Tris(2,2′-bipyridine-κ2 N,N′)cobalt(II) bis­(hexa­fluoridophosphate)

Ayfer Menteş; Kuldip Singh

doi:10.1107/S1600536812050234

. 2012 Dec 15;69(Pt 1):m58. doi: 10.1107/S1600536812050234

Tris(2,2′-bipyridine-κ² N,N′)cobalt(II) bis(hexafluoridophosphate)

Ayfer Menteş ^a,^*, Kuldip Singh ^b

PMCID: PMC3588389 PMID: 23476351

Abstract

In the title compound, [Co(C₁₀H₈N₂)₃](PF₆)₂, the Co^II atom is coordinated by the six N atoms of three 2,2′-bipyridyl ligands and adopts a highly distorted octahedral geometry. The crystal used was a merohedral twin, the refined ratio of twin components being 0.820 (1):0.180 (1). The crystal structure features weak C—H⋯F interactions, forming a three-dimensional network.

Related literature

For related structures, see: Chygorin et al. (2012 ▶); Liu et al. (2008 ▶, 2010 ▶).

Experimental

Crystal data

[Co(C₁₀H₈N₂)₃](PF₆)₂
M _r = 817.42
Trigonal,
a = 10.3524 (18) Å
c = 26.140 (6) Å
V = 2426.2 (8) Å³
Z = 3
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 150 K
0.35 × 0.16 × 0.13 mm

Data collection

Bruker APEX 2000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.581, T _max = 0.862
19252 measured reflections
6285 independent reflections
5344 reflections with I > 2σ(I)
R _int = 0.087

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.088
S = 0.94
6285 reflections
461 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ▶), 3114 Friedel pairs
Flack parameter: 0.010 (18)

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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(38.6KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812050234/lr2090sup1.cif

e-69-00m58-sup1.cif^{(38.6KB, cif)}

Click here for additional data file.^{(307.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050234/lr2090Isup2.hkl

e-69-00m58-Isup2.hkl^{(307.6KB, 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
C24—H24⋯F2ⁱ	0.95	2.49	3.324 (7)	146
C23—H23⋯F4ⁱ	0.95	2.55	3.253 (7)	131
C18—H18⋯F11ⁱⁱ	0.95	2.52	3.149 (6)	124
C13—H13⋯F10ⁱⁱⁱ	0.95	2.50	3.208 (6)	131
C10—H10⋯F11^iv	0.95	2.51	3.265 (6)	137
C9—H9⋯F7^iv	0.95	2.33	3.136 (6)	142
C7—H7⋯F8^v	0.95	2.38	3.160 (7)	139
C2—H2⋯F2^vi	0.95	2.33	3.081 (7)	136

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

Acknowledgments

The authors are grateful to Leicester University for the use of the X-ray diffractometer.

supplementary crystallographic information

Comment

The reaction of Cobalt(II) pentafluoropropionate with NaPF₆ in the presence of 2,2'-bipyridine yields the coordination compound tris(bipyridine)cobalt(II) hexafluorophosphate (1), [Co(bipy)₃][PF₆]₂. Crystals were grown by allowing slow evaporation of the complex in ethanol. The title complex crystallizes in the space group P3(2) in contrast to the related compound [Co(bipy)₃][Mo₆O₁₉]₂ which crystallizes in P2₁/n (Liu et al., 2010). The structure of (1) is shown in Fig. 1. Within the divalent complex cations, the cobalt atoms are each surrounded by six N atoms of three chelating bipy ligands to complete a distorted octahedral coordination with d(Co—N) = 2.098 (7) – 2.149 (8) Å, the cis and trans N—Co—N bond angles in the range 76.6 (3) – 96.9 (3) and 167.6 (3) – 170.5 (3)°, respectively. Such distances are similar to those found in other related structures (Liu et al., 2008, Chygorin et al. 2012). There has been great interest in homoleptic imine complexes, because of great potential applications in many fields such as, catalysis, material science and medicine. The crystal packing of the title compound is presented in Fig. 2. The crystal structure is stabilized by weak intermolecular C—H···F bonds.

Experimental

Tris(bipyridine)cobalt(II) hexafluorophosphate was prepared by stirring a mixture of a solution containing Co(O₂CC₂F₅)₂ (0.100 g, 0.25 mmol) and bipyridine (0.120 g, 0.77 mmol) in ethanol (10 ml). The reaction mixture was stirred for 2 h. After this time NaPF₆ (0.100 g, 0.59 mmol) was added and stirred for 1 h. Solid of title compound was obtained by slow evaporation of an ethanol solution in refrigerator (Yield 0.150 g, 79%; m.p. 594 K). Yellow block crystals were obtained in acetonitrile/ethanol (1:1) solution after few days. ATR-IR: 1603 ν(C=N), 1566 ν(C=C) cm^-1.