Poly[[tetra­aqua­tris­(μ3-hexane-1,6-di­carboxyl­ato)diterbium(III)] 0.25-hydrate]

Fei-Fei Li; Hui-Ju Zhang; Li-Na Zhang

doi:10.1107/S1600536811007719

. 2011 Mar 9;67(Pt 4):m412. doi: 10.1107/S1600536811007719

Poly[[tetraaquatris(μ₃-hexane-1,6-dicarboxylato)diterbium(III)] 0.25-hydrate]

Fei-Fei Li ^a,^*, Hui-Ju Zhang ^a, Li-Na Zhang ^a

PMCID: PMC3099756 PMID: 21753944

Abstract

In the title terbium coordination polymer, {[Tb₂(C₆H₈O₄)₃(H₂O)₄]·0.25H₂O}_n, the Tb^III atom is nine-coordinated, forming a TbO₉ polyhedra. Furthermore, two symmetric TbO₉ polyhedra share their edges, forming Tb₂O₁₆ dimers, which are linked by adipate bridges into a layered structure. Intermolecular O—H⋯O hydrogen bonds link these layers into a three-dimensional network. One of the C atoms of the adipate ligand is disordered over two positions with site-occupancy factors of 0.622 (9) and 0.378 (9). The structure also contains a disordered molecule of water of hydration, lying close to a special position, with partial occupancy.

Related literature

For background to coordination polymers, see: Moulton & Zaworotko (2001 ▶); Wood & Thompson (2007 ▶). For the structures of rare earth--adipate compounds, see: Dimos et al. (2002 ▶); Duan et al. (2004 ▶); Kim et al. (2004 ▶); Kiritsis et al. (1998 ▶). For isotypic La(III) and Dy(III) structures, see: Kim et al. (2004 ▶); Lill et al. (2005 ▶).

Experimental

Crystal data

[Tb₂(C₆H₈O₄)₃(H₂O)₄]·0.25H₂O
M _r = 826.78
Monoclinic,
a = 11.603 (6) Å
b = 13.886 (7) Å
c = 8.969 (4) Å
β = 111.017 (7)°
V = 1348.9 (11) Å³
Z = 2
Mo Kα radiation
μ = 5.27 mm⁻¹
T = 298 K
0.25 × 0.05 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) ▶ T _min = 0.352, T _max = 0.779
7908 measured reflections
2335 independent reflections
2008 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.066
S = 1.06
2335 reflections
176 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −1.85 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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/S1600536811007719/pv2390sup1.cif

e-67-0m412-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007719/pv2390Isup2.hkl

e-67-0m412-Isup2.hkl^{(114.8KB, 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
O8—H3⋯O4ⁱ	0.97	1.83	2.764 (4)	160
O8—H4⋯O5ⁱⁱ	0.92	1.78	2.691 (4)	170
O7—H1⋯O2ⁱ	0.91	1.75	2.657 (4)	170
O7—H2⋯O3ⁱⁱⁱ	0.98	1.81	2.682 (4)	146

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

Acknowledgments

The authors acknowledge the Doctoral Foundation of Henan Polytechnic University (B648174).

supplementary crystallographic information

Comment

In recent years, a great interest has been focused on the crystal engineering of novel coordination polymers, not only due to their intriguing topological structures but also potential application as functional materials in areas such as ion exchange, catalysis, optics, gas separation/storage and sensing (Moulton & Zaworotko, 2001; Wood & Thompson, 2007). The RE-adipate (RE = rare earth metal) system has been examined extensively owing to the rich structural diversity of this family of materials. A great many of compounds have been reported which exhibit structure types ranging from 1-D chain to 2-D layer and 3-D framework topologies (Dimos et al., 2002; Duan et al., 2004; Kim et al., 2004; Kiritsis et al., 1998). Arguably much of this diversity is related to the flexibility of the aliphatic dicarboxylic backbone. In this paper, we report the hydrothermal synthesis and single-crystal X-ray diffraction analysis of a novel Tb-adipate compound, which is isotypic with La(III) (Kim et al., 2004) and Dy(III) (Lill et al., 2005) analogous complexes.

The crystal structure of the title complex consists of nine oxygen atoms coordinated to Tb(III) (Fig. 1) of which seven oxygen atoms are from four adipate ligands and two from two independent coordinated water molecules. Two symmetric TbO₉ polyhedra share their edges to form a Tb₂O₁₆ dimeric unit about an inversion centet. These dimers are further linked through adipate anions to form a two-dimensional layer perpendicular to (010) (Fig. 2).

C9-atom of the adipate ligand was disordered over two sites with site occupancy factors 0.622 (9) and 0.378 (9). The structure also contains a disordered molecule of water of hydration lying close to a special position with partial occupancy.

Experimental

Colorless prismatic single crystals of the title complex were obtained using hydrothermal methods in a sealed 20 ml Teflon-lined Parr bomb. TbCl₃^. 6H₂O (0.2 g), adipic acid (0.1 g) and H₂O (10 ml) were placed in the bomb and sealed. The bomb was then heated under autogenous pressure for 7 d at 433 K and finally cooled to room temperature. Upon opening the bomb, a few single crystals was obtained for X-ray single-crystal diffraction analysis.