Poly[(μ2-4,4′-bipyridine)bis­(μ4-5-tert-butyl­isophthalato)bis­(μ3-5-tert-butyl­isophthalato)di-μ3-hydroxido-penta­zinc(II)]

Dong-Sheng Zhou; Di Sun; Shi-Yao Yang; Rong-Bin Huang

doi:10.1107/S1600536809031365

. 2009 Aug 15;65(Pt 9):m1078–m1079. doi: 10.1107/S1600536809031365

Poly[(μ₂-4,4′-bipyridine)bis(μ₄-5-tert-butylisophthalato)bis(μ₃-5-tert-butylisophthalato)di-μ₃-hydroxido-pentazinc(II)]

Dong-Sheng Zhou ^a, Di Sun ^a, Shi-Yao Yang ^a,^*, Rong-Bin Huang ^a

PMCID: PMC2969937 PMID: 21577432

Abstract

The asymmetric unit of the title compound, [Zn₅(C₁₂H₁₂O₄)₄(OH)₂(C₁₀H₈N₂)]_n, consists of three Zn^II ions (one of which is located on a twofold rotation axis), two 5-tert-butylisophthalate ligands, one 4,4′-bipyridine ligand and one hydroxide group. The five Zn^II ions form a pentanuclear zinc cluster, which is further bridged by ten organic ligands, forming two-dimensional sheets. The central zinc ion of the cluster has site symmetry 2 and is octahedrally coordinated in a N₂O₄ donor set, whereas the other four zinc atoms are tetrahedrally coordinated by four O atoms. The coordination modes for the 5-tert-butylisophthalates are bis(bidentate) or bidentate-monodentate. Hydrogen bonds are formed between adjacent sheets through the hydroxide groups and the O atoms of the monodentate carboxylate groups. The two tert-butyl groups are disordered over two positions with ratios of 0.64 (2):0.36 (2) and 0.85 (3):0.15 (3).

Related literature

For general background to the structures and potential applications of isophthalic acid and its derivatives, see Li & Huang (2008 ▶); Ma et al. (2007 ▶); Pan et al. (2006 ▶); Yang et al. (2002 ▶, 2005 ▶). For related structures, see Li et al. (2004 ▶); Wang et al. (2005 ▶).

Experimental

Crystal data

[Zn₅(C₁₂H₁₂O₄)₄(OH)₂(C₁₀H₈N₂)]
M _r = 1397.91
Monoclinic,
a = 26.1995 (5) Å
b = 11.2592 (2) Å
c = 19.6223 (4) Å
β = 102.0444 (18)°
V = 5660.87 (19) Å³
Z = 4
Mo Kα radiation
μ = 2.16 mm⁻¹
T = 173 K
0.34 × 0.30 × 0.20 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.527, T _max = 0.671
13453 measured reflections
5494 independent reflections
4246 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.066
S = 1.00
5494 reflections
401 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.25 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031365/dn2465sup1.cif

e-65-m1078-sup1.cif^{(29.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031365/dn2465Isup2.hkl

e-65-m1078-Isup2.hkl^{(269.1KB, 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
O9—H9⋯O7ⁱ	0.838 (10)	2.04 (2)	2.783 (3)	148 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful for financial support by the National Natural Science Foundation of China (grant No. 20471049) and Xiamen University.

supplementary crystallographic information

Comment

Isophthalic acid and its derivatives have been used to construct coordination polymers. Some of these compounds display interesting structures and potential application properties (Li et al., 2008; Ma et al., 2007; Pan et al., 2006; Yang et al., 2002; Yang et al., 2005). In this paper we report a coordination polymer [Zn₅(µ₃-OH)₂(tbip)₄(bpy)]_n, 1 (tbip = 5-tert-butylisophthalate, bpy = 4,4'-bipyridine) synthesized by hydrothermal reaction.

The structure of 1 contains pentanuclear zinc clusters, (Fig. 1) in which each µ₃-OH links three crystallographically unique Zn^II ions. The Zn^II ions exhibit two different coordination geometries: Zn1 coordinates to two µ₃-OH moieties and two carboxylate oxygen atoms from two different tbips in the plane and two nitrogen atoms from two bpy ligands at the apexes giving a slightly distorted octahedral geometry; Zn2 or Zn3 atom is coordinated by three oxygen atoms from three tbips and one µ₃-OH atom to complete a distorted tetrahedral environment. Coordination polymers with similar but different pentanuclear zinc clusters have been recently reported (Li et al., 2004; Wang et al., 2005). Two coordination modes for the tbips have been found: one is bis(bidentate), and the other one adopts bidentate and monodentate for each of its carboxyl groups. As a result, each pentanuclear zinc cluster is surrounded by ten organic ligands, eight tbips and two bpys. Each pentanuclear zinc cluster is further linked to six nearest-neighbors, forming a two-dimensional sheet parallel to bc plane (Fig. 2). The two-dimensional sheets are further packed along a axis (Fig. 3). Hydrogen bonds are formed between adjacent sheets by the hydroxyl groups and the oxygen atoms of the monodentate carboxyl groups.

Experimental

The suspension of 5-tert-butylisophthalic acid (H₂tbip, 0.045 g, 0.20 mmol) and 4,4'-bipyridine (bpy, 0.039 g, 0.20 mmol) in H₂O (10 ml), and 25% tetramethylammonium hydroxide aqueous solution was slowly added until the pH of the solution was adjusted to 7, then Zn(NO₃)₂^.6H₂O (0.12 g, 0.40 mmol) was added. The mixture was placed in a 20 ml Teflon-lined vessel, heated to 170°C at the rate of 0.2°C/min, and kept at 170°C for 3 days, then slowly cooled down to room temperature at the rate of 0.1°C /min. Colorless platelet crystals (0.045 g, yield 64%) were separated by filtration, washed with deionized water and dried in air. Elemental Analysis: C₅₈H₅₈N₂O₁₈Zn₅, found (calc.) C 49.82 (49.83), H 4.27 (4.18), N 1.99 (2.00). FTIR (KBr, cm^-1): 3412(s), 2960 (s), 1610(s), 1552(m), 1369 (m), 1069 (w), 808 (w), 719 (w).