Poly[tetra­aquadi-μ4-oxalato-potassium­ytterbium(III)]

Zhang, F.-M.; Hou, G.-F.; Yan, P.-F.; Li, G.-M.

doi:10.1107/S1600536811046022

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1719

https://doi.org/10.1107/S1600536811046022

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Poly[tetraaquadi-μ₄-oxalato-potassiumytterbium(III)]

Feng-Ming Zhang,^a Guang-Feng Hou,^a Peng-Fei Yan ^a and Guang-Ming Li ^a ^*

^aKey Laboratory of Functional Inorganic Materials Chemistry (MOE), School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China
^*Correspondence e-mail: gmli_2000@163.com

(Received 17 October 2011; accepted 1 November 2011; online 9 November 2011)

In the title compound, [KYb(C₂O₄)₂(H₂O)₄]_n, the Yb^III ion lies on a site of $[\overline{4}]$ symmetry in a dodecahedral environment defined by eight O atoms from four oxalate ligands. The K atom lies on a different $[\overline{4}]$ axis and is coordinated by four O atoms from four oxalate ligands and four water O atoms. The oxalate ligand has an inversion center at the mid-point of the C—C bond. The metal ions are linked by the oxalate ligands into a three-dimensional framework. O—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For related structures, see: Camara et al. (2003 ); Zhang et al. (2009 ).

Experimental

Crystal data

[KYb(C₂O₄)₂(H₂O)₄]
M_r = 460.24
Tetragonal, I 4₁ /a
a = 11.3502 (16) Å
c = 8.9142 (18) Å
V = 1148.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 8.57 mm⁻¹
T = 293 K
0.08 × 0.07 × 0.07 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.562, T_max = 0.606
5407 measured reflections
648 independent reflections
585 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.039
S = 0.94
648 reflections
41 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Selected bond lengths (Å)

K1—O1	2.8402 (19)
K1—O3	2.871 (3)
Yb1—O1	2.3629 (19)
Yb1—O2ⁱ	2.304 (2)
Symmetry code: (i) -x, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1⋯O3ⁱⁱ	0.85	2.08	2.899 (3)	163
O3—H2⋯O2ⁱⁱⁱ	0.85	2.06	2.837 (3)	152
Symmetry codes: (ii) $[-y+{\script{5\over 4}}, x+{\script{3\over 4}}, z-{\script{1\over 4}}]$ ; (iii) $[-y+{\script{3\over 4}}, x+{\script{3\over 4}}, -z+{\script{3\over 4}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811046022/hy2482sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046022/hy2482Isup2.hkl

checkCIF report

Comment top

Lanthanide complexes with spectroscopic and magnetic properties are currently of considerable interest. Oxalate ligand can serve as bridging ligand in high dimensional frameworks (Camara et al., 2003; Zhang et al., 2009). In this paper, we present the synthesis and crystal structure of the title compound.

The title compound was obtained as a byproduct by the decomposition of 1,3,5-triazine-2,4,6-tricarboxylate ligand. In the title compound, [YbK(C₂O₄)₂(H₂O)₄]_n, the eight-coordinated Yb^III ion lies on a 4 site symmetry in a distorted dodecahedral geometry defined by eight O atoms from four oxalate ligands. The eight-coordinated K ion is also locate on another site of 4 symmetry in a distorted dodecahedral geometry defined by four O atoms from oxalate ligands and four O atoms from water molecules (Fig. 1, Table 1).

In the crystal, each oxalate ligand links two Yb and two K atoms, forming a three-dimensional framework (Fig. 2). O—H···O hydrogen bonds are present (Table 2).

Related literature top

For related structures, see: Camara et al. (2003); Zhang et al. (2009).

Experimental top

The title compound was obtained as a byproduct caused by the decomposition of 1,3,5-triazine-2,4,6-tricarboxylate ligand. Yb(NO₃)_3.6H₂O (14.01 mg, 0.03 mmol) and potassium salt of 1,3,5-triazine-2,4,6-tricarboxylate (9.8 mg, 0.03 mmol) were dissolved in 15 ml water. After stirring at room temperature for 0.5 h, the solution was allowed to stand for about one week. Colorless block crystals were obtained in 36% yield.

Structure description top

In the crystal, each oxalate ligand links two Yb and two K atoms, forming a three-dimensional framework (Fig. 2). O—H···O hydrogen bonds are present (Table 2).

For related structures, see: Camara et al. (2003); Zhang et al. (2009).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) -x, 1-y, -z; (ii) 1/4-y, 3/4+x, -1/4+z; (iii) -3/4+y, 3/4-x, -1/4-z; (iv) 3/4-y, 3/4+x, -1/4-z; (v) -1/4+y, 3/4-x, -1/4+z; (vi) x, 1/2+y, z; (vii) -x, 3/2-y, z; (viii) 3/4-y, 3/4+x, 3/4-z; (ix) -3/4+y, 3/4-x, 3/4-z.]
	Fig. 2. A packing view along [001], showing the three-dimensional framework.

Poly[tetraaquadi-µ₄-oxalato-potassiumytterbium(III)] top

Crystal data top

[KYb(C₂O₄)₂(H₂O)₄]	D_x = 2.662 Mg m⁻³
M_r = 460.24	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 4696 reflections
Hall symbol: -I 4ad	θ = 3.6–27.4°
a = 11.3502 (16) Å	µ = 8.57 mm⁻¹
c = 8.9142 (18) Å	T = 293 K
V = 1148.4 (3) Å³	Block, colorless
Z = 4	0.08 × 0.07 × 0.07 mm
F(000) = 868

Data collection top

Rigaku R-AXIS RAPID diffractometer	648 independent reflections
Radiation source: fine-focus sealed tube	585 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scan	θ_max = 27.4°, θ_min = 3.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
T_min = 0.562, T_max = 0.606	k = −13→14
5407 measured reflections	l = −10→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.039	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
648 reflections	(Δ/σ)_max < 0.001
41 parameters	Δρ_max = 0.55 e Å⁻³
3 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[KYb(C₂O₄)₂(H₂O)₄]	Z = 4
M_r = 460.24	Mo Kα radiation
Tetragonal, I4₁/a	µ = 8.57 mm⁻¹
a = 11.3502 (16) Å	T = 293 K
c = 8.9142 (18) Å	0.08 × 0.07 × 0.07 mm
V = 1148.4 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	648 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	585 reflections with I > 2σ(I)
T_min = 0.562, T_max = 0.606	R_int = 0.051
5407 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	3 restraints
wR(F²) = 0.039	H-atom parameters constrained
S = 0.94	Δρ_max = 0.55 e Å⁻³
648 reflections	Δρ_min = −0.43 e Å⁻³
41 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.0038 (3)	0.5244 (3)	0.0802 (3)	0.0159 (6)
K1	0.0000	0.7500	0.3750	0.0296 (4)
O1	0.0084 (2)	0.63272 (19)	0.0937 (2)	0.0209 (5)
O2	0.0045 (2)	0.44765 (18)	0.1836 (2)	0.0224 (5)
O3	0.2057 (3)	0.8934 (3)	0.3322 (3)	0.0509 (8)
H1	0.2363	0.9125	0.2486	0.076*
H2	0.2520	0.8473	0.3787	0.076*
Yb1	0.0000	0.7500	−0.1250	0.01065 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0188 (16)	0.0154 (15)	0.0136 (12)	0.0004 (12)	−0.0010 (11)	0.0004 (11)
K1	0.0345 (6)	0.0345 (6)	0.0198 (7)	0.000	0.000	0.000
O1	0.0346 (14)	0.0125 (11)	0.0156 (9)	−0.0003 (10)	−0.0013 (8)	−0.0017 (8)
O2	0.0399 (14)	0.0122 (11)	0.0150 (9)	−0.0010 (10)	−0.0009 (9)	−0.0006 (8)
O3	0.0374 (17)	0.075 (2)	0.0402 (13)	0.0106 (16)	−0.0038 (12)	0.0195 (15)
Yb1	0.01004 (12)	0.01004 (12)	0.01186 (15)	0.000	0.000	0.000

Geometric parameters (Å, º) top

C1—O1	1.236 (4)	Yb1—O1	2.3629 (19)
C1—O2	1.269 (4)	Yb1—O2ⁱ	2.304 (2)
C1—C1ⁱ	1.536 (5)	O3—H1	0.8500
K1—O1	2.8402 (19)	O3—H2	0.8499
K1—O3	2.871 (3)

O1—C1—O2	127.7 (3)	O2ⁱ—Yb1—O1^v	137.29 (7)
O1—C1—C1ⁱ	116.9 (3)	O2ⁱⁱ—Yb1—O1^vi	137.29 (7)
O2—C1—C1ⁱ	115.4 (3)	O2ⁱⁱⁱ—Yb1—O1^vi	82.21 (8)
O1—K1—O3	96.95 (7)	O2^iv—Yb1—O1^vi	68.87 (7)
C1—O1—Yb1	118.53 (17)	O2ⁱ—Yb1—O1^vi	76.19 (8)
C1—O1—K1	123.44 (17)	O1^v—Yb1—O1^vi	132.92 (6)
Yb1—O1—K1	117.59 (8)	O2ⁱⁱ—Yb1—O1	76.19 (8)
C1—O2—Yb1ⁱ	120.27 (18)	O2ⁱⁱⁱ—Yb1—O1	137.29 (7)
K1—O3—H1	126.4	O2^iv—Yb1—O1	82.21 (8)
K1—O3—H2	95.1	O2ⁱ—Yb1—O1	68.87 (7)
H1—O3—H2	109.3	O1^v—Yb1—O1	68.77 (10)
O2ⁱⁱ—Yb1—O2ⁱⁱⁱ	92.95 (2)	O1^vi—Yb1—O1	132.92 (6)
O2ⁱⁱ—Yb1—O2^iv	153.79 (9)	O2ⁱⁱ—Yb1—O1^vii	68.87 (7)
O2ⁱⁱⁱ—Yb1—O2^iv	92.95 (2)	O2ⁱⁱⁱ—Yb1—O1^vii	76.19 (8)
O2ⁱⁱ—Yb1—O2ⁱ	92.95 (2)	O2^iv—Yb1—O1^vii	137.29 (7)
O2ⁱⁱⁱ—Yb1—O2ⁱ	153.79 (9)	O2ⁱ—Yb1—O1^vii	82.21 (8)
O2^iv—Yb1—O2ⁱ	92.95 (2)	O1^v—Yb1—O1^vii	132.92 (6)
O2ⁱⁱ—Yb1—O1^v	82.21 (8)	O1^vi—Yb1—O1^vii	68.77 (10)
O2ⁱⁱⁱ—Yb1—O1^v	68.87 (7)	O1—Yb1—O1^vii	132.92 (6)
O2^iv—Yb1—O1^v	76.19 (8)

Symmetry codes: (i) −x, −y+1, −z; (ii) y−1/4, −x+3/4, z−1/4; (iii) x, y+1/2, −z; (iv) −y+1/4, x+3/4, z−1/4; (v) −x, −y+3/2, z; (vi) y−3/4, −x+3/4, −z−1/4; (vii) −y+3/4, x+3/4, −z−1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O3^viii	0.85	2.08	2.899 (3)	163
O3—H2···O2^ix	0.85	2.06	2.837 (3)	152

Symmetry codes: (viii) −y+5/4, x+3/4, z−1/4; (ix) −y+3/4, x+3/4, −z+3/4.

Experimental details

Crystal data
Chemical formula	[KYb(C₂O₄)₂(H₂O)₄]
M_r	460.24
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	293
a, c (Å)	11.3502 (16), 8.9142 (18)
V (Å³)	1148.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.57
Crystal size (mm)	0.08 × 0.07 × 0.07

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.562, 0.606
No. of measured, independent and observed [I > 2σ(I)] reflections	5407, 648, 585
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.039, 0.94
No. of reflections	648
No. of parameters	41
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.43

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Selected bond lengths (Å) top

K1—O1	2.8402 (19)	Yb1—O1	2.3629 (19)
K1—O3	2.871 (3)	Yb1—O2ⁱ	2.304 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O3ⁱⁱ	0.85	2.08	2.899 (3)	163
O3—H2···O2ⁱⁱⁱ	0.85	2.06	2.837 (3)	152

Symmetry codes: (ii) −y+5/4, x+3/4, z−1/4; (iii) −y+3/4, x+3/4, −z+3/4.

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (Nos. 20872030 and 20972043), Heilongjiang Province (Nos. 2009RFXXG201, GC09A402 and 2010 t d03) and Heilongjiang University.

References

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