Aqua­(2,9-dimethyl-1,10-phenanthroline-κ2 N,N′)(formato-κ2 O,O′)(formato-κO)cobalt(II) monohydrate

Sheng-Liang Ni; Ping Xia; Feng Cao

doi:10.1107/S1600536810050051

. 2010 Dec 4;67(Pt 1):m39–m40. doi: 10.1107/S1600536810050051

Aqua(2,9-dimethyl-1,10-phenanthroline-κ² N,N′)(formato-κ² O,O′)(formato-κO)cobalt(II) monohydrate

Sheng-Liang Ni ^a,^*, Ping Xia ^a, Feng Cao ^a

PMCID: PMC3050392 PMID: 21522561

Abstract

The asymmetric unit of the title compound, [Co(HCO₂)₂(C₁₄H₁₂N₂)(H₂O)]·H₂O, contains a mononuclear complex molecule hydrogen bonded to a lattice water molecule. The Co^II cation is in a distorted octahedral coordination environment defined by the two N atoms of the 2,9-dimethyl-1,10-phenanthroline ligand and four O atoms. Two of these are from a chelating formate anion, one from a monodentate formate and the last from an aqua ligand. In the crystal, molecules are connected by O—H⋯O hydrogen bonds, forming double chains along [100] with the 2,9-dimethyl-1,10-phenanthroline ligands pointing outwards from each chain. These chains are further linked into layers parallel to (011) by inter-chain π–π stacking interactions with centroid–centroid distances of 3.61 (1) Å.

Related literature

For background to the formation and applications of supramolecular metal complexes, see: Moulton & Zaworotko (2001 ▶); Aakeroy & Seddon (1993 ▶). For related structures, see: Cai et al. (2008 ▶); Chen et al. (2009 ▶).

Experimental

Crystal data

[Co(HCO₂)₂(C₁₄H₁₂N₂)(H₂O)]·H₂O
M _r = 393.25
Triclinic,
a = 7.4220 (15) Å
b = 10.441 (2) Å
c = 11.419 (2) Å
α = 82.92 (3)°
β = 81.62 (3)°
γ = 76.01 (3)°
V = 845.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.05 mm⁻¹
T = 295 K
0.16 × 0.10 × 0.08 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1996 ▶) T _min = 0.880, T _max = 0.912
4797 measured reflections
3897 independent reflections
3362 reflections with I > 2σ(I)
R _int = 0.017
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.098
S = 1.03
3897 reflections
227 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810050051/sj5068sup1.cif

e-67-00m39-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050051/sj5068Isup2.hkl

e-67-00m39-Isup2.hkl^{(191KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co—O4	2.0552 (16)
Co—O1	2.0710 (17)
Co—N1	2.1194 (18)
Co—N2	2.1430 (16)
Co—O3	2.1622 (18)
Co—O2	2.2024 (17)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O5ⁱ	0.85	1.84	2.688	173
O1—H1C⋯O6ⁱⁱ	0.84	1.98	2.774	156
O6—H6B⋯O3	0.85	1.96	2.809	176
O6—H6C⋯O4ⁱⁱⁱ	0.85	2.33	3.098	151

Open in a new tab

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

Acknowledgments

This project was supported by the Foundation of the Education Department of Zhejiang Province (ky23022) and the Huzhou Municipal Foundation of Science and Technology (2006YG21).

supplementary crystallographic information

Comment

In the past decade, a variety of supramolecular architectures based on non–covalent intermolecular interactions such as hydrogen bonding, van der Walls forces and π–π interactions have been achieved by using transition metal centers and organic ligands due to their possible intriguing structural topologies and potential applications in optics, catalysis, ion exchange, gas storage, and the molecular–based magnetic materials (Aakeroy & Seddon, 1993). Carboxylate ligands have been actively utilized as construction units to obtain many supramolecular complexes (Moulton & Zaworotko, 2001) Herein, we are interested in self–assemblies of Co^II ions and 2,9-dimethyl-1,10-phenanthroline with formic acid, leading to the successful preparation of the complex [Co(H₂O)(C₁₄H₁₂N₂)(HCO₂)₂].H₂O.

The asymmetric unit of the title compound consists of one Co^II ion, a H₂O molecule, a 2,9-dimethyl-1,10-phenanthroline molecule, one O,O'–chelated formate anion and another coordinated formate anion, and one lattice H₂O molecule (Fig. 1). Each Co^II atom is coordinated two N atoms from one 2,9-dimethyl-1,10-phenanthroline, three O atoms from two formate anions and one aqua ligand to complete a distorted octahedral CoN₂O₄ chromophore. The Co–N/O distances of 2.055 (2)–2.143 (2) Å, Table 1, fall within the normal range (Cai et al., 2008, Chen et al., 2009), both the cisoid and transoid bond angles in the range 59.90 (8)–112.35 (7) Å and 167.31 (7)–176.05 (6) Å, respectively, indicating that the octahedral CoN₂O₄ geometry is a highly distorted one. For the two formate anions, the angle (O2–C15–O3, 122.6 (3)°) in the chelated formate is smaller than that in the anion that binds in a monodentate fashion (O4–C16–O5, 128.8 (2)°). The 2,9-dimethyl-1,10-phenanthroline ligand is almost coplanar with a mean square deviation 0.0163 Å. The O6 solvent water molecule is not coordinated to Co atom with the distance between the cobalt and water oxygen atoms of 4.800 (2) Å. However it is linked to the complex molecule in the asymmetric unit by an O6—H6B—O3 hydrogen bond.

The molecules are connected by (O1–H1B···O5^#1, O1–H1C···O6^#2 and O6–H6C···O4^#3) hydrogen bonds, Table 1, to form one-dimensional double chains along [100] with 2,9-dimethyl-1,10-phenanthroline orientating outwards. The resulting chains are further linked into two-dimensional layers parallel to (011) by interchain π–π stacking interactions with centroid – centroid distances 3.61 (1) Å), Fig. 2.

Experimental

Dropwise addition of 2.0 ml of 1.0 M aqueous Na₂CO₃ to a stirred aqueous solution of CoCl₂.6H₂O (0.2380 g, 1.0 mmol) in 5.0 ml H₂O produced a pink precipitate, Co(OH)_2–2x (CO₃)_x.yH₂O, which was centrifuged and washed with water until no Cl^- anions were detected in the supernatant. The precipitate was added to a stirred aqueous methanolic solution of 2,9-dimethyl-1,10-phenanthroline in 30 ml CH₃OH–H₂O (1/1 v/v). 1.77 ml of 1.0 M aqueous formic acid was added dropwise and stirred continuously until the pink precipitate dissolved. The pink solution (pH = 4.06) was allowed to stand at room temperature. Slow evaporation over several days afforded pink block shaped crystals. Yield:45% based on the initial CoCl₂.6H₂O input.