Poly[[tetra­aqua­bis­(μ3-pyridine-2,6-dicarboxyl­ato)(μ2-pyridine-2,6-dicarboxyl­ato)dilanthanum(III)] dihydrate]

Shie Fu Lush; Fwu Ming Shen

doi:10.1107/S1600536811030807

. 2011 Aug 6;67(Pt 9):m1195–m1196. doi: 10.1107/S1600536811030807

Poly[[tetraaquabis(μ₃-pyridine-2,6-dicarboxylato)(μ₂-pyridine-2,6-dicarboxylato)dilanthanum(III)] dihydrate]

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

PMCID: PMC3200968 PMID: 22064837

Abstract

There are two independent La^III cations in the polymeric title compound, {[La₂(C₇H₃NO₄)₃(H₂O)₄]·2H₂O}_n. One is nine-coordinated in an LaN₂O₇ tricapped trigonal–prismatic geometry formed by three pyridine-2,6-dicarboxylate anions and two water molecules, while the other is ten-coordinated in an LaNO₉ bicapped square-antiprismatic geometry formed by four pyridine-2,6-dicarboxylate anions and two water molecules. The two La^III cations are separated by a non-bonding distance of 5.026 (3) Å. The pyridine-2,6-dicarboxylate anions bridge the La^III cations, forming a three-dimensional polymeric complex. The crystal structure contains extensive classical O—H⋯O hydrogen bonds and weak intermolecular C—H⋯O hydrogen bonds. The crystal structure is further consolidated by π–π stacking between pyridine rings, the shortest centroid–centroid distance between parallel pyridine rings being 3.700 (5) Å.

Related literature

For applications of lanthanide metal carboxylate systems in supramolecular chemistry and functional materials, see: Yang et al. (2011 ▶); Chantal et al. (2008 ▶). For similar structures, see: Brouca et al. (2002 ▶); Ghosh & Bharadwaj (2004 ▶).

Experimental

Crystal data

[La₂(C₇H₃NO₄)₃(H₂O)₄]·2H₂O
M _r = 881.23
Triclinic,
a = 10.4910 (2) Å
b = 10.9197 (2) Å
c = 13.0850 (3) Å
α = 77.915 (1)°
β = 76.702 (1)°
γ = 86.049 (1)°
V = 1426.14 (5) Å³
Z = 2
Mo Kα radiation
μ = 3.04 mm⁻¹
T = 293 K
0.17 × 0.13 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.592, T _max = 0.699
10097 measured reflections
4496 independent reflections
4014 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.126
S = 1.03
4496 reflections
398 parameters
H-atom parameters constrained
Δρ_max = 3.36 e Å⁻³
Δρ_min = −1.06 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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 datablock(s) global, I. DOI: 10.1107/S1600536811030807/xu5269sup1.cif

e-67-m1195-sup1.cif^{(35.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030807/xu5269Isup2.hkl

e-67-m1195-Isup2.hkl^{(220.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

La1—N1	2.644 (5)
La1—N2ⁱ	2.728 (6)
La1—O1	2.502 (5)
La1—O3	2.614 (5)
La1—O8ⁱ	2.575 (5)
La1—O11ⁱ	2.578 (5)
La1—O11ⁱⁱ	2.600 (5)
La1—O13	2.593 (5)
La1—O14	2.525 (5)
La2—N3ⁱⁱⁱ	2.688 (6)
La2—O3	2.674 (5)
La2—O4	2.605 (5)
La2—O5	2.865 (6)
La2—O6	2.591 (5)
La2—O6ⁱⁱⁱ	2.615 (5)
La2—O7	2.524 (5)
La2—O10ⁱⁱⁱ	2.539 (5)
La2—O15	2.574 (5)
La2—O16	2.575 (6)

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O5	0.85	2.04	2.766 (8)	143
O13—H13B⋯O1^iv	0.85	1.91	2.721 (7)	160
O14—H14A⋯O5	0.97	2.23	3.062 (8)	143
O14—H14B⋯O9^v	0.83	2.44	3.225 (10)	160
O14—H14B⋯O10^v	0.83	2.22	2.712 (8)	119
O15—H15A⋯O7ⁱⁱⁱ	0.85	2.14	2.948 (8)	160
O15—H15B⋯O12ⁱⁱ	0.85	2.16	2.849 (7)	138
O16—H16A⋯O8	0.85	2.12	2.760 (8)	132
O16—H16B⋯O17ⁱⁱⁱ	0.85	2.05	2.843 (15)	155
O17—H17A⋯O9^vi	0.82	2.13	2.816 (17)	141
O17—H17B⋯O9^vii	0.82	2.39	2.758 (15)	108
O18—H18A⋯O2^viii	0.82	2.31	2.75 (2)	114
O18—H18B⋯O18^ix	0.88	2.46	2.89 (3)	110
C11—H11⋯O2^x	0.93	2.45	3.320 (11)	155
C12—H12⋯O18^xi	0.93	2.51	3.36 (2)	152

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Symmetry codes: (ii) Inline graphic ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) .

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

Pyridine-2,6-dicarboxylic acid (pydH₂) and its deprotonated anion behave as multifunctional ligands to act as bridging ligands in metal complexes with five coordination sites involving the oxygen atoms of the carboxylate groups and the nitrogen atom of the pyridine ring. In recent years, the chemistry of lanthanide metal carboxylate systems is of great interest because of their extensive usage in supramolecular chemistry and functional materials (Brouca et al. 2002; Ghosh et al. 2004; Yang et al. 2011; Chantal et al. 2008). Here, we report a new La^III complex with pyridine-2,6-dicarboxylic acid, [[La₂(pyd)₃(H₂O)₄].2H₂O]_n, from hydrothermal reaction.

The structure of the title compound is shown as Fig 1. There are two independent La^III ions where La(1) is nine coordinated with N₂O₇ donors sets to form tricapped trigonal prism geometries, where La(2) is ten coordinated with NO₉ donor sets to from bicapped square antiprisms geometries. The selected bond lengths (Å) of title compound are listed in Table 2. The La^III—O and La^III—N distances are similar to those found in other La^III complex (Brouca, et al.2002; Ghosh, et al. 2004). The bond distances and bond angles in the ligand moiety are within normal ranges.

The structure consists of two types of ligand-binding modes contributing to link the LaO₅N₂(H₂O)₂ and LaO₇N(H₂O)₂ polyhedral chains to three-dimensional network. This network can be described in terms of a 20-membered ring related to each other by the intermediate C8 carboxylate group. It results in a La1—La1 distance equal to 4.440 (1) Å. A projection of one 20-membered ring along x axis is shown in Fig. 2. Rings built from eight lanthanum atoms can be seen. In these rings, long La—La distances are found:La1—La2 = 6.190 (3) Å through C8 carboxylate group of pda1, La1—La2 =5.026 (3) Å through C7 carboxylate group of pda2. The La2—La2 distance through theµ-O6 atom is apart from the others with the shortest value of 4.514 (2) Å.

In the title crystal structure stabilized via O—H···O and weak C—H···O hydrogen bonds (Fig.3) (full details and symmetry codes are given in Table 3). The π–π stacking interaction is also observed, the centroid···centroid distance between the parallel aryl ring being 3.969 (4)Å and 3.700 (5) Å [Cg2^vi···Cg2(N2/C9—C13), Cg3^vii···Cg3(N3/C16—C20)] (symmetry code: (vi)1-X, 1-Y, 1-Z,(vii) 2-X, 1-Y, –Z). C1—O2···Cg1^viii((N1/C2—C6) is 3.892 (6) Å((viii) –X, –Y, 1-Z).

Experimental

LaCl₃.6H₂O (0.0899 g, 0.25 mmol), pydridine-2,6-dicarboxylic acid (0.0418 g, 0.25 mmol) and 1,2-bis(4-pyridyl)ethane were mixed in 10 ml of deionized water. After stirring for 30 min, the mixture was placed in a 23 ml Teflon-lined reactor, heated at 453 K for 72 h, then cooled slowly to room temperature. The colorless transparent single crystals of the title compound were obtained in 35.10% yield (based on La).