Bis(μ-pyridine-2,5-dicarboxyl­ato)-κ3 N,O 2:O 5;κ3 O 5:N,O 2-bis­[aqua­(2,2′-bipyridine-κ2 N,N′)cobalt(II)] dihydrate

Shie Fu Lush

doi:10.1107/S1600536811003059

. 2011 Jan 29;67(Pt 2):m278–m279. doi: 10.1107/S1600536811003059

Bis(μ-pyridine-2,5-dicarboxylato)-κ³ N,O ²:O ⁵;κ³ O ⁵:N,O ²-bis[aqua(2,2′-bipyridine-κ² N,N′)cobalt(II)] dihydrate

Shie Fu Lush ^a,^*

PMCID: PMC3051640 PMID: 21522925

Abstract

In the centrosymmetric title compound, [Co₂(C₇H₃NO₄)₂(C₁₀H₈N₂)₂(H₂O)₂]·2H₂O, the two Co^II cations are bridged by pairs of pyridine-2,5-dicarboxylate anions across an inversion center. Besides two pyridine-2,5-dicarboxylate anions, one bidentate 2,2′-bipyridine and one water molecule coordinate to the Co cation, completing a distorted octahedral coordination geometry. Within the dinuclear molecule, π–π stacking occurs between parallel pyridine rings with centroid–centroid distances of 3.802 (2) Å. The crystal structure contains extensive O—H⋯O and weak C—H⋯O hydrogen bonds and C—H⋯π interactions.

Related literature

For multi-dentate coordination modes of the pyridine-3,5-dicarboxylate anion, see: Gao et al. (2005 ▶). For related structures, see: Aghabozorg et al. (2007 ▶); Lu et al. (2006 ▶); Xu et al. (2004 ▶).

Experimental

Crystal data

[Co₂(C₇H₃NO₄)₂(C₁₀H₈N₂)₂(H₂O)₂]·2H₂O
M _r = 832.50
Triclinic,
a = 7.2731 (11) Å
b = 9.7123 (15) Å
c = 12.2887 (19) Å
α = 98.447 (3)°
β = 103.283 (3)°
γ = 91.564 (3)°
V = 834.0 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.928, T _max = 0.971
4799 measured reflections
2903 independent reflections
2557 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.145
S = 1.14
2903 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 1.58 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: SMART (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: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003059/xu5145sup1.cif

e-67-0m278-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811003059/xu5145Isup2.hkl

e-67-0m278-Isup2.hkl^{(139.6KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O1	2.059 (3)
Co1—O2	2.056 (3)
Co1—O5ⁱ	2.089 (3)
Co1—N1	2.126 (3)
Co1—N2	2.155 (3)
Co1—N3	2.204 (3)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the N-pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O3ⁱⁱ	0.84	1.82	2.629 (4)	159
O1—H1B⋯O6	0.88	1.94	2.755 (5)	154
O6—H6A⋯O4ⁱⁱⁱ	0.85	2.40	3.232 (5)	166
O6—H6B⋯O4^iv	0.83	2.01	2.829 (5)	170
C4—H4A⋯O2^v	0.93	2.52	3.202 (5)	131
C7—H7A⋯O6^vi	0.93	2.57	3.332 (6)	140
C8—H8A⋯O4^vii	0.93	2.55	3.461 (6)	169
C9—H9A⋯O3^viii	0.93	2.59	3.330 (6)	137
C12—H12A⋯O4^ix	0.93	2.44	3.317 (5)	158
C15—H15A⋯O3ⁱⁱ	0.93	2.36	3.249 (5)	160
C2—H2A⋯Cg^iv	0.93	2.72	3.547 (5)	150

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

Acknowledgments

This work was supported financially by Yuanpei University, Taiwan.

supplementary crystallographic information

Comment

2,5-PydH₂ can be easily deprotonated to get a O-donors to N-donor multidentate anion (pyd^2-), enabling the ligand coordinates to two or more metal ions in a briding mode and chelating mode (Gao et al., 2005). The complexation of metal ions using the deprotonated conjugate base of 2,5-pydH₂ as a ligand has been reported in the literature (Aghabozorg et al., 2007; Lu et al., 2006; Xu et al., 2004).

The symmetric unit of the title compound contain two Co^II cations, two pyd anions, two bpy molecules and two coordinated water molecules. Each Co^II ion is surrounded by one bpy ligand, two pyd anions and one coordinated water molecule, to give a distorted octahedral geometry. Two pyd anions bridges two Co^II ions to form a centrosymmetric dimeric complex (Table 1 and Fig. 1).

The crystal structure contains an extensive network of classical O—H···O and weak C—H···O hydrogen bonds (full details and symmetry codes are given in Table 2 and Fig. 2). C—H ···π(full detail and symmetry code is given in Table 2) and π-π stacking are present in the crystal structure, the shortest centroids distance between parallel pyridine rings is 3.8023 (17) Å [Cg5ⁱ···Cg5 (N3/C11—C15)] [symmetry code: 1 - x, 1 - y, 1 - z].

Experimental

An aqueous solution (5 ml) of bpy (0.0312 g, 0.20 mmol) was mixed with aqueous solution (5 ml) containing Co(NO₃)₂.6H₂O (0.0450 g, 0.20 mmol) and 2,5-pydH₂ (0.0346 g, 0.2 mmol). The mxiture was put in a 23-ml Teflon liner reactor and heated at 418 K in oven for 48 h. The resulting solution was slowly cooled to room temperature. The orange transparent single crystals of the title complex were obtained in 35.5% yield (based on Co).