Poly[tetra­aquadi-μ4-oxalato-lutetium(III)potassium]

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

doi:10.1107/S1600536811042061

metal-organic compounds

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Volume 67| Part 11| November 2011| Page m1591

doi:10.1107/S1600536811042061

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Poly[tetraaquadi-μ₄-oxalato-lutetium(III)potassium]

Feng-Ming Zhang,^a Tao-Zhu Sun,^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 19 September 2011; accepted 12 October 2011; online 22 October 2011)

In the title compound, [KLu(C₂O₄)₂(H₂O)₄]_n, the Lu^III ion lies on a site of $[\overline{4}]$ symmetry in a dodecahedron defined by eight O atoms from four oxalate ligands. The K atom lies on another site of the same symmetry and is coordinated by four oxalate O atoms and four O water atoms. The mid-point of the C—C bond of the oxalate group lies on an inversion center. In the packing structure, each oxalate ligand links two Lu(III) and two K atoms, forming a three-dimensional open framework with channels running along [001]. Intermolecular O—H⋯O hydrogen bonds occur.

Related literature

For background to oxalate anions as bridging ligands in high dimensional frameworks and for a similar structure, see: Camara et al. (2003 ); Zhang et al. (2009 ).

Experimental

Crystal data

[KLu(C₂O₄)₂(H₂O)₄]
M_r = 462.17
Tetragonal, I 4₁ /a
a = 11.3337 (16) Å
c = 8.9121 (18) Å
V = 1144.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 9.05 mm⁻¹
T = 293 K
0.08 × 0.08 × 0.06 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.546, T_max = 0.604
5421 measured reflections
655 independent reflections
594 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.014
wR(F²) = 0.035
S = 1.13
655 reflections
41 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H2⋯O1ⁱ	0.85	2.06	2.836 (4)	151
O3—H1⋯O3ⁱⁱ	0.85	2.06	2.891 (3)	166
Symmetry codes: (i) $[-x+1, -y+{\script{1\over 2}}, z]$ ; (ii) $[y+{\script{1\over 4}}, -x+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811042061/ng5233sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042061/ng5233Isup2.hkl

checkCIF report

Comment top

Lanthanide complexes with spectroscopic and magnetic properties are currently of considerable interest; the oxalate ligand can serve as bridging ligand in high dimensional frameworks (Camara et al., 2003; Zhang et al., 2009). In this paper, we present here 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, [LuK(C₂O₄)₂(H₂O)₄]_n, the eight-coordinated lutetium(III) ion lies on a 4-fold inverse axis in a distorted dodecahedron defined by eight oxygen atoms from four oxalate ligands, and while the eight-coordinated potassium is also locate on a 4-fold inverseaxis in a distorted dodecahedron defined by four oxygen atoms from oxalate ligands and four oxygen atoms from water molecules (Fig. 1, Table 1).

In the packing structure, each oxalate ligand links two Lu(III) and two K atoms to form a three-dimensional open framework with channels running along [001] (Fig. 2).

Related literature top

For background to the oxalate ligand as a bridging ligand in high dimensional frameworks and for a similar structure, 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. Lu(NO₃)_3.6H₂O (14.07 mg, 0.03 mmol) and the 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 40% yield.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level for non-H atoms, Symmetry codes: (I) 1 - x, 1 - y, -z; (II) 1.25 - y, -1/4 + x, -1/4 + z; (III) x, -1/2 + y, -z; (IV) 0.25+Y, 0.75-X, -0.25-Z; (V) 0.75 - y, -1/4 + x, -0.25 - z; (VI) -1/4 + y, 0.75 - x, -1/4 + z; (VII) 1 - x, 0.5 - y, z; (VIII) 0.75 - y, -1/4 + x, 0.75 - z; (IX) 1/4 + y, 0.75 - x, 0.75 - z.

Fig. 2. A partial packing view, showing the three-dimensional open framework along [001].

Poly[tetraaquadi-µ₄-oxalato-lutetium(III)potassium] top

Crystal data top

[KLu(C₂O₄)₂(H₂O)₄]	D_x = 2.682 Mg m⁻³
M_r = 462.17	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/a	Cell parameters from 4696 reflections
Hall symbol: -I 4ad	θ = 3.1–27.5°
a = 11.3337 (16) Å	µ = 9.05 mm⁻¹
c = 8.9121 (18) Å	T = 293 K
V = 1144.8 (3) Å³	Block, colorless
Z = 4	0.08 × 0.08 × 0.06 mm
F(000) = 872

Data collection top

Rigaku R-AXIS RAPID diffractometer	655 independent reflections
Radiation source: fine-focus sealed tube	594 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scan	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→14
T_min = 0.546, T_max = 0.604	k = −14→14
5421 measured reflections	l = −11→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)] = 0.014	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.035	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0077P)² + 3.796P] where P = (F_o² + 2F_c²)/3
655 reflections	(Δ/σ)_max = 0.001
41 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[KLu(C₂O₄)₂(H₂O)₄]	Z = 4
M_r = 462.17	Mo Kα radiation
Tetragonal, I4₁/a	µ = 9.05 mm⁻¹
a = 11.3337 (16) Å	T = 293 K
c = 8.9121 (18) Å	0.08 × 0.08 × 0.06 mm
V = 1144.8 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	655 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	594 reflections with I > 2σ(I)
T_min = 0.546, T_max = 0.604	R_int = 0.038
5421 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.014	0 restraints
wR(F²) = 0.035	H-atom parameters constrained
S = 1.13	Δρ_max = 0.64 e Å⁻³
655 reflections	Δρ_min = −0.40 e Å⁻³
41 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O3	0.3564 (3)	0.0435 (3)	0.4179 (4)	0.0588 (9)
H2	0.3981	−0.0060	0.3698	0.088*
H1	0.3356	0.0106	0.4995	0.088*
O2	0.5074 (2)	0.36714 (18)	0.0938 (2)	0.0216 (5)
O1	0.5037 (2)	0.55246 (18)	0.1842 (2)	0.0229 (5)
C1	0.5028 (3)	0.4761 (3)	0.0803 (3)	0.0167 (6)
K1	0.5000	0.2500	0.3750	0.0300 (3)
Lu1	0.5000	0.2500	−0.1250	0.01106 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.081 (2)	0.0483 (19)	0.0472 (19)	0.0081 (17)	0.0202 (18)	−0.0078 (15)
O2	0.0371 (13)	0.0112 (9)	0.0164 (11)	−0.0010 (8)	−0.0012 (9)	0.0000 (8)
O1	0.0411 (13)	0.0127 (10)	0.0149 (10)	0.0009 (9)	−0.0012 (10)	−0.0011 (8)
C1	0.0198 (14)	0.0159 (14)	0.0143 (14)	−0.0008 (11)	−0.0012 (11)	0.0010 (11)
K1	0.0351 (5)	0.0351 (5)	0.0199 (7)	0.000	0.000	0.000
Lu1	0.01045 (9)	0.01045 (9)	0.01229 (13)	0.000	0.000	0.000

Geometric parameters (Å, º) top

O3—K1	2.876 (3)	K1—O2^iv	2.837 (2)
O3—H2	0.8499	K1—O3ⁱⁱ	2.876 (3)
O3—H1	0.8500	K1—O3ⁱⁱⁱ	2.876 (3)
O2—C1	1.242 (4)	K1—O3^iv	2.876 (3)
O2—Lu1	2.361 (2)	Lu1—O1^v	2.300 (2)
O2—K1	2.837 (2)	Lu1—O1^vi	2.300 (2)
O1—C1	1.267 (4)	Lu1—O1^vii	2.300 (2)
O1—Lu1ⁱ	2.300 (2)	Lu1—O1ⁱ	2.300 (2)
C1—C1ⁱ	1.531 (6)	Lu1—O2^viii	2.361 (2)
K1—O2ⁱⁱ	2.837 (2)	Lu1—O2ⁱⁱ	2.361 (2)
K1—O2ⁱⁱⁱ	2.837 (2)	Lu1—O2^ix	2.361 (2)

K1—O3—H2	98.9	O2^iv—K1—O3^iv	120.99 (8)
K1—O3—H1	128.9	O2—K1—O3^iv	97.09 (9)
H2—O3—H1	107.2	O3—K1—O3^iv	91.015 (18)
C1—O2—Lu1	118.51 (19)	O3ⁱⁱ—K1—O3^iv	91.015 (18)
C1—O2—K1	123.38 (18)	O3ⁱⁱⁱ—K1—O3^iv	164.71 (13)
Lu1—O2—K1	117.74 (8)	O1^v—Lu1—O1^vi	93.01 (2)
C1—O1—Lu1ⁱ	119.80 (19)	O1^v—Lu1—O1^vii	93.01 (2)
O2—C1—O1	127.4 (3)	O1^vi—Lu1—O1^vii	153.50 (11)
O2—C1—C1ⁱ	116.4 (3)	O1^v—Lu1—O1ⁱ	153.50 (11)
O1—C1—C1ⁱ	116.2 (3)	O1^vi—Lu1—O1ⁱ	93.01 (2)
O2ⁱⁱ—K1—O2ⁱⁱⁱ	141.27 (5)	O1^vii—Lu1—O1ⁱ	93.01 (2)
O2ⁱⁱ—K1—O2^iv	141.27 (6)	O1^v—Lu1—O2^viii	81.67 (8)
O2ⁱⁱⁱ—K1—O2^iv	55.93 (8)	O1^vi—Lu1—O2^viii	69.06 (7)
O2ⁱⁱ—K1—O2	55.93 (8)	O1^vii—Lu1—O2^viii	137.39 (7)
O2ⁱⁱⁱ—K1—O2	141.27 (6)	O1ⁱ—Lu1—O2^viii	76.48 (8)
O2^iv—K1—O2	141.27 (5)	O1^v—Lu1—O2	137.39 (7)
O2ⁱⁱ—K1—O3	73.75 (8)	O1^vi—Lu1—O2	81.67 (8)
O2ⁱⁱⁱ—K1—O3	97.09 (9)	O1^vii—Lu1—O2	76.48 (8)
O2^iv—K1—O3	68.99 (8)	O1ⁱ—Lu1—O2	69.06 (7)
O2—K1—O3	120.99 (8)	O2^viii—Lu1—O2	133.04 (6)
O2ⁱⁱ—K1—O3ⁱⁱ	120.99 (8)	O1^v—Lu1—O2ⁱⁱ	69.06 (7)
O2ⁱⁱⁱ—K1—O3ⁱⁱ	68.99 (8)	O1^vi—Lu1—O2ⁱⁱ	76.48 (8)
O2^iv—K1—O3ⁱⁱ	97.09 (9)	O1^vii—Lu1—O2ⁱⁱ	81.67 (8)
O2—K1—O3ⁱⁱ	73.75 (8)	O1ⁱ—Lu1—O2ⁱⁱ	137.39 (7)
O3—K1—O3ⁱⁱ	164.71 (13)	O2^viii—Lu1—O2ⁱⁱ	133.04 (6)
O2ⁱⁱ—K1—O3ⁱⁱⁱ	97.09 (9)	O2—Lu1—O2ⁱⁱ	68.60 (10)
O2ⁱⁱⁱ—K1—O3ⁱⁱⁱ	120.99 (8)	O1^v—Lu1—O2^ix	76.48 (8)
O2^iv—K1—O3ⁱⁱⁱ	73.75 (8)	O1^vi—Lu1—O2^ix	137.39 (7)
O2—K1—O3ⁱⁱⁱ	68.99 (8)	O1^vii—Lu1—O2^ix	69.06 (7)
O3—K1—O3ⁱⁱⁱ	91.015 (18)	O1ⁱ—Lu1—O2^ix	81.67 (8)
O3ⁱⁱ—K1—O3ⁱⁱⁱ	91.015 (18)	O2^viii—Lu1—O2^ix	68.60 (10)
O2ⁱⁱ—K1—O3^iv	68.99 (8)	O2—Lu1—O2^ix	133.04 (6)
O2ⁱⁱⁱ—K1—O3^iv	73.75 (8)	O2ⁱⁱ—Lu1—O2^ix	133.04 (6)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, −y+1/2, z; (iii) y+1/4, −x+3/4, −z+3/4; (iv) −y+3/4, x−1/4, −z+3/4; (v) x, y−1/2, −z; (vi) y−1/4, −x+3/4, z−1/4; (vii) −y+5/4, x−1/4, z−1/4; (viii) −y+3/4, x−1/4, −z−1/4; (ix) y+1/4, −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—H2···O1ⁱⁱ	0.85	2.06	2.836 (4)	151
O3—H1···O3^x	0.85	2.06	2.891 (3)	166

Symmetry codes: (ii) −x+1, −y+1/2, z; (x) y+1/4, −x+1/4, z+1/4.

Experimental details

Crystal data
Chemical formula	[KLu(C₂O₄)₂(H₂O)₄]
M_r	462.17
Crystal system, space group	Tetragonal, I4₁/a
Temperature (K)	293
a, c (Å)	11.3337 (16), 8.9121 (18)
V (Å³)	1144.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	9.05
Crystal size (mm)	0.08 × 0.08 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.546, 0.604
No. of measured, independent and observed [I > 2σ(I)] reflections	5421, 655, 594
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.014, 0.035, 1.13
No. of reflections	655
No. of parameters	41
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.40

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H2···O1ⁱ	0.85	2.06	2.836 (4)	150.9
O3—H1···O3ⁱⁱ	0.85	2.06	2.891 (3)	165.9

Symmetry codes: (i) −x+1, −y+1/2, z; (ii) y+1/4, −x+1/4, z+1/4.

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

Camara, M., Daiguebonne, C., Boubekeur, K., Roisnel, T., Gérault, Y., Baux, C., Dret, F. L. & Guillou, O. (2003). C. R. Chim. 6, 405–415. Web of Science CSD CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, X.-J., Xing, Y.-H., Wang, C.-G., Han, J., Li, J., Ge, M.-F., Zeng, X.-Q. & Niu, S.-Y. (2009). Inorg. Chim. Acta, 362, 1058–1064. Web of Science CSD CrossRef CAS Google Scholar