Tetra­kis(μ2-2-phen­oxy­propionato)-κ3 O,O′:O′;κ3 O:O,O′;κ4 O:O′-bis­[(1,10-phenanthroline-κ2 N,N′)(2-phen­oxy­propionato-κ2 O,O′)cerium(III)]

Jin-Bei Shen; Jia-Lu Liu; Guo-Liang Zhao

doi:10.1107/S1600536811036129

. 2011 Sep 14;67(Pt 10):m1359–m1360. doi: 10.1107/S1600536811036129

Tetrakis(μ₂-2-phenoxypropionato)-κ³ O,O′:O′;κ³ O:O,O′;κ⁴ O:O′-bis[(1,10-phenanthroline-κ² N,N′)(2-phenoxypropionato-κ² O,O′)cerium(III)]

Jin-Bei Shen ^a, Jia-Lu Liu ^a, Guo-Liang Zhao ^a,^b,^*

PMCID: PMC3201429 PMID: 22064783

Abstract

In the centrosymmetric binuclear title complex, [Ce₂(C₉H₉O₃)₆(C₁₂H₈N₂)₂], the two Ce^III ions are linked by four 2-phenoxypropionate groups in bi- and tridentate bridging modes. Each Ce^III ion is nine-coordinated by one 1,10-phenanthroline molecule, two O atoms from a chelating carboxylate, two O atoms derived from a μ₃-carboxylate and two O atoms derived from two μ₂-carboxylate ligands in a distorted CeN₂O₇ monocapped square-antiprismatic geometry.

Related literature

For background to phenoxyalkanoic acids, see: Markus & Buser (1997 ▶). For a related Ce complex, see: Fu et al. (2007 ▶) and for a related La complex, see: Li et al. (2010 ▶). For isotypic structures, see: Shen et al. (2011a ▶) for Tb; Shen et al. (2011b ▶) for Pr; Shen et al. (2011c ▶) for Dy; Shen et al. (2011d ▶) for La; Shen et al. (2011e ▶) for Ho; Shen et al. (2011f ▶) for Gd.

Experimental

Crystal data

[Ce₂(C₉H₉O₃)₆(C₁₂H₈N₂)₂]
M _r = 1631.62
Monoclinic,
a = 11.5137 (2) Å
b = 25.9311 (6) Å
c = 13.9620 (3) Å
β = 120.149 (1)°
V = 3604.62 (13) Å³
Z = 2
Mo Kα radiation
μ = 1.32 mm⁻¹
T = 296 K
0.30 × 0.18 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.747, T _max = 0.848
26086 measured reflections
6351 independent reflections
5383 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.060
S = 1.10
6351 reflections
461 parameters
234 restraints
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536811036129/wm2527sup1.cif

e-67-m1359-sup1.cif^{(28.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036129/wm2527Isup2.hkl

e-67-m1359-Isup2.hkl^{(310.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ce1—O8ⁱ	2.4377 (19)
Ce1—O2ⁱ	2.448 (2)
Ce1—O3	2.483 (2)
Ce1—O5	2.531 (2)
Ce1—O4	2.549 (2)
Ce1—O7	2.5699 (19)
Ce1—N2	2.643 (2)
Ce1—N1	2.691 (2)
Ce1—O8	2.694 (2)

Open in a new tab

Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

The group of phenoxyalkanoic acids includes a considerable number of important herbicides. The desired biological activity is largely dependent on the length of the carbon chain of the alkanoic acid, the nature of the phenoxy group, and the position of its attachment to the carbon chain (Markus & Buser, 1997). The structures of 2-phenoxypropionic acid (HL) complexes coupled with their special functionality catched our interest. Here, we describe the Ce^III title complex, (I).

The structure of complex (I) is shown in Fig. 1 and the coordination environment of Ce(III) is shown in Fig. 2. The dimeric title compound (I) is centrosymmetric and is comprised of six L anions and two phenanthroline ligands. The two Ce(III) ions are linked together by four L groups through their bi- and tri-dentate bridging modes, forming a dimeric unit. The distance between two La(III) ions in the dimeric unit is 4.1025 (3) Å. Each Ce(III) ion is coordinated by nine atoms, five of which are oxygen atoms from the bridging carboxylates, two oxygen atoms from the bidentate chelating carboxylate group, and two nitrogen atoms from a 1,10-phenanthroline molecule. The Ce(III) ion adopts a distorted monocapped square antiprisatic geometry (Fig. 2). The Ce—O distances are within the range 2.4377 (19)–2.694 (2) Å, and the Ce—N distances rang from 2.643 (2)–2.691 (2) Å, all of which are within the range of those of other nine-coordinated Ce^III complexes with carboxylic donor ligands and 1,10-phenanthroline (Fu et al., 2007) (Table 1).

For background to phenoxyalkanoic acids, see: Markus & Buser (1997). For a related La complex, see: Li et al. (2010). For isotypic structures, see: for Tb (Shen et al., 2011a), for Pr (Shen et al., 2011b), for Dy (Shen et al., 2011c), for La (Shen et al., 2011d), for Ho (Shen et al., 2011e), for Gd (Shen et al., 2011f).

Experimental

Reagents and solvents used were of commercially available quality and without purified before use. 2-Phenoxypropionic acid (1.5 mmol), Ce(NO₃)₃^.6H₂O (0.5 mmol) and 1,10-phenanthroline (0.5 mmol) were dissolved in 20 ml enthanol, then 10 ml water were added to the above solution. The mixed solution was stirred for 12 h at room temperature. Finally, the deposit was filtered off and the colourless solution was kept in the open air. Colourless crystals were obtained after several days.