Potassium aqua­terbium(III) oxalate sulfate

Ya-Guang Sun; Mei-yan Guo; Gang Xiong; Bing Jiang; Lei Wang

doi:10.1107/S1600536809019679

. 2009 Jun 6;65(Pt 7):i48. doi: 10.1107/S1600536809019679

Potassium aquaterbium(III) oxalate sulfate

Ya-Guang Sun ^a,^*, Mei-yan Guo ^a, Gang Xiong ^a, Bing Jiang ^a, Lei Wang ^a

PMCID: PMC2969189 PMID: 21582643

Abstract

Single crystals of KTb(C₂O₄)(SO₄)(H₂O), potassium aquaterbium(III) oxalate sulfate, were obtained under hydrothermal conditions. In the crystal structure, the Tb(III) atom is coordinated by four O atoms from two oxalate anions, three O atoms from three sulfate anions and one O atom from a water molecule within a TbO₈ distorted square antiprismatic coordination. The potassium and terbium(III) atoms are bridged by the oxalate and sulfate groups, forming a three-dimensional structure. The coordination mode of the oxalate has not yet been reported. O—H⋯O hydrogen bonding between the water molecules and the oxygen atoms of oxalate and sulfate anions is also observed.

Related literature

For oxaltes and their coordination modes, see: Audebrand et al. (2003 ▶); Dean et al. (2004 ▶); Lu et al. (2004 ▶).

Experimental

Crystal data

KTb(C₂O₄)(SO₄)(H₂O)
M _r = 400.14
Monoclinic,
a = 6.5274 (13) Å
b = 8.5072 (17) Å
c = 14.591 (4) Å
β = 112.65 (3)°
V = 747.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 10.32 mm⁻¹
T = 113 K
0.06 × 0.04 × 0.02 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.576, T _max = 0.820
4812 measured reflections
1317 independent reflections
1079 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.051
S = 1.05
1317 reflections
127 parameters
24 restraints
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.78 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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, 1998 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019679/br2105sup1.cif

e-65-00i48-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019679/br2105Isup2.hkl

e-65-00i48-Isup2.hkl^{(65.1KB, 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—H9A⋯O2ⁱ	0.96 (6)	1.88 (4)	2.731 (4)	145 (5)
O9—H9B⋯O3ⁱⁱ	0.96 (6)	1.86 (3)	2.787 (5)	160 (9)
O9—H9B⋯O7ⁱ	0.97 (6)	2.83 (9)	3.149 (5)	100 (6)

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

Acknowledgments

This project was sponsored by SRF for ROCS, SEM, and the Research Foundation of Education Department of Liaoning Province (No. 2008581).

supplementary crystallographic information

Comment

Recently, rationally design of novel inorganic componds based on alkali metal ions and rare earth ions are currently of great interest because of their potential applications in photoluminescent fields. For purpose of enriching the chemistry field of this compound family, we have successfully synthesized the title compound.

In the title compound, the coordination environments of the rare earth Tb^III cations consist of eight O atoms which are associated with one water molecule, two sulfate groups and two oxalates. Tb^III cations are at the shared apex of two dicapped rectangular pyramids (Fig.1). The K⁺ cations are surrounded by nine O atoms, including one water O atom, six O atoms from oxalates and two O atoms from sulfate groups.

Oxalates are of considerable interest because many of them are natural minerals and in addition, the oxalate anion can adopt different coordination modes to bind metals to form infinite chains, sheets and networks, leading to the rich structural chemistry (Lu et al., 2004; Dean et al., 2004; Audebrand et al., 2003). In the title compound, the oxalate ligand has an unique coordination mode (κ³-κ²-µ₄)-(κ³-κ²-µ₄)-µ₆-ox^2-. Fig.2 shows coordination mode of the oxalate and sulfate ligands in the title compuond.

Two adjacent Tb^III ions were connected through the oxalates to form one-dimensional chain structure (see Fig.3), and then were connected through the sulfate anions and water molecules to form the three-dimensional framework (see Fig.4).

Experimental

A mixture of FeSO₄.7H₂O (0.1 mmol),Tb(NO₃)₃.5H₂O (0.1 mmol) and oxalic acid (0.2 mmol) in H₂O (10 mL) was adjust to pH=6.8 with KOH aqueous solution, sealed in a 25 mL Teflon-lined bomb at 430 K for 4 days and then slowly cooled to room temperature at a rate of 5° K per hour. Colorless block crystals were obtained by filtration.The structure was determined by single-crystal diffraction.