A one-dimensional triaqua­europium(III)–1H,3H-benzimidazol-3-ium-5,6-dicarboxyl­ate–sulfate polymeric structure

Xia Cai; Jing-Jun Lin; Hao-Zhao Chen; Lai-Chen Chen; Rong-Hua Zeng

doi:10.1107/S1600536811034337

. 2011 Aug 27;67(Pt 9):m1310–m1311. doi: 10.1107/S1600536811034337

A one-dimensional triaquaeuropium(III)–1H,3H-benzimidazol-3-ium-5,6-dicarboxylate–sulfate polymeric structure

Xia Cai ^a, Jing-Jun Lin ^a, Hao-Zhao Chen ^a, Lai-Chen Chen ^a, Rong-Hua Zeng ^a,^b,^*

PMCID: PMC3200740 PMID: 22058892

Abstract

In the title coordination polymer, catena-poly[[[triaquaeuropium(III)]-bis(μ-1H,3H-benzimidazol-3-ium-5,6-dicarboxylato-κ³ O ⁵,O ^5′:O ⁶)-[triaquaeuropium(III)]-di-μ-sulfato-κ³ O:O,O′;κ³ O,O′:O′] hexahydrate], [Eu₂(C₉H₅N₂O₄)₂(SO₄)₂(H₂O)₆]·6H₂O}_n, the 1H,3H-benzimidazol-3-ium-5,6-dicarboxylate ligand is protonated at the imidazole group (H₂bdc). The Eu^III ion is coordinated by nine O atoms from two H₂bdc ligands, two sulfate anions and three water molecules, displaying a bicapped trigonal prismatic geometry. The carboxylate groups of the H₂bdc ligands and the sulfate anions link the Eu^III ions, forming a chain along [010]. These chains are further connected by N—H⋯O and O—H⋯O hydrogen bonds and π–π interactions between the imidazole and benzene rings [centroid–centroid distances = 3.997 (4), 3.829 (4) and 3.573 (4) Å] into a three-dimensional supramolecular network.

Related literature

For background to 1H-benzimidazole-5,6-dicarboxylate complexes, see: Wang et al. (2010 ▶); Wei et al. (2008 ▶); Xie et al. (2010 ▶); Yao et al. (2008 ▶).

Experimental

Crystal data

[Eu₂(C₉H₅N₂O₄)₂(SO₄)₂(H₂O)₆]·6H₂O
M _r = 1122.58
Triclinic,
a = 7.1261 (16) Å
b = 9.581 (2) Å
c = 12.424 (3) Å
α = 100.496 (3)°
β = 98.060 (3)°
γ = 94.979 (3)°
V = 820.3 (3) Å³
Z = 1
Mo Kα radiation
μ = 4.03 mm⁻¹
T = 298 K
0.30 × 0.26 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.310, T _max = 0.446
4076 measured reflections
2841 independent reflections
2669 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.097
S = 1.02
2841 reflections
248 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.82 e Å⁻³
Δρ_min = −2.51 e Å⁻³

Data collection: APEX2 (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: ORTEPIII (Burnett & Johnson, 1996 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global. DOI: 10.1107/S1600536811034337/hy2456sup1.cif

e-67-m1310-sup1.cif^{(18.6KB, cif)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O4ⁱ	0.84	1.90	2.717 (6)	165
O1W—H2W⋯O7ⁱⁱ	0.84	2.24	3.049 (6)	163
O2W—H3W⋯O5ⁱⁱ	0.84	1.96	2.775 (6)	162
O2W—H4W⋯O3ⁱⁱⁱ	0.85	1.85	2.659 (6)	159
O3W—H5W⋯O4Wⁱⁱⁱ	0.84	2.07	2.810 (6)	146
O3W—H6W⋯O2^iv	0.85	2.10	2.864 (6)	149
O4W—H7W⋯O5ⁱⁱ	0.86	2.34	3.045 (6)	139
O4W—H8W⋯O1	0.84	2.04	2.869 (6)	168
O5W—H9W⋯O6W	0.84	2.03	2.864 (8)	171
O5W—H10W⋯O6^v	0.84	2.01	2.790 (7)	154
O6W—H11W⋯O6^vi	0.84	2.37	3.165 (8)	158
O6W—H12W⋯O5ⁱⁱ	0.85	2.20	2.895 (7)	139
O6W—H12W⋯O1W	0.85	2.46	3.060 (7)	129
N1—H1A⋯O5W^vii	0.86 (8)	1.96 (8)	2.752 (8)	153 (7)
N1—H1A⋯O4W^vii	0.86 (8)	2.48 (8)	2.989 (7)	119 (6)
N2—H2⋯O6W^viii	0.86	1.91	2.734 (7)	161

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

Acknowledgments

The authors acknowledge the Undergraduates’ Innovating Experimentation Project of Guangdong Province, the Undergraduates’ Innovating Experimentation Project of South China Normal University and the Students’ Extracurricular Scientific Research Project of South China Normal University for supporting this work.

supplementary crystallographic information

Comment

In recent years, research on coordination polymers has made considerable progress in the fields of supramolecular chemistry and crystal engineering, because of their intriguing structural motifs and functional properties, such as molecular adsorption, magnetism and luminescence. Ligands play a key role in the construction of coordination polymers with fascinating topology, intriguing architectures and useful physical-chemical properties. Benzimidazole-5,6-dicarboxylic acid (H₃bdc) is a potential bifunctional ligand with carboxylate and N-donor functional groups and has been used to prepare such metal-organic complexes in possession of multidimensional networks and interesting properties (Wang et al., 2010; Wei et al., 2008; Xie et al., 2010; Yao et al., 2008). Recently, we obtained the title coordination polymer, which was synthesized by the hydrothermal reaction of Eu₂O₃ with H₃bdc in an aqueous solution.

The title compound has a polymeric chain architecture. As shown in Fig. 1, the Eu^III ion is in a bicapped trigonal-prismatic geometry, defined by nine O atoms from two 1H,3H-benzimidazol-3-ium-5,6-dicarboxylate ligands (H₂bdc), which are protonated at the imidazole groups, two sulfate anions and three water molecules. The H₂bdc ligands and sulfate anions link the Eu^III ions into a chain along [0 1 0] (Fig. 2). The adjacent Eu···Eu separations are 4.272 (4) and 6.663 (5) Å. The Eu—O bond lengths range from 2.376 (4) to 2.610 (4) Å and O—Eu—O bond angles vary from 52.01 (1) to 143.68 (1) °. The chains are further connected by N—H···O and O—H···O hydrogen bonds (Table 1) and π–π interactions between the imidazole and benzene rings [centroid–centroid distances = 3.997 (4), 3.829 (4) and 3.573 (4) Å] into a three-dimensional supramolecular network.

Experimental

A mixture of Eu₂O₃ (0.352 g, 1 mmol), H₃bdc (0.206 g, 1 mmol), water (10 ml) in the presence of H₂SO₄ (0.038 g, 0.385 mmol) was stirred vigorously for 30 min and then sealed in a 20 ml Teflon-lined stainless-steel autoclave. The autoclave was heated and maintained at 443 K for 3 days, and then cooled to room temperature at 5 K h^-1. Colorless block crystals of the title compound were obtained.