Diaqua­bis­[N-(pyridin-4-yl)isonicotin­amide-κN]bis­(thio­cyanato-κN)cobalt(II)

Jacob W Uebler; Robert L LaDuca

doi:10.1107/S1600536812024105

. 2012 Jun 2;68(Pt 7):m867. doi: 10.1107/S1600536812024105

Diaquabis[N-(pyridin-4-yl)isonicotinamide-κN]bis(thiocyanato-κN)cobalt(II)

Jacob W Uebler ^a, Robert L LaDuca ^a,^*

PMCID: PMC3393148 PMID: 22807716

Abstract

In the title compound, [Co(NCS)₂(C₁₁H₉N₃O)₂(H₂O)₂], the octahedrally coordinated Co^II ion lies on a crystallographic inversion center and is bound by two isothiocyanate ligands, two aqua ligands and two N-(pyridin-4-yl)isonicotinamide (4-pina) ligands. The dihedral angle between the aromatic rings in the 4-pina ligand is 8.98 (11)°. In the crystal, the individual molecular units are aggregated in three dimensions by O—H⋯N, O—H⋯S and N—H⋯S hydrogen-bonding pathways.

Related literature

For other cobalt isothiocyanate coordination polymers containing dipyridyl ligands, see: Johnston et al. (2007 ▶); Martin et al. (2009 ▶). For other coordination polymers containing the 4-pina ligand, see: Uemura et al. (2008 ▶). For the synthesis of the 4-pina ligand, see: Gardner et al. (1954) ▶.

Experimental

Crystal data

[Co(NCS)₂(C₁₁H₉N₃O)₂(H₂O)₂]
M _r = 609.55
Triclinic,
a = 7.0651 (4) Å
b = 9.3943 (5) Å
c = 10.5943 (6) Å
α = 81.433 (1)°
β = 76.343 (1)°
γ = 71.697 (1)°
V = 646.58 (6) Å³
Z = 1
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 173 K
0.30 × 0.19 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.778, T _max = 0.873
10537 measured reflections
2348 independent reflections
2224 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.079
S = 1.06
2348 reflections
187 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.07 e Å⁻³
Δρ_min = −0.33 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812024105/hb6817sup1.cif

e-68-0m867-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024105/hb6817Isup2.hkl

e-68-0m867-Isup2.hkl^{(115.4KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O1	2.0964 (15)
Co1—N4	2.0994 (18)
Co1—N1	2.1410 (16)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯S1ⁱ	0.83 (2)	2.52 (2)	3.3129 (16)	162 (2)
O1—H1B⋯N3ⁱⁱ	0.84 (2)	1.95 (2)	2.755 (2)	162 (2)
N2—H2N⋯S1ⁱⁱⁱ	0.93 (2)	2.68 (2)	3.540 (2)	155 (2)

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

Acknowledgments

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund for funding this work.

supplementary crystallographic information

Comment

In an attempt to prepare cobalt isothiocyanato coordination polymers containing 4-pyridylisonicotinamide (4-pina), the title compound, [Co(H₂O)₂(NCS)₂(C₁₁H₉N₃O)₂], was isolated.

The asymmetric unit of the title compound contains a Co^II ion on a crystallographic inversion center, one aqua ligand, one N-bound isothiocyanato ligand, and one 4-pina ligand bound via the pyridyl ring closest to the amide N atom. Operation of the inversion center produces a complete [Co(H₂O)₂(NCS)₂(4-pina)₂] molecular complex (Fig. 1). The Co^II ion is octahedrally coordinated with trans aqua ligands, trans isothiocyanato ligands and trans 4-pina ligands. One of the pyridyl termini of the 4-pina ligand remains unligated and unprotonated.

Individual [Co(H₂O)₂(NCS)₂(4-pina)₂] complexes are connected into supramolecular chain motifs oriented along the [1 1 0] crystal direction (Fig. 2) via O—H···N hydrogen bonding between aqua ligands and unligated pyridyl N atoms. In turn these supramolecular chains aggregate into layer motifs (Fig. 3) by means of O—H···S hydrogen bonding between aqua ligands and terminal S atoms of the isothiocyanato ligands. These layers are coincident with the crystallographic (0 1 1) planes. These planes further aggregate into the three-dimensional crystal structure of the title compound (Fig. 4) through N—H···S hydrogen bonding between amide N—H groups of the 4-pina ligands and terminal S atoms of the isothiocyanato ligands.

Experimental

Cobalt(II) thiocyanate was obtained commercially. 4-Pyridylisonicotinamide was prepared by a published procedure (Gardner et al., 1954). Cobalt(II) thiocyanate (23 mg, 0.13 mmol) was dissolved in 3 ml water in a 15 ml glass vial. Onto this solution was layered 2 ml of a 1:1 water:ethanol solution, followed by a solution of 4-pina (19 mg, 0.10 mmol) dissolved in 3 ml 95% ethanol. Pink blocks of the title compound (16 mg, 0.026 mmol, 55% yield based on 4-pina) were obtained after 14 d at 298 K, and were isolated after washing with distilled water and acetone, and drying in air.