Poly[(acetato-κ2 O,O′)aqua­(μ4-1H-benzimidazole-5,6-dicarboxyl­ato-κ5 N 3:O 5,O 5′:O 5,O 6:O 6′)praseodymium(III)]

Zi-Yu Pan; Jin-Hua Chen; Jian-Fen Lin; Xuan Xu; Yi-Fan Luo

doi:10.1107/S1600536810036986

. 2010 Sep 25;66(Pt 10):m1302. doi: 10.1107/S1600536810036986

Poly[(acetato-κ² O,O′)aqua(μ₄-1H-benzimidazole-5,6-dicarboxylato-κ⁵ N ³:O ⁵,O ^5′:O ⁵,O ⁶:O ^6′)praseodymium(III)]

Zi-Yu Pan ^a, Jin-Hua Chen ^a, Jian-Fen Lin ^a, Xuan Xu ^a,^*, Yi-Fan Luo ^a

PMCID: PMC2983355 PMID: 21587441

Abstract

In the title complex, [Pr(C₉H₄N₂O₄)(C₂H₃O₂)(H₂O)]_n, the Pr^III ion is coordinated by five O atoms and one N atom from four benzimidazole-5,6-dicarboxylate ligands, two O atoms from an acetate ligand and one water molecule, giving a tricapped trigonal-prismatic geometry. The benzimidazole-5,6-dicarboxylate and acetate ligands connect the Pr^III ions, forming a layer in the ac plane; the layers are further linked by N—H⋯O and O—H⋯O hydrogen bonding and π–π stacking interactions between neighboring pyridine rings [the centroid–centroid distance is 3.467 (1) Å], assembling a three-dimensional supramolecular network. The acetate methyl group is disordered over two positions with site-occupancy factors of 0.75 and 0.25.

Related literature

For related structures, see: Gao et al. (2008 ▶); Lo et al. (2007 ▶); Wang et al. (2009 ▶); Wei et al. (2008 ▶); Yao et al. (2008 ▶); Zhai (2009 ▶).

Experimental

Crystal data

[Pr(C₉H₄N₂O₄)(C₂H₃O₂)(H₂O)]
M _r = 422.11
Triclinic,
a = 7.4284 (5) Å
b = 9.0109 (7) Å
c = 9.7239 (7) Å
α = 87.075 (1)°
β = 86.498 (1)°
γ = 84.274 (1)°
V = 645.77 (8) Å³
Z = 2
Mo Kα radiation
μ = 3.81 mm⁻¹
T = 296 K
0.26 × 0.22 × 0.19 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.386, T _max = 0.485
3963 measured reflections
2327 independent reflections
2184 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.072
S = 1.04
2327 reflections
199 parameters
22 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.23 e Å⁻³
Δρ_min = −1.45 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036986/pk2264sup1.cif

e-66-m1302-sup1.cif^{(22.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036986/pk2264Isup2.hkl

e-66-m1302-Isup2.hkl^{(112.4KB, hkl)}

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
N1—H1⋯O6ⁱ	0.85 (2)	1.90 (3)	2.712 (5)	159 (5)
O1W—H1W⋯O2ⁱⁱ	0.83 (2)	2.06 (3)	2.854 (4)	159 (6)
O1W—H2W⋯O5ⁱⁱⁱ	0.84 (2)	1.96 (2)	2.794 (4)	176 (5)

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

Acknowledgments

The authors acknowledge the Natural Science Foundation of Guangdong Province (No. 9151063101000037) for supporting this work.

supplementary crystallographic information

Comment

In recent years, studies of coordination polymers built using metals and multifunctional organic ligands, has been a rapidly expanding field. This has been due to their intriguing structural motifs and functional properties, such as molecular adsorption, magnetism, and luminescence. Benzimidazole-5,6-dicarboxylic acid (H₂L) is such a multifuctional ligand with both nitrogen and oxygen donor atoms (Gao et al., 2008; Lo et al., 2007; Wang et al., 2009; Wei et al., 2008; Yao et al., 2008; Zhai et al., 2009). For example, Yao and co-workers have successfully synthesized six novel two-dimensional coordination polymers based on this ligand, namely, [MnL]_n (1), {[Ni₂L₂(H₂O)₄].(H₂O)₃}_n (2), {[Tb(L)(HL)(H₂O)].(H₂O)}_n (3) and {[Ln₂L₂(HL)₂(H₂O)₂]}_n (Ln=Ho (4), Er (5), Lu (6)) (Yao et al., 2008). Wei et al. also obtained a novel five coordinated Mn(II) polymer ([Mn(HL)])_n possessing abundant hydrogen bonds and π-π stacking interactions (Wei et al., 2008). Herein, we report the hydrothermal synthesis, structure of the novel coordination polymer.

In the structure of the title compound (Fig. 1), each Pr^III centre is nine-coordinated by five oxygen atoms and one N atom from four benzimidazole-5,6-dicarboxylato ligands, two oxygen atoms from an acetate ligand, and one water molecule. The structure can described as having a bicapped trigonal prismatic geometry with Pr···O distances and O···Pr···O angles ranging from 2.373 (3) Å to 2.645 (3) Å and 69.84 (9) ° to 152.88 (1) °, respectively. The benzimidazole-5,6-dicarboxylate and acetate ligands, act as bridging ligands, linking the Pr^III metal centres into a layer parallel to the ac plane (Fig. 2). Those layers are further connected via O—H···O and N—H···O hydrogen bonding interactions (Table 1) to form a three-dimensional supramolecular motif, which is stabilized by π-π stacking interactions between neighboring pyridyl rings (the centroid···centroid distance is 3.467 (1) Å).

Experimental

A mixture of Pr₆O₁₁ (0.170 g; 0.17 mmol), benzimidazole-5,6-dicarboxylic acid (0.206 g; 1 mmol), acetic acid (0.06 g; 1 mmol), water (10 ml) was stirred vigorously for 30 min and then sealed in a teflon-lined stainless-steel autoclave (20 ml, capacity). The autoclave was heated and maintained at 423 K for 3 days, and then cooled to room temperature at 5 K h^-1, which produced colorless block-shaped crystals.