catena-Poly[[(2,9-dimethyl-1,10-phenanthroline-κ2 N,N′)cobalt(II)]-μ-malonato-κ4 O 1,O 1′:O 3,O 3′]

Ling-Feng Qiu; Bai-Lu Zhou; Wei Xu

doi:10.1107/S1600536810038043

. 2010 Sep 30;66(Pt 10):m1327. doi: 10.1107/S1600536810038043

catena-Poly[[(2,9-dimethyl-1,10-phenanthroline-κ² N,N′)cobalt(II)]-μ-malonato-κ⁴ O ¹,O ^1′:O ³,O ^3′]

Ling-Feng Qiu ^a, Bai-Lu Zhou ^a, Wei Xu ^a,^*

PMCID: PMC2983174 PMID: 21587459

Abstract

In the title compound, [Co(C₃H₂O₄)(C₁₄H₁₂N₂)]_n, the Co^II ion is in a distorted octahedral coordination being chelated by a 2,9-dimethyl-1,10-phenanthroline molecule (dmphen) and two carboxylate groups of two malonate ligands The malonate ligand acts in a bridging mode, forming coordination chains along [100]. π–π stacking interactions between dmphen ligands [interplanar distances = 3.414 (4) and 3.447 (4) Å] organize the coordination polymers into supramolecular double chains.

Related literature

For coordination polymers with dicarboxylate ligands, see: Rao et al. (2004 ▶); Zheng et al. (2004 ▶).

Experimental

Crystal data

[Co(C₃H₂O₄)(C₁₄H₁₂N₂)]
M _r = 369.23
Triclinic,
a = 6.8767 (14) Å
b = 9.5293 (19) Å
c = 11.149 (2) Å
α = 86.83 (3)°
β = 89.53 (3)°
γ = 89.52 (3)°
V = 729.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 295 K
0.33 × 0.11 × 0.07 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.653, T _max = 0.782
7245 measured reflections
3309 independent reflections
2590 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.127
S = 1.06
3309 reflections
222 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810038043/gk2299sup1.cif

e-66-m1327-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038043/gk2299Isup2.hkl

e-66-m1327-Isup2.hkl^{(162.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O1	2.180 (3)
Co1—O2	2.145 (3)
Co1—O3ⁱ	2.229 (3)
Co1—O4ⁱ	2.126 (4)
Co1—N1	2.122 (3)
Co1—N2	2.103 (3)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

This project was sponsored by the K. C. Wong Magna Fund in Ningbo University and the Scientific Research Fund of Ningbo University (grant No. XYL09078).

supplementary crystallographic information

Comment

Metal-phenanthroline complexes and their derivatives have attracted much attention because of their peculiar features. In turn dicarboxylate ligands play an important role in modern coordination chemistry and many complexes have been published with them as ligands (Rao et al., 2004; Zheng et al., 2004). The title complex, (I), was recently prepared and its crystal structure is reported here.

The crystal structure of the title compound consists of [Co(C₁₄H₁₂N₂)(C₃H₂O₄)]_n chains (Fig. 1). Each Co atom is surrounded by two nitrogen atoms of one 2,9-dimethyl-1,10-phenanthroline ligand and four oxygen atoms of two bis-chelating malonate anions to complete a seriously distorted octahedral coordination (Table 1). The malonate ligands bridge the Co atoms to form neutral one-dimensional chains [Co(C₁₄H₁₂N₂)(C₃H₂O₄)]_n along [100] with parallel orientated phen ligands at the same side. As shown in Fig. 2, through π-π stacking interactions the dmphen ligands of two adjacent coordination chains form supramolecular double chains. The interplanar distances between the neighbouring dmphen ligands are 3.414 (4) and 3.447 (4) Å.

Experimental

Addition of 2.0 ml (1 M) NaOH to an aqueous solution of CoCl₂.6H₂O (0.238 g, 1.00 mmol) in 10.0 ml H₂O produced a pink precipitate, which was centrifugated and washed with doubly destilled water for several times until no Cl^- anions were detectable. The fresh precipitate was then added to a stirred solution of malonic acid (0.104 g, 1.00 mmol) and 2,9-dimethyl-1,10-phenanthroline hydrate (0.226 g, 1 mmol) in CH₃OH/H₂O (1:1 30 ml). The red mixture was allowed to stand at room temperature and after several days, red plate-like crystals suitable for X-ray analysis were formed. grown by slow evaporation.