Poly[(μ3-pyridine-4-carboxyl­ato-κ3 O:O′:N)(pyridin-1-ium-4-carboxyl­ato-κO)(thio­cyanato-κN)cobalt(II)]

Tristan Neumann; Julia Werner; Inke Jess; Christian Näther

doi:10.1107/S1600536812044431

. 2012 Nov 3;68(Pt 12):m1435. doi: 10.1107/S1600536812044431

Poly[(μ₃-pyridine-4-carboxylato-κ³ O:O′:N)(pyridin-1-ium-4-carboxylato-κO)(thiocyanato-κN)cobalt(II)]

Tristan Neumann ^a, Julia Werner ^a, Inke Jess ^a, Christian Näther ^a,^*

PMCID: PMC3588705 PMID: 23468670

Abstract

In the title compound, [Co(C₆H₅NO₂)(NCS)(C₆H₄NO₂)]_n, the Co²⁺ cation is coordinated by one N and two O atoms of three bridging pyridine-4-carboxylate anions, one O atom of one zwitterionic pyridinium-4-carboxylate ligand and one terminal N-bonding thiocyanate anion within a distorted N₂O₃ trigonal bipyramid. The bridging coordination mode of the ligands leads to the formation of layers parallel to (-101). N—H⋯O hydrogen-bonding interactions within the layers and S⋯S contacts of 3.257 (3) Å between the layers lead to the cohesion of the structure.

Related literature

For general background information on the synthesis and properties of transition metal–thiocyanate coordination polymers, see: Boeckmann & Näther (2010 ▶, 2011 ▶); Wöhlert et al. (2011 ▶).

Experimental

Crystal data

[Co(C₆H₅NO₂)(NCS)(C₆H₄NO₂)]
M _r = 362.22
Monoclinic,
a = 8.7857 (7) Å
b = 13.5401 (8) Å
c = 12.2054 (9) Å
β = 95.740 (6)°
V = 1444.67 (18) Å³
Z = 4
Mo Kα radiation
μ = 1.35 mm⁻¹
T = 293 K
0.18 × 0.13 × 0.04 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T _min = 0.808, T _max = 0.954
12489 measured reflections
2844 independent reflections
2353 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.098
S = 1.13
2844 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2011 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(21.8KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812044431/wm2684sup1.cif

e-68-m1435-sup1.cif^{(21.8KB, cif)}

Click here for additional data file.^{(139.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044431/wm2684Isup2.hkl

e-68-m1435-Isup2.hkl^{(139.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—O22	2.004 (2)
Co1—O21ⁱ	2.004 (2)
Co1—N1	2.010 (4)
Co1—O12	2.097 (2)
Co1—N21ⁱⁱ	2.146 (2)

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H1N⋯O11ⁱⁱⁱ	0.86	1.80	2.561 (4)	147

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Symmetry code: (iii) Inline graphic .

Acknowledgments

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

supplementary crystallographic information

Comment

The title compound was prepared within a project on the synthesis and properties of transition metal thiocyanato coordination polymers (Boeckmann & Näther, 2010, 2011; Wöhlert et al., 2011). During our attempts to prepare a one-dimensional coordination polymer based on pyridine-4-carboxylic acid as a co-ligand, crystals of the title compound, [Co(NCS)(C₆H₄NO₂)(C₆H₅NO₂)], (I), were obtained serendipitously and characterized by single crystal X-ray diffraction.

In the crystal structure of (I), the cobalt(II) cation is coordinated by one terminally O-bonded pyridinium-4-carboxylate ligand, one terminally N-bonded thiocyanate anion, one N-bonded µ-1,3,6-bridging pyridine-4-carboxylate and two O-bonded µ-1,3,6-bridging pyridine-4-carboxylate anions (Fig. 1). The coordination polyhedron of the Co²⁺ cations can be described as a distorted trigonal bipyramid (Fig. 1, Table 1).

The Co²⁺ cations are µ-1,3 bridged via pyridine-4-carboxylato anions into dimers, which are further connected into layers parallel to (101) (Fig. 2). The Co···Co distance within the dimer amounts to 3.4951 (6) Å. Within the layers N—H···O hydrogen bonding between the bridging pyridine-4-carboxylate anions and the non-bridging pyridinium carboxylate ligands (Fig. 3 and Table 2) is present. A short S···S contact of 3.257 (3) Å between the layers is also observed.

Experimental

Cobalt thiocyanate and pyridine-4-carboxylic acid were purchased from Alfa Aesar. The title compound was prepared by the reaction of 43.8 mg Co(NCS)₂ (0.25 mmol), and 61.6 mg pyridine-4-carboxylic acid (0.50 mmol) in 1.5 mL ethanol at 354 K in a closed 10 ml glas culture tube. After several days pink block-shaped crystals of the title compound were obtained.