Poly[[dodeca­aqua­bis­(μ3-pyridine-2,6-dicarboxyl­ato)tetra­kis­(μ2-pyridine-2,6-dicarboxyl­ato)tri­calciumdieuropium(III)] 10.5-hydrate]

Shi, F.; Deng, J.; Dai, H.

doi:10.1107/S1600536812018028

Volume 68
Part 5
Pages m685-m686
May 2012

Received 29 March 2012
Accepted 23 April 2012
Online 28 April 2012

Key indicators
Single-crystal X-ray study
T = 113 K
Mean (C-C) = 0.008 Å
H completeness 86%
Disorder in solvent or counterion
R = 0.042
wR = 0.094
Data-to-parameter ratio = 11.3
Details

Poly[[dodecaaquabis(₃-pyridine-2,6-dicarboxylato)tetrakis(₂-pyridine-2,6-dicarboxylato)tricalciumdieuropium(III)] 10.5-hydrate]

Fengjuan Shi,^a Jiguang Deng ^a and Hongxing Dai ^a ^*

^aLaboratory of Catalysis Chemistry and Nanoscience, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, People's Republic of China
Correspondence e-mail: hxdai@bjut.edu.cn

In the title compound, {[Ca₃Eu₂(C₇H₃NO₄)₆(H₂O)₁₂]·10.5H₂O}_n, the Eu^III ion is nine-coordinated by three tridentate pyridine-2,6-dicarboxylate (PDA) ligands, forming a [Eu(PDA)₃]^3- building block. The Ca²⁺ ions adopt two types of coordination geometries. One Ca²⁺ ion, lying on a twofold rotation axis, is eight-coordinated by four carboxylate O atoms from four PDA ligands and four water molecules, and the other two Ca²⁺ ions, each lying on an inversion center, are six-coordinated by two carboxylate O atoms from two PDA ligands and four water molecules. The carboxylate groups bridge the Eu^III and Ca²⁺ ions into a three-dimensional porous framework, with channels extending along [010] and [001] in which lattice water molecules are located. Two of the lattice water molecules are disordered over two sets of sites with equal occupancy and one water molecule is 0.25-occupied. Numerous O-HO hydrogen bonds involving the water molecules and carboxylate O atoms are present.

Related literature

For 3d-4f and 4d-4f metal complexes with pyridine-2,6-dicarboxylate ligands, see: Zhao et al. (2006, 2007, 2011); Zhao, Zhao et al. (2009). For Ln-Ba (Ln = lanthanide) complexes with pyridine-2,6-dicarboxylate ligands, see: Zhao, Zuo et al. (2009).

Experimental

Crystal data

[Ca₃Eu₂(C₇H₃NO₄)₆(H₂O)₁₂]·10.5H₂O
M_r = 1820.14
Monoclinic, P 2/c
a = 16.070 (4) Å
b = 9.471 (2) Å
c = 23.540 (6) Å
= 107.685 (4)°
V = 3413.5 (14) Å³
Z = 2
Mo K radiation
= 2.16 mm^-1
T = 113 K
0.20 × 0.19 × 0.16 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009) T_min = 0.672, T_max = 0.724
27531 measured reflections
6015 independent reflections
4964 reflections with I > 2(I)
R_int = 0.054

Refinement

R[F² > 2(F²)] = 0.042
wR(F²) = 0.094
S = 1.14
6015 reflections
531 parameters
30 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 1.31 e Å^-3
_min = -1.29 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O13-H13AO10ⁱ	0.85 (1)	1.97 (2)	2.796 (6)	163 (5)
O13-H13BO20ⁱⁱ	0.85 (1)	1.85 (1)	2.696 (6)	175 (6)
O14-H14AO16ⁱⁱⁱ	0.85 (1)	1.96 (2)	2.774 (6)	160 (5)
O14-H14BO9ⁱⁱⁱ	0.85 (1)	1.91 (2)	2.723 (5)	160 (5)
O15-H15AO21^iv	0.85 (1)	1.99 (1)	2.839 (6)	172 (6)
O15-H15BO5	0.85 (1)	1.90 (1)	2.734 (5)	165 (5)
O16-H16AO13^iv	0.78 (6)	2.38 (7)	3.079 (6)	150 (6)
O16-H16BO1^iv	0.84 (6)	1.88 (7)	2.704 (6)	169 (6)
O17-H17AO3ⁱⁱⁱ	0.85 (1)	1.91 (1)	2.745 (6)	167 (5)
O17-H17BO19^v	0.85 (1)	1.93 (3)	2.722 (7)	155 (6)
O18-H18AO22'^vi	0.85 (1)	2.37 (6)	2.990 (15)	130 (6)
O18-H18AO22^vi	0.85 (1)	2.16 (7)	2.657 (14)	117 (6)
O18-H18BO4ⁱⁱⁱ	0.85 (1)	1.98 (2)	2.772 (6)	155 (5)
O19-H19AO24^vii	0.86 (1)	2.31 (3)	3.12 (2)	159 (6)
O19-H19BO7^viii	0.85 (1)	2.07 (4)	2.828 (6)	148 (6)
O20-H20AO15	0.85 (1)	2.04 (2)	2.862 (6)	161 (6)
O20-H20BO23	0.85 (1)	2.03 (4)	2.758 (10)	143 (6)
O20-H20BO22'^ix	0.85 (1)	2.32 (4)	3.042 (13)	143 (5)
O21-H21AO11	0.85 (1)	1.94 (2)	2.774 (6)	167 (6)
O21-H21BO17	0.85 (1)	2.42 (4)	3.113 (7)	138 (5)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+1, y-1, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) x, y+1, z; (v) x, y, z-1; (vi) -x, -y+1, -z+1; (vii) -x+1, -y+1, -z+1; (viii) x, y, z+1; (ix) $[x, -y+2, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2009); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2534 ).

Acknowledgements

This work was supported by the National High Technology Research and Development (863) Key Program of the Ministry of Science and Technology of China (grant No. 2009AA063201).

References

Rigaku/MSC (2009). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Zhao, X.-Q., Cui, P., Zhao, B., Shi, W. & Cheng, P. (2011). Dalton Trans. 40, 805-819.
Zhao, B., Gao, H.-L., Chen, X.-Y., Cheng, P., Shi, W., Liao, D.-Z., Yan, S.-P. & Jiang, Z.-H. (2006). Chem. Eur. J. 12, 149-158.
Zhao, X.-Q., Zhao, B., Ma, Y., Shi, W., Cheng, P., Jiang, Z.-H., Liao, D.-Z. & Yan, S.-P. (2007). Inorg. Chem. 46, 5832-5834.
Zhao, X.-Q., Zhao, B., Shi, W. & Cheng, P. (2009). CrystEngComm, 11, 1261-1269.
Zhao, X.-Q., Zuo, Y., Gao, D.-L., Zhao, B., Shi, W. & Cheng, P. (2009). Cryst. Growth Des. 9, 3948-3957.

metal-organic compounds

Poly[[dodecaaquabis(3-pyridine-2,6-dicarboxylato)tetrakis(2-pyridine-2,6-dicarboxylato)tricalciumdieuropium(III)] 10.5-hydrate]