Poly[triaqua­tris­(μ4-pyridine-3,5-dicarboxyl­ato)dicerium(III)]

Fwu Ming Shen; Shie Fu Lush

doi:10.1107/S1600536811000286

. 2011 Jan 15;67(Pt 2):m161–m162. doi: 10.1107/S1600536811000286

Poly[triaquatris(μ₄-pyridine-3,5-dicarboxylato)dicerium(III)]

Fwu Ming Shen ^a, Shie Fu Lush ^b,^*

PMCID: PMC3051676 PMID: 21522842

Abstract

The asymmetric unit of the title compound, [Ce₂(C₇H₃NO₄)₃(H₂O)₃]_n, contains two Ce^III cations, three pyridine-3,5-dicarboxylate (pyd) anions and three coordinated water molecules. One Ce^III cation is coordinated by seven carboxylate O atoms from six pyd anions and two water molecules in a square-face-capped square-antiprismatic geometry. Another Ce^III cation is coordinated by seven O atoms from six pdy anions and one water molecule in a bicapped trigonal–prismatic geometry. The pdy anions bridge the Ce^III cations, forming the three-dimensional polymeric structure. The crystal structure contains extensive O—H⋯O, O—H⋯N and weak C—H⋯O hydrogen bonds. π–π stacking is present in the crystal structure, the shortest centroid–centroid distance between parallel pyridine rings being 3.509 (4) Å.

Related literature

3,5-PydH₂ can be easily deprotonated to the N-donor multidentate anion (pyd²⁻), enabling the ligand to act as a bridge to 3d and/or 4f metal ions, see: Jia et al. (2006 ▶). For related structures, see: Guo et al. (2009 ▶); Li (2007 ▶); Yi et al. (2009 ▶).

Experimental

Crystal data

[Ce₂(C₇H₃NO₄)₃(H₂O)₃]
M _r = 829.60
Triclinic,
a = 8.959 (3) Å
b = 9.429 (3) Å
c = 14.582 (4) Å
α = 98.115 (6)°
β = 95.501 (6)°
γ = 105.030 (6)°
V = 1166.4 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.94 mm⁻¹
T = 295 K
0.15 × 0.08 × 0.02 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.756, T _max = 0.975
12583 measured reflections
5586 independent reflections
2847 reflections with I > 2σ(I)
R _int = 0.090

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.076
S = 0.74
5586 reflections
370 parameters
H-atom parameters not refined
Δρ_max = 1.36 e Å⁻³
Δρ_min = −1.15 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) ▶; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) ▶; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000286/xu5131sup1.cif

e-67-0m161-sup1.cif^{(31.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000286/xu5131Isup2.hkl

e-67-0m161-Isup2.hkl^{(273.5KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Ce1—O1ⁱ	2.349 (6)
Ce1—O3	2.773 (5)
Ce1—O4	2.570 (5)
Ce1—O5ⁱⁱ	2.384 (5)
Ce1—O7	2.538 (5)
Ce1—O9	2.538 (5)
Ce1—O11ⁱⁱⁱ	2.405 (5)
Ce1—O13	2.560 (5)
Ce2—O2^iv	2.404 (5)
Ce2—O3	2.594 (5)
Ce2—O6^v	2.431 (5)
Ce2—O7	2.847 (6)
Ce2—O8	2.657 (6)
Ce2—O10^vi	2.526 (5)
Ce2—O12ⁱⁱⁱ	2.444 (5)
Ce2—O14	2.606 (6)
Ce2—O15	2.646 (6)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O4^vii	0.82	2.28	2.901 (7)	132
O13—H13B⋯N1^viii	0.81	1.87	2.659 (9)	164
O14—H14A⋯N2^vi	0.89	2.06	2.802 (9)	140
O14—H14B⋯O10^vi	0.88	2.40	3.031 (9)	129
O15—H15A⋯O10^vi	0.82	2.40	2.853 (9)	115
O15—H15B⋯N3	0.82	2.00	2.815 (9)	174
C8—H8⋯O12^ix	0.93	2.43	3.354 (9)	172
C12—H12⋯O9	0.93	2.57	3.354 (9)	143
C15—H15⋯O7	0.93	2.38	3.258 (9)	157

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Symmetry codes: (vi) Inline graphic ; (vii) ; (viii) ; (ix) .

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

3,5-PydH₂ can be easily deprotonated to get a O-donors to N-donor multidentate anion (pyd^2-), enabling the ligand to act as a bridge to 3 d and/or 4f metal ions (Jia et al., 2006). Some examples of coordination polymer with 3,5-pydH₂ have been reported (Guo et al., 2009; Li, 2007; Yi et al., 2009).

The asymmetric unit of the title compound contain two independent Ce^III atoms, three pyridine-3,5-dicarboxylate(3,5-pyd) ligands and three coordinated water molecules. One Ce^III atom is coordinated by nine O atoms from six 3,5-pyd groups and two water molecules, forming a square-face capped square antiprism. Another Ce^III atom is coordinated by seven O atoms from six 3,5-pdy groups and one O atom from one water molecule, forming a 4,4'-bicapped trigonal prism. By sharing two carboxylate O atoms via a mono atomic bridging mode, two Ce centers are connected into a binuclear unit(Table 1 and Fig.1).

The crystal structure contains an extensive network of classical O—H···O, O—H···N and weak C—H···O hydrogen bonds(full details and symmetry codes are given in Table 2 and Fig. 2).The π···π stacking interactions are also observed, the centroid-centroid distance between the pyridine rings of unbridging 3,5-pyd is 3.509 (4)Å [Cg5ⁱⁱⁱ···Cg5 (N3/C15—C19)] [symmetry code: -x, 1 - y, -z].

Experimental

A mixture of Ce(NO₃)₃.6H₂O (0.867 g, 0.2 mmole), 3,5-pydH₂ (0.495 g, 0.3 mmol) and 10 ml H₂O was sealed in a 25 ml teflon-lined bomb at 423 K for 3 days and then cooled to room temperature. Colorless crystals were collected (yield 45%, based on Ce(NO₃)₃).