Poly[[diaqua­bis­(μ2-4,4′-bipyrid­yl)cobalt(II)] dinitrate tetra­hydrate]

Asma Lehleh; Mehdi Boutebdja; Adel Beghidja; Chahrazed Beghidja; Hocine Merazig

doi:10.1107/S1600536813005230

. 2013 Mar 2;69(Pt 4):m177–m178. doi: 10.1107/S1600536813005230

Poly[[diaquabis(μ₂-4,4′-bipyridyl)cobalt(II)] dinitrate tetrahydrate]

Asma Lehleh ^a, Mehdi Boutebdja ^a, Adel Beghidja ^a,^*, Chahrazed Beghidja ^a, Hocine Merazig ^a

PMCID: PMC3629466 PMID: 23633984

Abstract

The title compound, {[Co(C₁₀H₈N₂)₂(H₂O)₂](NO₃)₂·4H₂O}_n, (C₁₀H₈N₂ = 4,4′-bipyridine = 4,4′-bpy) is a layered coordination polymer built up from a cationic square grid extending in (101) enclosing uncoordinating nitrate ions and water molecules. The Co^II ion has site symmetry 2 and one of the 4,4′-bpy ligands is generated by twofold symmetry [two N atoms and two C atoms lie on the rotation axis and the dihedral angle between the pyridine rings is 45.66 (5)°]. The other 4,4′-bpy ligand is generated by a crystallographic inversion center. The Co^II ion exhibits a slightly distorted octahedral coordination geometry defined by two O atoms of two coordinating water molecules and four N atoms from four bridging 4,4′-bpy ligands. The structure is consolidated by O—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds.

Related literature

For related structures with 4,4′-bpy ligands, see: Aoyagi et al. (2000 ▶); Felloni et al. (2002 ▶); Jin et al. (2006 ▶); Tong et al. (2000 ▶).

Experimental

Crystal data

[Co(C₁₀H₈N₂)₂(H₂O)₂](NO₃)₂·4H₂O
M _r = 603.41
Monoclinic,
a = 18.6093 (19) Å
b = 11.5447 (13) Å
c = 12.1216 (13) Å
β = 95.625 (4)°
V = 2591.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 296 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
18421 measured reflections
3942 independent reflections
3660 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.083
S = 1.05
3942 reflections
198 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.49 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: ATOMS (Dowty, 1995 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Click here for additional data file.^{(27.1KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813005230/hb7035sup1.cif

e-69-0m177-sup1.cif^{(27.1KB, cif)}

Click here for additional data file.^{(189.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813005230/hb7035Isup2.hkl

e-69-0m177-Isup2.hkl^{(189.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O1W	2.0741 (10)
Co1—N1	2.2235 (10)
Co1—N2	2.1898 (13)
Co1—N3ⁱ	2.2306 (14)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H12⋯O3W ⁱⁱ	0.877 (12)	1.801 (12)	2.675 (2)	174.2 (14)
O1W—H13⋯O2W ⁱⁱⁱ	0.884 (12)	1.790 (12)	2.6744 (18)	178.7 (16)
O2W—H14⋯O1	0.878 (13)	1.959 (12)	2.827 (2)	170.1 (13)
O2W—H15⋯O2^iv	0.882 (14)	1.906 (14)	2.765 (2)	164.2 (14)
O3W—H16⋯O1	0.873 (13)	1.908 (13)	2.769 (3)	168.9 (14)
O3W—H17⋯O3^iv	0.887 (11)	2.109 (11)	2.958 (2)	159.9 (15)
C1—H1⋯O1W ^v	0.93	2.54	3.0860 (15)	117
C11—H11⋯N1^vi	0.93	2.58	3.1974 (15)	124
C11—H11⋯O3^vii	0.93	2.46	3.209 (2)	137

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

Acknowledgments

The authors thank the MESRS (Algeria) for financial support. AL thanks the DG–RSDT and ANDRU (Direction Générale de la Recherche Scientifique et du Développement Technologique et l’Agence Nationale pour le Développement de la Recherche Universitaire, Algeria) for support through the PNR project.

supplementary crystallographic information

Comment

The structure of (I) is a two dimensional layer with no interpenetration and no enclathration of organic guest molecules. The Co^II atom being located on a twofold crystallographic axis, has slightly distorted octahedral geometry, being ligated by two aqua ligands [Co—O1w = 2.074 (10) Å] and four pyridil groups from 4,4'-bpy ligands (Fig. 1), with a distance Co—N in the range of 2.1898 (13) - 2.2306 (14) Å which is almost similar to that observed in {[{Co(H₂O)₂}(µ-4,4'-bpy)₂][NO₃]₂. 2(4,4'-bpy).2H₂O}_n; {[{Co(H₂O)₂(4,4'-bpy)₂}(µ-4,4'-bpy)]. 1.5[NO₃].0.5OH. 2(4,4'-bpy).2.5H₂O}_n, Felloni et al. (2002) and {[Co(µ-4,4'-bpy)(4,4'-bpy)₂(H₂O)₂].(OH)₃.(NMe₄).4,4'-bpy.4H₂O}_n, Jin et al. (2006), these last act as a bidentate bridging ligands giving rise to a 2-D square grid sheet of (4,4) topology lying in the (101) plane. The basal coordinated 4,4'-bpy is located on an inversion center, it is planar with a 0° interplanar angle between the two pyridil rings, the same thing is observed in {[Cd(4,4'-bpy)₂(H₂O)₂]. (NO₃)₂.4H₂O}_n, Aoyagi et al. (2000), whereas the axially one is nonplanar with an angle of 45.60° between the pyridil rings. The dihedral angle between the two basal coordinated 4,4'-bpy molecules is 46.92°. Each layer features a perfectly planar, though slightly distorted, square with Co(II) atom and 4,4'-bpy at each corner and side, respectively (cis N—Co—N = 88.64 (2)°, 91.37 (2)°) (Fig. 2). The square cavity has dimensions of 11.54 × 11.59 Å, which are comparable to those of closely related compound {[Cd(4,4'-bpy)₂(H₂O)₂].(NO₃)₂.2H₂O}_n, Tong et al. (2000). The nitrate ion and lattice water molecules are situated between the coordination layers and form extensive hydrogen bonds among the aqua ligands, 4,4'-bpy, uncoordinated water molecules and nitrate ion, which extend the two-dimensional coordination layers into a three-dimensional molecular network (Fig. 3).

Experimental

A mixture of Co(NO₃)2. 6H₂O (0.291 g, 1 mmole), trans-cinnamic acid (0.148 g, 1 mmole), NaOH (0.04 g, 1 mmole) and 4,4'-bpy (0.156 g, 1 mmole) were dissolved with 10 ml of mixed solution (MeOH/H₂O: 2/1) in a 20 ml Teflon-lined stainless steel reactor and heated to 120°C for 24 h. The reactor was cooled to room temperature over a period of 24 h, the reaction was filtered. The orange filtrate was kept for several weeks at room temperature. Orange crystals suitable for X-ray analysis were obtained. Note: the measured crystal is a fragment cut from a larger crystal.