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

Abstract

In the title compound, [KLu(C₂O₄)₂(H₂O)₄]_n, the Lu^III ion lies on a site of 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,

• a = 11.3337 (16) Å

• c = 8.9121 (18) Å

• V = 1144.8 (3) ų

• 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[F ² > 2σ(F ²)] = 0.014

• wR(F ²) = 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

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.

Supplementary Material

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
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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Water H atoms were initially located in a differece Fourier map, but they were treated as riding on their parent atoms with O—H = 0.85 Å, and with U_iso(H) = 1.5U_eq(O).

Figures

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].

Crystal data

[KLu(C2O4)2(H2O)4]	Dx = 2.682 Mg m−3
Mr = 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

Rigaku R-AXIS RAPID diffractometer	655 independent reflections
Radiation source: fine-focus sealed tube	594 reflections with I > 2σ(I)
graphite	Rint = 0.038
ω scan	θmax = 27.5°, θmin = 3.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→14
Tmin = 0.546, Tmax = 0.604	k = −14→14
5421 measured reflections	l = −11→11

Refinement

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(Fo2) + (0.0077P)2 + 3.796P] where P = (Fo2 + 2Fc2)/3
655 reflections	(Δ/σ)max = 0.001
41 parameters	Δρmax = 0.64 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

O3—K1	2.876 (3)	K1—O2iv	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—O3iv	2.876 (3)
O2—Lu1	2.361 (2)	Lu1—O1v	2.300 (2)
O2—K1	2.837 (2)	Lu1—O1vi	2.300 (2)
O1—C1	1.267 (4)	Lu1—O1vii	2.300 (2)
O1—Lu1i	2.300 (2)	Lu1—O1i	2.300 (2)
C1—C1i	1.531 (6)	Lu1—O2viii	2.361 (2)
K1—O2ii	2.837 (2)	Lu1—O2ii	2.361 (2)
K1—O2iii	2.837 (2)	Lu1—O2ix	2.361 (2)
K1—O3—H2	98.9	O2iv—K1—O3iv	120.99 (8)
K1—O3—H1	128.9	O2—K1—O3iv	97.09 (9)
H2—O3—H1	107.2	O3—K1—O3iv	91.015 (18)
C1—O2—Lu1	118.51 (19)	O3ii—K1—O3iv	91.015 (18)
C1—O2—K1	123.38 (18)	O3iii—K1—O3iv	164.71 (13)
Lu1—O2—K1	117.74 (8)	O1v—Lu1—O1vi	93.01 (2)
C1—O1—Lu1i	119.80 (19)	O1v—Lu1—O1vii	93.01 (2)
O2—C1—O1	127.4 (3)	O1vi—Lu1—O1vii	153.50 (11)
O2—C1—C1i	116.4 (3)	O1v—Lu1—O1i	153.50 (11)
O1—C1—C1i	116.2 (3)	O1vi—Lu1—O1i	93.01 (2)
O2ii—K1—O2iii	141.27 (5)	O1vii—Lu1—O1i	93.01 (2)
O2ii—K1—O2iv	141.27 (6)	O1v—Lu1—O2viii	81.67 (8)
O2iii—K1—O2iv	55.93 (8)	O1vi—Lu1—O2viii	69.06 (7)
O2ii—K1—O2	55.93 (8)	O1vii—Lu1—O2viii	137.39 (7)
O2iii—K1—O2	141.27 (6)	O1i—Lu1—O2viii	76.48 (8)
O2iv—K1—O2	141.27 (5)	O1v—Lu1—O2	137.39 (7)
O2ii—K1—O3	73.75 (8)	O1vi—Lu1—O2	81.67 (8)
O2iii—K1—O3	97.09 (9)	O1vii—Lu1—O2	76.48 (8)
O2iv—K1—O3	68.99 (8)	O1i—Lu1—O2	69.06 (7)
O2—K1—O3	120.99 (8)	O2viii—Lu1—O2	133.04 (6)
O2ii—K1—O3ii	120.99 (8)	O1v—Lu1—O2ii	69.06 (7)
O2iii—K1—O3ii	68.99 (8)	O1vi—Lu1—O2ii	76.48 (8)
O2iv—K1—O3ii	97.09 (9)	O1vii—Lu1—O2ii	81.67 (8)
O2—K1—O3ii	73.75 (8)	O1i—Lu1—O2ii	137.39 (7)
O3—K1—O3ii	164.71 (13)	O2viii—Lu1—O2ii	133.04 (6)
O2ii—K1—O3iii	97.09 (9)	O2—Lu1—O2ii	68.60 (10)
O2iii—K1—O3iii	120.99 (8)	O1v—Lu1—O2ix	76.48 (8)
O2iv—K1—O3iii	73.75 (8)	O1vi—Lu1—O2ix	137.39 (7)
O2—K1—O3iii	68.99 (8)	O1vii—Lu1—O2ix	69.06 (7)
O3—K1—O3iii	91.015 (18)	O1i—Lu1—O2ix	81.67 (8)
O3ii—K1—O3iii	91.015 (18)	O2viii—Lu1—O2ix	68.60 (10)
O2ii—K1—O3iv	68.99 (8)	O2—Lu1—O2ix	133.04 (6)
O2iii—K1—O3iv	73.75 (8)	O2ii—Lu1—O2ix	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, °)

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···O3x	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.