Hydro­thermal synthesis and crystal structure of a new lanthanum(III) coordination polymer with fumaric acid

Hayet Anana; Chahrazed Trifa; Sofiane Bouacida; Chaouki Boudaren; Hocine Merazig

doi:10.1107/S2056989015007008

. 2015 Apr 22;71(Pt 5):m114–m115. doi: 10.1107/S2056989015007008

Hydrothermal synthesis and crystal structure of a new lanthanum(III) coordination polymer with fumaric acid

Hayet Anana ^a, Chahrazed Trifa ^a, Sofiane Bouacida ^b,^a,^*, Chaouki Boudaren ^a, Hocine Merazig ^a

PMCID: PMC4420125 PMID: 25995891

Abstract

The title compound, poly[diaquatris(μ₄-but-2-enedioato)(μ₂-but-2-enedioic acid)dilanthanum(III)], [La₂(C₄H₂O₄)₃(C₄H₄O₄)(H₂O)₂]_n, was synthesized by the reaction of lanthanum chloride pentahydrate with fumaric acid under hydrothermal conditions. The asymmetric unit comprises an La^III cation, one and a half fumarate dianions (L ²⁻), one a half-molecule of fumaric acid (H₂ L) and one coordinated water molecule. Each La^III cation has the same nine-coordinate environment and is surrounded by eight O atoms from seven distinct fumarate moieties, including one protonated fumarate unit and one water molecule in a distorted tricapped trigonal–prismatic environment. The LaO₈(H₂O) polyhedra centres are edge-shared through three carboxylate bridges of the fumarate ligand, forming chains in three dimensions to construct the MOF. The crystal structure is stabilized by O—H⋯O hydrogen-bond interactions between the coordinated water molecule and the carboxylate O atoms, and also between oxygen atoms of fumaric acid

Keywords: crystal structure, hydrothermal synthesis, lanthanum(III) coordination polymer, fumaric acid

Related literature

For general background to metal coordination polymers, see: Fujita et al. (1994 ▸); Bénard et al. (2000 ▸); Zhang et al. (2000 ▸). For structures involving fumarate ligands and transition metals, see: Dalai et al. (2002 ▸); Xie et al. (2003 ▸); Devereux et al. (2000 ▸). For rare earth fumarates, see: Zhang et al. (2006 ▸); Li & Zou (2006 ▸); Liu et al. (2011 ▸). For reported La—O distances, see: Dan et al. (2005 ▸). graphic file with name e-71-0m114-scheme1.jpg

Experimental

Crystal data

[La₂(C₄H₂O₄)₃(C₄H₄O₄)(H₂O)₂]
M _r = 386.05
Monoclinic,
a = 8.4299 (5) Å
b = 14.6789 (8) Å
c = 8.8096 (5) Å
β = 103.318 (3)°
V = 1060.80 (11) Å³
Z = 4
Mo Kα radiation
μ = 4.07 mm⁻¹
T = 295 K
0.12 × 0.11 × 0.08 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▸) T _min = 0.677, T _max = 0.796
17677 measured reflections
4523 independent reflections
3901 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.020
wR(F ²) = 0.043
S = 1.02
4523 reflections
171 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.06 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▸); cell refinement: SAINT (Bruker, 2011 ▸); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg & Berndt, 2001 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and CRYSCAL (T. Roisnel, local program).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015007008/lh5759sup1.cif

e-71-0m114-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007008/lh5759Isup2.hkl

e-71-0m114-Isup2.hkl^{(217.1KB, hkl)}

Click here for additional data file.^{(1.4MB, tif)}

ORTEP-3 . DOI: 10.1107/S2056989015007008/lh5759fig1.tif

An ORTEP-3 (Farrugia, 2012) drawing of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.8MB, tif)}

. DOI: 10.1107/S2056989015007008/lh5759fig2.tif

A packing diagram of (I), showing the two-dimensional layered framework structure.

Click here for additional data file.^{(3MB, tif)}

. DOI: 10.1107/S2056989015007008/lh5759fig3.tif

A packing diagram of (I), showing the three-dimensional open-framework structure.

CCDC reference: 1058359

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1WH1WO8ⁱ	0.80(3)	2.06(3)	2.7995(19)	154(3)
O1WH2WO4ⁱⁱ	0.75(3)	2.17(3)	2.8913(18)	163(3)
O5H5O2ⁱⁱⁱ	0.82	1.85	2.655(2)	167

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

Acknowledgments

The authors thank Professor Mhamed Boudraa, Unité de Recherche de Chimie de l’Environnement et Moléculaire Structurale, CHEMS, Université Constantine 1 Algeria, for his technical assistance with the single-crystal X-ray data collection.

supplementary crystallographic information

S1. Comment

Coordination polymers of metal cations with organic multifunctional ligands have been received increasing interest, for these coordination polymers have one-, two-, three dimensional structures as well as potential applications as catalysts, magnetic and porous materials (Fujita et al., 1994; Bénard et al., 2000; Zhang et al., 2000). Multi-carboxyle ligands are useful to construct unique architectures of metal-coordination polymers. The synthesis of novel lanthanide polymers and studies on luminescent, electric and magnetic properties of the compounds are of interest. Some metal coordination polymers using fumaric acid as ligand have been reported in the literature containing transition metals Cu (Dalai et al., 2002), Zn (Xie et al., 2003), and Mn (Devereux et al., 2000). A series of rare earth fumarate complexes have also been reported (Zhang et al., 2006; Li & Zou., 2006; Liu et al., 2011). Hydrothermal synthesis has some advantages over conventional methods for the formation of a polymer framework with higher dimensions. Fumaric acid was used to synthesize a new lanthanum (III) coordination polymer, [La₂(C₄H₂O₄)₃(C₄H₄O₄)(H₂O)₂]n, (I), by using hydrothermal synthesis method and the crystal structure is reported in the present article.

The structure of the asymmetric unit of the title complex is shown in Fig. 1. It comprises a La^III cation, 1.5 fumarate dianions (L^2-), 0.5 fumaric acid (H₂L) and one water ligand. Overall there are three types of La—O bridging modes in (I), the fumarate dianion exhibits full monodentate and µ2-oxo-bridged chelating patterns, respectively, whereas the fumaric acid shows a double monodentate coordination mode. The La^III cation is sited within a distorted tricapped trigonal prism defined by nine O atoms derived from seven different bridging ligands and a coordinated water molecule. One of the carboxylate groups, derived from L^2-, is chelating, and the remaining six carboxylates coordinate in a monodentate mode. The average La—O bond distance of LaO₈(H₂O) polyhedra is 2.56 Å; the shortest La—O separation is 2.4510 (12) Å, resulting from the La1—O1 bond of a bridging carboxylate, and the longest is 2.7696 (12) Å for La1—O7 from the edge-sharing La—O bond. Other distances of La—O(fum) vary in the range of 2.4963 (12)–2.6117 (13) Å, comparable to the usual La—O(carboxylate) bonds reported (Dan et al., 2005). The LaO₈(H₂O) coordination polyhedra are edge-shared through one monodentate carboxylate O atoms (O7) and two bidentate carboxylate groups (O3—C4—O4 and O1—C1—O2) to generate infinite lanthanum-oxygen chains (Fig. 2). The adjacent lanthanum (III) centres have a general separation of 4.739 Å. Furthermore, the one-dimensional infinite chains are linked together with monodentate fumarate ligands to form a two-dimensional layered paralell to the crystallographic (100) (Fig.2), and the shortest interlayer distance of La···La is 8.430 Å (calculated between the two lanthanum atom centres). This type of organic-inorganic layered structure has been reported of the lanthanide fumarates: [Ln₂(fum)₃(H₂fum)(H₂O)₂ (Ln: Ce or Nd)] (Zhang et al., 2006). Finally, the two-dimensional layered structure is further constructed into a three-dimensional open framework by the ligands (Fig.3). The crystal is stabilized by hydrogen bond interactions between the coordinated water and carboxylate O atoms.

S2. Experimental

All chemicals were purchased from commercial sources and used as received without further purification. The title compound, was synthesized by using a hydrothermal method. Typically mixtures of fumaric acid (1 mmol, 0.116 g), lanthanum (III) chloride pentahydrate (0.5 mmol, 0.185 g) were suspended in H₂O (ca 10 ml). The mixture was then placed in a Teflon lined autoclave, sealed and heated to 413 K for 2 days. The reactor was cooled to room temperature over a period of 1 h. The light brown crystals suitable for X-ray diffraction were filtered, washed with water and dried in air.