Poly[[diaqua­tris­(μ2-3-methyl­pyridine-2-carboxyl­ato)(3-methyl­pyridine-2-car­boxyl­ato)sodiumterbium(III)] ethanol monosolvate monohydrate]

Taewoo Lee; Sung Kwon Kang

doi:10.1107/S1600536810038456

. 2010 Oct 2;66(Pt 11):m1347–m1348. doi: 10.1107/S1600536810038456

Poly[[diaquatris(μ₂-3-methylpyridine-2-carboxylato)(3-methylpyridine-2-carboxylato)sodiumterbium(III)] ethanol monosolvate monohydrate]

Taewoo Lee ^a, Sung Kwon Kang ^a,^*

PMCID: PMC3009174 PMID: 21588794

Abstract

In the title compound, {[NaTb(C₇H₆NO₂)₄(H₂O)₂]·C₂H₅OH·H₂O}_n, the Tb^III atom is eight-coordinated in a slightly distorted square-antiprismatic geometry defined by four carboxylate O atoms and four pyridine N atoms. The bond lengths lie within the range 2.3000 (2)–2.326 (2) Å for the Tb—O bonds and 2.543 (3)–2.553 (3) Å for the Tb—N bonds. The Na^I atom is five-coordinated by two water O atoms and three carboxylate O atoms in a distorted square-pyramidal geometry. In the crystal, intermolecular O—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For general background to luminescent compounds, see: Fan et al. (2009 ▶); Oh et al. (2010 ▶); Seo et al. (2010 ▶); Zhou et al. (2010 ▶). For luminescence properties of metal compounds, see: Godlewska et al. (2008 ▶); Kang (2010 ▶); Kim et al. (2010 ▶); Legendziewicz (2002 ▶); Lis et al. (2009 ▶); Seo et al. (2009 ▶).

Experimental

Crystal data

[NaTb(C₇H₆NO₂)₄(H₂O)₂]·C₂H₆O·H₂O
M _r = 826.54
Orthorhombic,
a = 18.4662 (6) Å
b = 18.5290 (5) Å
c = 9.8939 (3) Å
V = 3385.30 (18) Å³
Z = 4
Mo Kα radiation
μ = 2.17 mm⁻¹
T = 174 K
0.16 × 0.11 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.704, T _max = 0.856
44141 measured reflections
6652 independent reflections
5995 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.045
S = 1.07
6652 reflections
460 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.56 e Å⁻³
Absolute structure: Flack (1983 ▶), 2234 Friedel pairs
Flack parameter: 0.001 (6)

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810038456/is2603sup1.cif

e-66-m1347-sup1.cif^{(25.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038456/is2603Isup2.hkl

e-66-m1347-Isup2.hkl^{(319KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Na41—O9	2.324 (2)
Na41—O29ⁱ	2.390 (3)
Na41—O39ⁱⁱ	2.374 (2)
Na41—O42	2.265 (3)
Na41—O43	2.476 (3)

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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
O42—H42A⋯O47	0.81 (2)	1.95 (2)	2.742 (4)	163 (4)
O42—H42B⋯O38ⁱⁱ	0.81 (2)	2.01 (2)	2.819 (3)	169 (4)
O43—H43A⋯O28ⁱ	0.82 (2)	1.99 (2)	2.796 (3)	171 (4)
O43—H43A⋯O29ⁱ	0.82 (2)	2.53 (3)	3.050 (3)	122 (3)
O43—H43B⋯O44ⁱ	0.81 (2)	2.02 (2)	2.794 (4)	162 (3)
O44—H44A⋯O8	0.80 (4)	2.31 (4)	3.103 (4)	170 (4)
O44—H44A⋯O9	0.80 (4)	2.34 (4)	2.943 (4)	133 (4)
O44—H44B⋯O43	0.80 (4)	2.07 (4)	2.790 (4)	151 (4)
O47—H47⋯O19ⁱⁱ	0.80 (2)	1.96 (2)	2.726 (3)	159 (4)

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

Acknowledgments

The X-ray data were collected at the center for Research Facilities at Chungnam National University.

supplementary crystallographic information

Comment

Luminescent metal compounds with N-containing ligands have been reported in the investigation of their interesting photophysical properties and various coordination modes (Seo et al., 2010; Zhou et al., 2010; Fan et al., 2009). Especially, lanthanide metal complexes have been extensively studied due to their unique luminescence properties (Lis et al., 2009; Godlewska et al., 2008; Legendziewicz, 2002). As an extension of our work (Kang, 2010; Oh et al., 2010; Kim et al., 2010; Seo et al., 2009) on luminescent complexes, herein, we report the crystal structure and luminescent properties of the title Tb(III) chloride complex with 3-methylpyridine-2-carboxylic acid (3-methylpicolinic acid), (I).

In the title compound, {[NaTb(H₂O)₂(C₇H₆NO₂)₄].C₂H₅OH.H₂O}_n, the Tb^III atom is eight-coordinated within a slightly distorted square antiprismatic geometry. The Tb^III atom is coordinated to the four carboxylate-O atoms and four pyridine-N atoms. The Tb—O bond distances are within the range of 2.300 (2)–2.326 (2) Å (Table 1), which are significantly shorter than the sum of the covalent radii of Tb and O atoms (2.420 Å). The Na⁺ ion is five-coordinated with two water-O atoms and three carboxylate-O atoms to form a distorted square pyramidal geometry. In the crystal structure, intermolecular O—H···O hydrogen bonds (Table 2) link the uncoordinated water molecule to the coordinated picolinic ligands and further link the molecules into a three-dimensional network.

The title compound exhibits an intense emission at 543 nm upon 326 nm excitation in PL spectra with 325 nm of He—Cd laser excitation wavelength

Experimental

Terbium trichloride solution was prepared by dissolving TbCl₃.6H₂O (0.27 g, 1.0 mmol; Aldrich) in absolute ethanol (20 ml) at room temperature with stirring. The ligand solution was prepared by dissolving 3-methylpicolinic acid (0.55 g, 4.0 mmol; Aldrich) in absolute ethanol (30 ml) at room temperature with stirring. The pH of the ligand solution was adjusted to about 5.1 with 2 N NaOH solution. The Terbium trichloride solution was added dropwise slowly to the ligand solution. The reaction mixture was stirred for 1 h at room temperature. Colourless crystals of (I) were obtained at room temperature over a period of a few weeks. The complex was recrystallized from the mixture of distilled water and absolute ethanol solution.