(Carbonato-κ2 O,O′)bis­(1,10-phenan­throline-κ2 N,N′)cobalt(III) nitrate monohydrate

Ömer Andaç; Zuhal Yolcu; Orhan Büyükgüngör

doi:10.1107/S1600536809052763

. 2009 Dec 12;66(Pt 1):m46–m47. doi: 10.1107/S1600536809052763

(Carbonato-κ² O,O′)bis(1,10-phenanthroline-κ² N,N′)cobalt(III) nitrate monohydrate

Ömer Andaç ^a, Zuhal Yolcu ^a, Orhan Büyükgüngör ^b,^*

PMCID: PMC2980272 PMID: 21579944

Abstract

The crystal structure of the title compound, [Co(CO₃)(C₁₂H₈N₂)₂]NO₃·H₂O, consists of Co^III complex cations, nitrate anions and uncoordinated water molecules. The Co^III cation is chelated by a carbonate anion and two phenanthroline ligands in a distorted octahedral coordination geometry. A three-dimensional supramolecular structure is formed by O—H⋯O and C—H⋯O hydrogen bonding, C—H⋯π and aromatic π–π stacking [centroid–centroid distance = 3.995 (1)Å] interactions.

Related literature

For Co(III) complexes with carbonate and phen ligands, see: Fu et al. (2006 ▶); Guild et al. (1980 ▶); Hadadzadeh et al. (2007 ▶); Hennig et al. (1980 ▶); McAuliffe et al. (1992 ▶); Niederhoffer et al. (1982 ▶); Sharma et al. (2009 ▶). For a Co^II coordination compound with carbonate and phen ligands, see: Li et al. (2004 ▶).

Experimental

Crystal data

[Co(CO₃)(C₁₂H₈N₂)₂]NO₃·H₂O
M _r = 559.37
Monoclinic,
a = 13.6986 (9) Å
b = 10.8583 (5) Å
c = 16.1494 (10) Å
β = 106.386 (5)°
V = 2304.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.80 mm⁻¹
T = 296 K
0.41 × 0.26 × 0.15 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.818, T _max = 0.905
21353 measured reflections
5713 independent reflections
4021 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.102
S = 1.02
5713 reflections
349 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052763/xu2707sup1.cif

e-66-00m46-sup1.cif^{(27.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052763/xu2707Isup2.hkl

e-66-00m46-Isup2.hkl^{(279.7KB, 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
O7—H7A⋯O5	0.86 (2)	1.98 (2)	2.830 (3)	168 (5)
O7—H7B⋯O3ⁱ	0.81 (5)	2.03 (5)	2.809 (4)	164 (6)
C3—H3⋯O3ⁱⁱ	0.93	2.54	3.362 (3)	148
C5—H5⋯O1ⁱⁱ	0.93	2.56	3.415 (3)	153
C8—H8⋯O7ⁱⁱⁱ	0.93	2.31	3.130 (4)	146
C9—H9⋯O6^iv	0.93	2.35	3.234 (3)	158
C15—H15⋯O6^v	0.93	2.45	3.370 (3)	170
C17—H17⋯O4^v	0.93	2.50	3.416 (3)	167
C1—H1⋯Cg1^vi	0.93	2.92	3.705 (3)	143

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

Acknowledgments

We would like to thank the Research Foundation of Ondokuz Mayis University for financial support to this work under the Project number F474.

supplementary crystallographic information

Comment

The stucture of the title compound, (I), is shown below. Dimensions are available in the archived CIF. The combination of cobalt(II) cations, carbonate and phenantroline ligands often results in Co^III-containing products as a result of an autoxidation reaction. CCDC search revealed that several crystal structures of Co^III mixed ligand complexes of phenanthroline and carbonate ligands have been reported (Guild et al., 1980; Fu et al., 2006; Hadadzadeh et al., 2007; McAuliffe et al.,1992; Hennig et al., 1980; Niederhoffer et al., 1982; Sharma et al., 2009). Co^II coordination compound with carbonate and phen ligand has also been reported (Li et al., 2004).

In this study, we describe the synthesis and structure of the title compound, (I). The Co^III atom in the discrete [Co(CO₃)(phen)₂]⁺ cation (Fig. 1) displays a distorted octahedral geometry, being coordinated by four N atoms of two 1,10-phenanthroline ligands and two O atoms of the bidentate carbonate anion. Both phen ligands are planar with r.m.s. deviation of 0.04 Å and involve in π–π interactions with neighboring phen rings. The carbonate ligand is also planar with r.m.s. deviation of 0.002 Å. The charge-balancing nitrate ion is essencially planar with r.m.s. deviation of 0.0015 Å and exibits slight deviation from D_3h symmetry. Non-coordinated water molecule is involved in hydrogen bonding (Table 1) and contrubutes stabilization of the 3 d structure forming. As shown in Fig. 2, the hydrogen bonds are supplemented by aromatic π–π stacking interactions of neighboring phen rings, C–H···O and C–H···π interactions.

Experimental

Co(NO₃)₂.6H₂O (0.291 g, 1.0 mmol) was added to a solution containing phen (0.396 g, 2.0 mmol) and adenine (0.135 g, 1.0 mmol) in water-ethanol (10:90, 100 ml). The reaction mixture was stirred for 1 h at 343 K. Thereafter, NaHCO₃ solution (0.168 g, 2.00 mmol in 10 ml water-ethanole, 10:90) was added to the mixture for adjusting the pH to 7 by using solid-state pH sensor. The resulting solution was cooled to room temperature and filtered. The filtrate was left to stand in air for slow evaporation and red prism single crystals of (I) were obtained after several months.