A trinuclear cobalt–cerium complex: bis­(2,2′-bipyridine)-1κ2 N,N′;3κ2 N,N′-hexa-μ-methacrylato-1:2κ6 O:O′;2:3κ6 O:O′-nitrato-2κ2 O,O′-2-cerium(III)-1,3-dicobalt(II)

Bin Wu; Tingting Hou

doi:10.1107/S1600536810010299

. 2010 Mar 27;66(Pt 4):m457. doi: 10.1107/S1600536810010299

A trinuclear cobalt–cerium complex: bis(2,2′-bipyridine)-1κ² N,N′;3κ² N,N′-hexa-μ-methacrylato-1:2κ⁶ O:O′;2:3κ⁶ O:O′-nitrato-2κ² O,O′-2-cerium(III)-1,3-dicobalt(II)

Bin Wu ^a,^*, Tingting Hou ^a

PMCID: PMC2984076 PMID: 21580543

Abstract

In the title trinuclear cobalt-cerium complex, [CeCo₂(C₄H₅O₂)₆(NO₃)(C₁₀H₈N₂)₂], the Ce^III and each of the two Co^II ions are bridged by three bidentate methacrylate ligands. The Ce^III center is coordinated by six O atoms from six methacrylate ligands and two O atoms from the nitrate anion in a distorted square-antiprismatic geometry. Each Co^II ion is coordinated by three O atoms from three methacrylate ligands and two N atoms from a 2,2′-bipyridine ligand in a distorted trigonal-pyramidal geometry. In the crystal structure, π–π interactions between the aromatic rings [centroid–centroid distances of 3.816 (8) and 3.756 (8) Å] link the molecules into chains propagated in [01 Inline graphic ]. Weak intermolecular C—H⋯O hydrogen bonds further stabilize the crystal packing.

Related literature

For the crystal structures of analogous complexes, see: Wu & Guo (2004 ▶); Zhu et al. (2004a ▶,b ▶; 2005 ▶). For the preparation of CeL ₃·2H₂O (HL = CH₂C(CH₃)COOH), see: Lu et al. (1995 ▶).

Experimental

Crystal data

[CeCo₂(C₄H₅O₂)₆(NO₃)(C₁₀H₈N₂)₂]
M _r = 1142.84
Triclinic,
a = 11.4445 (8) Å
b = 13.6484 (9) Å
c = 16.5051 (10) Å
α = 104.108 (9)°
β = 99.937 (8)°
γ = 100.115 (7)°
V = 2398.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.69 mm⁻¹
T = 292 K
0.35 × 0.30 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.559, T _max = 0.623
17512 measured reflections
8121 independent reflections
7037 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.054
S = 1.03
8121 reflections
610 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810010299/cv2700sup1.cif

e-66-0m457-sup1.cif^{(32.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010299/cv2700Isup2.hkl

e-66-0m457-Isup2.hkl^{(397.2KB, 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
C2—H2⋯O7ⁱ	0.93	2.59	3.322 (4)	136
C3—H3⋯O9ⁱ	0.93	2.45	3.307 (5)	154
C7—H7⋯O3ⁱⁱ	0.93	2.58	3.452 (4)	156
C37—H37⋯O9ⁱⁱⁱ	0.93	2.51	3.364 (4)	152

Open in a new tab

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

Acknowledgments

This work was supported by the Natural Science Foundation of Zhejiang Province (M203105).

supplementary crystallographic information

Comment

As a contribution to a structural study of heterometallic complexes containing d-transition metal and rare-earth(III) cations (Wu & Guo, 2004; Zhu et al., 2004a,b; Zhu et al., 2005), herewith we report the synthesis and crystal structure of the title compound.

The crystal structure of the title Co—Ce—Co trinuclear complex is similar to the known crystal structures of the Zn—Nd—Zn, Zn—Pr—Zn, Zn—La—Zn and Zn—Ce—Zn complexes (Wu & Guo, 2004; Zhu et al., 2004a,b; Zhu et al., 2005). The Ce^III center is coordinated by six O atoms from six methacrylato ligands and two O atoms from nitrate anion in a distorted square-antiprismatic geometry. Each Co^II ion is coordinated by three O atoms from three methacrylato ligands and two N atoms from 2,2'-bipyridine ligand in a distorted pyramidal geometry. The Ce^III and each of two Co^II ions are bridged by three bidentate methacrylato ligands. Two Ce···Co separations are almost equal being 3.944 (1) and 3.993 (1) Å, respectively.

In the crystal structure, π-π interactions between the aromatic rings (Table 1) link molecules into chains propagated in direction [01-1]. Weak intermolecular C—H···O hydrogen bonds (Table 2) stabilize further the crystal packing.

Experimental

CeL₃.2H₂O (870 mg, 2.0 mmol; HL = CH₂C(CH₃)COOH ) prepared in accordance with Lu et al. (1995) and Co(NO₃)₂.6H₂O (435 mg, 1.5 mmol) were dissolved in 15 ml H₂O, and the pH adjusted to 4.0 using HL. Three mililiters of ethanol solution 2,2'-bipyridine (234 mg, 1.5 mmol) were added into the mixed solution with stirring. After filtration, the filtrate was allowed to stand at room temperature and single crystals suitable for X-ray work were obtained after two weeks.