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 296 (2) K
0.29 × 0.22 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.716, T _max = 0.845
15716 measured reflections
3949 independent reflections
3021 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.130
S = 1.05
3949 reflections
260 parameters
91 restraints
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536808035484/su2072sup1.cif

e-64-m1501-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035484/su2072Isup2.hkl

e-64-m1501-Isup2.hkl^{(193.6KB, hkl)}

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

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

Cu1—O1	1.933 (2)
Cu1—O3ⁱ	1.956 (2)
Cu1—N1	1.985 (3)
Cu1—N2	1.983 (3)

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O1—Cu1—O3ⁱ	88.17 (11)
O1—Cu1—N1	94.83 (11)
O3ⁱ—Cu1—N1	172.79 (11)
O1—Cu1—N2	173.34 (11)
O3ⁱ—Cu1—N2	96.69 (11)
N1—Cu1—N2	80.88 (11)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Luo Yang Normal University for supporting this work.

supplementary crystallographic information

Comment

It is well known that organic ligands play a crucial role in the design and construction of desirable frameworks. The changes in flexibility, length and symmetry of organic ligands can result in a remarkable class of materials bearing diverse architectures and functions. Thus, the construction of target molecules is a challenge for synthetic chemists (Ma et al., 2008; Chang et al., 2005; Xu et al., 2006). Benzene-1,3-dicarboxylic acid (isophthalic acid, H2isop) and its derivatives, with special conformations such as, an angle of 120° between two carboxylic groups, present versatile coordination modes that can yield predetermined networks. Such ligands have been widely used to construct coordination polymers (Pan et al., 2006; Yang et al., 2002; Ma et al., 2008).

The title compound, (I), was prepared by hydrothermal synthesis using 5-tert-butyl isophthalic acid, 2,2'-bipyridine and copper(II) actate. The asymmetric unit of (I) consists of one copper(II) ion, one tbip and one bipy ligand molecules (Fig. 1). Each copper(II) ion is four-coordinated by two nitrogen atoms from one bipy molecule and two oxygen atoms from two tbip ligands (Table 1). The coordination geometry of the copper(II) ion is distorted tetrahedral. The Cu—O bond lengths [1.933 (2)–1.965 (2) Å] are within the range reported for tetrahedral environments, and the Cu—N bond lengths [1.983 (3)–1.985 (3) Å] are also similar to those found in other tetrahedral copper complexes of bipy (Allen et al., 1987). Each tbip ligand adopts the bis-monodentated coordination mode to connect two symmetry related copper(II) ions so forming a zigzag polymer chain (Fig. 2).

Experimental

A mixture of 5-tert-butyl isophthalic acid (0.1 mmol, 23.1 mg), 2,2'-bipyridine (0.1 mmol, 15.8 mg), Cu(OAc).2.4H₂O (0.05 mmol, 11.5 mg), NaOH (0.1 mmol, 4.0 mg) and H₂O (15 ml) was placed in a Teflon-lined stainless steel vessel, and heated to 160 °C for 4 days. It was then cooled to room temperature over a period of 24 h. Blue block-like crystals of compound (I) were obtained.