Tetra­aqua­(2,2′-bipyridine-5,5′-dicarboxyl­ato-κ2 N,N′)nickel(II) dihydrate

Hua Yang

doi:10.1107/S1600536809035910

. 2009 Sep 12;65(Pt 10):m1207. doi: 10.1107/S1600536809035910

Tetraaqua(2,2′-bipyridine-5,5′-dicarboxylato-κ² N,N′)nickel(II) dihydrate

Hua Yang ^a,^*

PMCID: PMC2970486 PMID: 21577733

Abstract

In the title compound, [Ni(C₁₂H₆N₂O₄)(H₂O)₄]·2H₂O, obtained from a basic solution of 2,2′-bipyridine-5,5′-dicarboxylate and nickel(II) chloride in water, the central Ni(II) cation (site symmetry 2) is coordinated by two N atoms from the 2,2′-bipyridine-5,5′-dicarboxylate ligand and four aqua O atoms. The N—Ni—N angle is 78.64 (8)°. Weak but significant π–π stacking interactions exist between the pyridine rings with a centroid–centroid distance of 3.652 (8) Å. In addition, four O atoms of the two carboxyl groups form hydrogen bonds with both coordinated and uncoordinated water molecules, forming an infinite three-dimensional network.

Related literature

For attempts to synthesize 5,5′- and 6,6′-substituted 2,2′-bipyridine derivatives, see: He et al. (2009 ▶); Karaca et al. (2009 ▶); Yousefi et al. (2008 ▶).

Experimental

Crystal data

[Ni(C₁₂H₆N₂O₄)(H₂O)₄]·2H₂O
M _r = 408.97
Monoclinic,
a = 12.4787 (2) Å
b = 9.8152 (2) Å
c = 12.6533 (2) Å
β = 92.107 (2)°
V = 1548.74 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.31 mm⁻¹
T = 120 K
0.18 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.730, T _max = 0.828
8276 measured reflections
1691 independent reflections
1379 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.065
S = 0.98
1691 reflections
138 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035910/ng2636sup1.cif

e-65-m1207-sup1.cif^{(15.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035910/ng2636Isup2.hkl

e-65-m1207-Isup2.hkl^{(83.4KB, 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
O5—H52⋯O3ⁱ	0.837 (10)	2.178 (16)	2.9566 (19)	155 (3)
O2—H22⋯O3ⁱⁱ	0.834 (10)	1.921 (12)	2.7410 (18)	168 (3)
O5—H51⋯O4ⁱⁱⁱ	0.834 (10)	1.913 (11)	2.7286 (19)	166 (2)
O2—H21⋯O4^iv	0.833 (10)	1.852 (10)	2.6831 (17)	175 (2)
O1—H11⋯O4^iv	0.843 (9)	2.650 (17)	3.1740 (18)	121.6 (16)
O1—H11⋯O3^iv	0.843 (9)	2.097 (10)	2.9386 (18)	175.9 (19)
O1—H12⋯O5	0.834 (10)	1.861 (11)	2.688 (2)	171 (3)

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

Acknowledgments

The author thanks the financial support of Natural Foundation of Heilongjiang Province.

supplementary crystallographic information

Comment

2,2'-Bipyridine was used very commonly as ending complexing ligand. Great efforts have been made to synthesize 5,5' and 6,6' position substituted derivatives (He et al., 2009; Karaca et al., 2009; Yousefi et al., 2008). Here we reported the crystal structure of a complexing compound of Ni(II) coordinating to 4,4'dicarboxyl substituted 2,2'-bipyridine derivative.

The central Ni cation coordinated to two N atoms from dianions of one 2,2'-bipyridine-5,5'-dicarboxylate and four O atoms from four waters, forming a distorted octahedral system. Ni(II) cation lies on the twofold axis of the crystal lattice. Two Ni—N bonds were generated by C2 symmetry operation from each other with bond length 2.0706 (14). Four Ni—O bond lengths are nearly equal, two of which 2.0610 (12), and another two 2.0801 (13). Each of two equivalent carboxyl anions has two unequivalent oxygen atoms, C—O bond lengths of which are equalized to be 1.266 (2) and 1.254 (2), respectively. All O atoms of carboxyls formed hydrogen bonds with both complexed waters from another complexing supermolecule and free waters into three dimentional infinite hydrgon bonding network, which stablized the whole crystal structure, along with pi-pi stacking of aromatic pyridine rings.

Experimental

A solution of 2,2'-bipyridine-5,5'-dicarboxylate (23.2 mg, 0.1 mmol) and NiCl₂.6H₂O (23.8 mg, 0.1 mmol) was added an aqueous solution of NaOH (0.1 mmol/ml) to adjust pH as 7.0–7.5 at room temperature. A small amount of white precipitate was removed from the resulting solution. Prism colorless crystals were obtained by slow evaporation at room temperature over a period of 10 days.