Poly[[triaqua­(μ3-4-oxidopyridine-2,6-dicarboxyl­ato)terbium(III)] monohydrate]

Dong-Yu Lv; Zhu-Qing Gao; Jin-Zhong Gu

doi:10.1107/S1600536811005447

. 2011 Feb 23;67(Pt 3):m357–m358. doi: 10.1107/S1600536811005447

Poly[[triaqua(μ₃-4-oxidopyridine-2,6-dicarboxylato)terbium(III)] monohydrate]

Dong-Yu Lv ^a,^*, Zhu-Qing Gao ^b, Jin-Zhong Gu ^a

PMCID: PMC3052142 PMID: 21522284

Abstract

In the title coordination polymer, {[Tb(C₇H₂NO₅)(H₂O)₃]·H₂O}_n, the Tb^III atom is eight-coordinated by a tridentate 4-oxidopyridine-2,6-dicarboxylate trianion, two adjacent monodentate anions and three water molecules, forming a distorted bicapped trigonal–prismatic TbNO₇ coordination environment. The anions bridge adjacent Tb^III ions into double chains. Adjacent chains are further connected into sheets parallel to (10 Inline graphic ). O—H⋯O hydrogen bonds involving both coordinated and uncoordinated water molecules generate a three-dimensional network.

Related literature

For structures and properties of luminescent lanthanide coordination compounds, see: Kustaryono et al. (2010 ▶); He et al. (2010 ▶); Li et al. (2008 ▶); Luo et al. (2008 ▶). For the use of multi-carboxylate and heterocyclic acids in coordination chemistry, see: Li et al. (2008 ▶); Luo et al. (2008 ▶). For the dicarboxylate ligand 4-oxido-pyridine-2,6-dicarboxylate, see: Gao et al. (2008 ▶). For the isotypic structures of the Dy and Eu analogues, see: Gao et al. (2006 ▶) and Lv et al. (2010 ▶), respectively. For bond lengths and angles in other complexes with eight-coordinate Tb^III, see: Chen et al. (2008 ▶); Ramya et al. (2010 ▶).

Experimental

Crystal data

[Tb(C₇H₂NO₅)(H₂O)₃]·H₂O
M _r = 411.08
Monoclinic,
a = 9.953 (2) Å
b = 7.5454 (16) Å
c = 15.461 (3) Å
β = 105.126 (2)°
V = 1120.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 6.35 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.162, T _max = 0.247
7828 measured reflections
2080 independent reflections
1929 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.019
wR(F ²) = 0.051
S = 1.10
2080 reflections
196 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.34 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 ▶) and DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005447/wm2449sup1.cif

e-67-0m357-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005447/wm2449Isup2.hkl

e-67-0m357-Isup2.hkl^{(102.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Tb1—O5ⁱ	2.3035 (19)
Tb1—O8	2.368 (2)
Tb1—O6	2.383 (2)
Tb1—O4ⁱⁱ	2.4106 (19)
Tb1—O3	2.415 (2)
Tb1—O7	2.416 (2)
Tb1—O1	2.424 (2)
Tb1—N1	2.471 (2)

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

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H1W⋯O1ⁱⁱⁱ	0.85 (4)	2.10 (3)	2.799 (3)	139 (3)
O6—H2W⋯O5^iv	0.86 (4)	1.93 (3)	2.725 (3)	154 (3)
O7—H3W⋯O9^v	0.88 (2)	1.84 (2)	2.687 (3)	162 (4)
O7—H4W⋯O9	0.85 (4)	2.23 (3)	2.995 (4)	151 (3)
O8—H5W⋯O2^vi	0.85 (2)	1.85 (2)	2.693 (3)	175 (4)
O8—H6W⋯O3ⁱⁱ	0.85 (4)	1.85 (4)	2.680 (3)	167 (4)
O9—H7W⋯O2^vii	0.86 (4)	1.84 (2)	2.699 (3)	175 (4)
O9—H8W⋯O4ⁱ	0.85 (4)	2.37 (4)	3.073 (4)	141 (5)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

supplementary crystallographic information

Comment

The design and synthesis of luminescent lanthanide coordination polymers have achieved great progress during the last years owing to their potential applications in biomedical imaging, as luminescent sensors or as fluorescent probes (Kustaryono et al., 2010; He et al., 2010). Eu and Tb are the most useful lanthanides due to their good fluorescence properties (Li et al., 2008; Luo et al., 2008). Many multi-carboxylate or heterocylic carboxylic acids are used for designing such materials (Li et al., 2008; Luo et al., 2008). For lanthanide coordination polymers, 4-hydroxy-pyridine-2,6-dicarboxylic acid is an excellent bridging pyridine dicarboxylate ligand (Lv et al., 2010; Gao et al., 2008), which can provide at most one nitrogen atom and five O coordination sites. In order to extend the investigation in this field, we synthesized the lanthanide coordination polymer {[Tb(C₇H₂NO₅)(H₂O)₃]^.H₂O}, and report its structure here.

The title compound is isotypic with its Dy (Gao et al., 2006) and Eu (Lv et al., 2010) analogues. As shown in Fig.1, the asymmetric unit contains one Tb(III) ion, one 4-oxidopyridine-2,6-dicarboxylate anion, three coordinated water molecules, and one water molecule of crystallisation. The Tb atom is eight-coordinated by seven oxygen atoms from three anions and three coordinated water molecules and by one nitrogen atom from one tridentate anion (the other two anions are monodentate), forming a distorted bicapped trigonal-prismatic coordination environment.

Important bond distances and angles are presented in Table 1. The Tb—O bond lengths [2.3035 (19) to 2.424 (2) Å] are shorter than the Tb—N bond length [2.471 (2) Å], which is in agreement with the bond lengths observed in other Tb(III) complexes (Chen et al., 2008; Ramya et al., 2010). The anion adopts a µ₃-pentadentate coordination mode, as shown in Fig. 1. The anions bridge adjacent Tb^III ions to form infinite double chains (Fig. 2). Adjacent chains are further connected by the coordination of the anions and Tb(III) ions into a two-dimensional sheet parallel to (101) (Fig. 3), which are further extended into a three-dimensional framework through O—H···O hydrogen-bonding interactions including both coordinated and uncoordinated water molecules (Table 2).

Experimental

To a solution of terbium(III) nitrate hexahydrate (0.136 g, 0.3 mmol) in water (5 ml) was added an aqueous solution (5 ml) of the ligand (0.060 g, 0.3 mmol) and a drop of triethylamine. The reactants were sealed in a 25-ml Teflon-lined stainless-steel Parr bomb. The bomb was heated at 433 K for 3 days. The cool solution contained single crystals in ca 60% yield. Anal. Calcd for C₇H₁₀TbNO₉: C, 20.45; H, 2.45; N, 3.41. Found: C, 20.16; H, 2.17; N, 3.74.