Poly[[aqua­tris­(μ4-benzene-1,2-dicarboxyl­ato)dilanthanum(III)] hemihydrate]

Shie Fu Lush; Fwu Ming Shen

doi:10.1107/S1600536811036282

. 2011 Sep 14;67(Pt 10):m1370–m1371. doi: 10.1107/S1600536811036282

Poly[[aquatris(μ₄-benzene-1,2-dicarboxylato)dilanthanum(III)] hemihydrate]

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

PMCID: PMC3201334 PMID: 22064614

Abstract

The asymmetric unit of the title coordination polymer, {[La₂(C₈H₄O₄)₃(H₂O)]·0.5H₂O}_n, contains two independent La^III atoms, one of which is surrounded by eight carboxylate-O atoms from six benzene-1,2-dicarboxylate (BDC) anions in a bicapped trigonal–prismatic geometry. The other La^III atom is nine-coordinated in a tricapped trigonal–prismatic geometry, formed by eight carboxylate-O atoms from six BDC anions and a coordinated water molecule. The BDC anions bridge the La^III atoms, forming a two-dimensional polymeric complex parallel to (001). The crystal structure contains weak O—H⋯O and non-classical C—H⋯O hydrogen bonds. A C—H⋯π interaction is also present in the crystal structure. The uncoordinated water molecule shows half-occupation.

Related literature

For a related structure, see: Wang et al. (2009 ▶).

Experimental

Crystal data

[La₂(C₈H₄O₄)₃(H₂O)]·0.5H₂O
M _r = 1594.36
Triclinic,
a = 8.6269 (19) Å
b = 10.5832 (17) Å
c = 14.323 (2) Å
α = 97.271 (18)°
β = 102.199 (6)°
γ = 104.489 (8)°
V = 1215.1 (4) Å³
Z = 1
Mo Kα radiation
μ = 3.54 mm⁻¹
T = 150 K
0.47 × 0.24 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.287, T _max = 0.871
8765 measured reflections
4145 independent reflections
3430 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.087
S = 1.11
4145 reflections
356 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 1.25 e Å⁻³
Δρ_min = −0.91 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/S1600536811036282/xu5316sup1.cif

e-67-m1370-sup1.cif^{(32.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036282/xu5316Isup2.hkl

e-67-m1370-Isup2.hkl^{(203.1KB, hkl)}

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

Table 1. Selected bond lengths (Å).

La1—O1	2.599 (4)
La1—O2	2.645 (5)
La1—O3	2.695 (6)
La1—O4	2.613 (4)
La1—O5ⁱ	2.617 (4)
La1—O7ⁱⁱ	2.439 (5)
La1—O17ⁱⁱⁱ	2.543 (4)
La1—O20	2.478 (5)
La1—O22	2.611 (4)
La2—O1	2.535 (4)
La2—O4^iv	2.482 (4)
La2—O5^iv	2.625 (4)
La2—O6ⁱⁱⁱ	2.466 (4)
La2—O8^v	2.549 (5)
La2—O17	2.608 (4)
La2—O18ⁱⁱⁱ	2.495 (4)
La2—O19	2.417 (5)

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

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

Cg is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O22—H22A⋯O1ⁱⁱ	0.90	2.20	3.001 (6)	148
O22—H22B⋯O20ⁱⁱ	0.88	2.15	3.009 (8)	164
O27—H27A⋯O2^vi	0.91	2.38	3.17 (2)	146
O27—H27B⋯O3ⁱ	0.88	1.86	2.69 (2)	158
C3—H3⋯O27^vii	0.93	2.15	2.96 (2)	145
C16—H16⋯O2ⁱ	0.93	2.58	3.331 (10)	138
C19—H19⋯Cg^v	0.93	2.98	3.902 (9)	169

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

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

Benzene-1,2-dicarboxylic acid (H₂BDC) are widely used in the construction of coordination polymers due to their capability of acting as bridging ligands in various coordination modes. But to the best of our knowledge, H₂BDC is seldom involved in lanthanide complexes (Wang et al., 2009). In this paper, we describe the hydrothermal synthesis and structure properties of a lanthanide phthalate coordination complex {[La₂(C₈H₄O₄)₃(H₂O)].0.5 H₂O}_n.

The molecular structure of the title compound is shown in Fig. 1.There are two independent lanthanum ions in the asymmetric unit. The La(1) ion is nine-coordinated with O₉ donors sets to form tricapped trigonal prismatic geometries by eight carboxylate O atoms and one water molecule, where La(2) ion is eight-coordinated with O₈ donors sets to form distorted bicapped trigonal-prismatic geometries by eight carboxylate O atoms, from six benzene-1,2-dicarboxylate anions. The selected bond lengths (Å) of title compound are listed in Table 1. The two La^III cations are separated by a non-bonding distance of 4.453 (9) and 4.419 (10) Å. The benzene-1,2-dicarboxylate anions bridge the La^III cations, forming a two-dimensional polymeric complex.

There are extensive intermolecular O—H···O and weak C—H···O hydrogen bonds, which cause the stability of the crystal structure (Fig. 2, Table 2). There are no π-π stacking interactions in the title compound. Furthermore, there is C—H···π interaction between C—H group of the BDC ligand, with an C—H···centroid distance of 3.902 (9) Å [C19—H19···Cg1^v(C2—C7)] (Symmetry code:-1-X, –Y, 1-Z).

Experimental

LaCl₃.6H₂O (0.0868 g, 0.20 mmol), benzene-1,2-dicarboxylic acid (0.0348 g, 0.20 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 48 h, then cooled slowly to room temperature. The colorless transparent single crystals of the title compound were obtained in 36.76% yield (based on La).