Poly[[nona­aqua­bis­(μ-5-hy­droxy­benzene-1,3-di­carboxyl­ato)(5-hy­droxy­benzene-1,3-di­carboxyl­ato)dicerium(III)] hexa­hydrate]

Xiao Fan; Carole Daiguebonne; Olivier Guillou; Magatte Camara

doi:10.1107/S1600536814007727

. 2014 Apr 16;70(Pt 5):m181–m182. doi: 10.1107/S1600536814007727

Poly[[nonaaquabis(μ-5-hydroxybenzene-1,3-dicarboxylato)(5-hydroxybenzene-1,3-dicarboxylato)dicerium(III)] hexahydrate]

Xiao Fan ^a, Carole Daiguebonne ^a, Olivier Guillou ^a, Magatte Camara ^b,^*

PMCID: PMC4011209 PMID: 24860313

Abstract

In the title coordination polymer, {[Ce₂(C₈H₄O₅)₃(H₂O)₉]·6H₂O}_n, the asymmetric unit is formed by two Ce^III atoms, three 5-hydroxybenzene-1,3-dicarboxylate ligands, nine coordinating water molecules and six water molecules of crystallization. The two Ce^III atoms are bridged by 5-hydroxybenzene-1,3-dicarboxylate ligands acting in a bis-bidentate coordination mode, generating infinite chains along [101]. Both independent metal atoms are nine-coordinated, one by four O atoms from the carboxylate groups of two bridging 5-hydroxybenzene-1,3-dicarboxylate ligands and five O atoms from water molecules, generating a tricapped trigonal–prismatic geometry. The coordination around the second Ce^III atom is similar, except that one of the water molecules is replaced by an O atom from an additional 5-hydroxybenzene-1,3-dicarboxylate ligand acting in a monodentate coordination mode and forming a capped square-antiprismatic geometry.

Related literature

For background to this field of research, see: Daiguebonne et al. (1998 ▶); Qiu et al. (2007 ▶); Eddaoudi et al. (2002 ▶); Kerbellec et al. (2008 ▶); Jeon & Clérac (2012 ▶); Calvez et al. (2008 ▶); Binnemans (2009 ▶); Daiguebonne et al. (2008 ▶); Freslon et al. (2014 ▶). For previously reported crystal structures that involve 5-hydroxybenzene-1,3-dicarboxylate, see: Ermer & Neudörfl (2001 ▶); Lin et al. (2010 ▶); Xu & Li (2004 ▶); Chen et al. (2012 ▶); Huang et al. (2008 ▶). For details concerning the synthesis, see: Henisch & Rustum (1970 ▶); Henisch (1988 ▶); Daiguebonne et al. (2003 ▶).

Experimental

Crystal data

[Ce₂(C₈H₄O₅)₃(H₂O)₉]·6H₂O
M _r = 1090.82
Monoclinic,
a = 10.7150 (3) Å
b = 11.1039 (2) Å
c = 16.3611 (4) Å
β = 100.975 (2)°
V = 1911.01 (8) Å³
Z = 2
Mo Kα radiation
μ = 2.46 mm⁻¹
T = 293 K
0.14 × 0.05 × 0.04 mm

Data collection

Kappa CCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.763, T _max = 0.866
26639 measured reflections
8644 independent reflections
7711 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.088
S = 1.06
8644 reflections
506 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.46 e Å⁻³
Δρ_min = −1.28 e Å⁻³
Absolute structure: Flack (1983 ▶), 4150 Friedel pairs
Absolute structure parameter: 0.166 (19)

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: COLLECT; data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814007727/lr2124sup1.cif

e-70-0m181-sup1.cif^{(26KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814007727/lr2124Isup2.hkl

e-70-0m181-Isup2.hkl^{(422.8KB, hkl)}

CCDC reference: 995942

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

Acknowledgments

The French Cooperation Agency in Senegal and the China Scholarship Council in China are acknowledged for financial support. The Centre de Diffractométrie X of the University of Rennes 1 is acknowledged for the data collection.

supplementary crystallographic information

1. Introduction

For more than a decade, our group has been involved in the synthesis of benzene-poly-carboxylate lanthanide-based coordination polymers: (Daiguebonne et al., 1998), (Qiu et al., 2007); because of their great interest in gas storage: (Eddaoudi et al. 2002), (Kerbellec et al., 2008); molecular magnetism: (Jeon et al., 2012), (Calvez et al., 2008) or luminescence: (Binnemans, 2009), (Daiguebonne et al., 2008). In the frame of this work we have recently proved that lanthanide-based coordination polymers can exhibit original luminescence properties when a donor group is present in the vicinity of the lanthanide ion: (Freslon et al., 2014). Therefore we have undertaken the study of lanthanide-based coordination polymers that involves 5-hydroxybenzene-1,3-dicarboxylate as ligand. This ligand has previously led to extended molecular networks in association with organic molecules: (Ermer & Neudörfl, 2001), transition metal ions: ( Lin et al., 2010) or lanthanide ions: (Xu & Li , 2004), (Chen et al., 2012), (Huang et al. , 2008). Previously reported lanthanide-based coordination polymers have been obtained by hydrothermal methods. The structure described here has been obtained on the basis of single crystals that have grown in gel medium.

2. Experimental

2.1. Synthesis and crystallization

5-Hydroxybenzene-1,3-dicarboxylic acid was purchased from Alfa Aesar and used without further purification. Its di-sodium salt was prepared by addition of two equivalent of sodium hydroxide to an aqueous suspension of the acid. Then the obtained clear solution was evaporated to dryness. The resulting solid was suspended in a small amount of ethanol. The mixture was stirred and refluxed for 1 hour. Upon addition of ethoxyethane, precipitation occurred. After filtration and drying the white powder of the di-sodium salt was obtained in 90% yield.

Hydrated cerium chloride was purchased from A.M.P.E.R.E Industrie and used without further purification. Tetramethylorthosilicate (TMOS) was purchased from Acros Organics and jellified according to established procedures: (Henisch, 1988),( Henisch & Rustum, 1970), (Daiguebonne et al. ,2003). Dilute aqueous solutions (0.1 mol.L^-1) of cerium (III) chloride and di-sodium 5-hydroxybenzene-1,3-di-carboxylate were allowed to slowly diffuse through gel media in U-shaped tubes. After few weeks needle-like single crystals were obtained in the tubes that have been filled with a 7.5% gel (expressed in weight percent).

2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

H-atoms from water molecules have not been assigned and were thus not included in the refinement, but they were taken into account for the chemical formula sum, moiety, weight, as well as for the absorption coefficient and the number of electrons in the unit cell.

3. Results and discussion

The crystal structure of [Ce₂(C₈H₄O₅)₃(H₂O)₉,6H₂O]_∞ can be described on the basis of chains molecular motifs that spread in the (a+c) direction. Each chain is constituted by an alternation of cerium ions bridged by 5-hydroxybenzene-1,3-di-carboxylate ligands. There are two crystallographically independent cerium (III) ions in the asymmetric unit. Both are nine-coordinated. Ce1 is bound by four oxygen atoms from carboxylate groups and five oxygen atoms from water molecules that form a tricapped trigonal prism. On the other hand, Ce2 is bound by five oxygen atoms from carboxylate groups and four oxygen atoms from water molecules that form a capped square antiprism. There are three crystallographically independent ligands in the asymmetric unit. Two out of the three bridge the metal ions in a bis-bidentate manner. A third ligand is only linked to the Ce2 atom in a monodentate fashion. Its second carboxylate clip is not bound and point toward the inter-molecular motifs space (Figure 1). This is in agreement with the IR spectrum that shows no characteristic peak of any protonated carboxylate group.

The short distances ( in the range 2.7–2.8 Å) between some oxygen atoms allow to assume that neighboring chains are held together by strong intermolecular hydrogen bond interactions forming a double-chains molecular motif (Figure 2). Ligands that are bound in a unidentate fashion are pointing between the double-chains molecular motifs. Oxygen atoms from the free carboxylate clip are involved, with coordination and crystallization water molecules, in a complex Hydrogen-bonds network that ensure the stability of the crystal packing.