Poly[[bis­(μ-4,4′-bipyridyl-κ2 N:N′)bis­(thio­cyanato-κN)manganese(II)] diethyl ether disolvate]

Mario Wriedt; Inke Jess; Christian Näther

doi:10.1107/S1600536810021665

. 2010 Jun 16;66(Pt 7):m781. doi: 10.1107/S1600536810021665

Poly[[bis(μ-4,4′-bipyridyl-κ² N:N′)bis(thiocyanato-κN)manganese(II)] diethyl ether disolvate]

Mario Wriedt ^a,^*, Inke Jess ^a, Christian Näther ^a

PMCID: PMC3006735 PMID: 21587708

Abstract

In the title compound, {[Mn(NCS)₂(C₁₀H₈N₂)₂]·2C₄H₁₀O}_n, the Mn^II ion is coordinated by four N-bonded 4,4′-bipyridine (bipy) ligands and two N-bonded thiocyanate anions in a distorted octahedral coordination geometry. The asymmetric unit consists of one Mn^II ion and two bipy ligands each located on a twofold rotation axis, as well as one thiocyanate anion and one diethyl ether molecule in general positions. In the crystal structure, the metal centers with terminally bonded thicyanate anions are bridged by the bipy ligands into layers parallel to (001). The diethyl ether solvent molecules occupy the voids of the structure.

Related literature

For general background to thermal decomposition reactions as an alternative tool for the discovery and preparation of new ligand-deficient coordination polymers with defined magnetic properties, see: Wriedt & Näther (2009a ▶,b ▶); Wriedt et al. (2009a ▶,b ▶). For the isotypic cobalt(II) structure, see: Lu et al. (1997 ▶).

Experimental

Crystal data

[Mn(NCS)₂(C₁₀H₈N₂)₂]·2C₄H₁₀O
M _r = 631.71
Monoclinic,
a = 11.702 (2) Å
b = 11.6391 (18) Å
c = 13.424 (2) Å
β = 106.75 (2)°
V = 1750.8 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 230 K
0.22 × 0.14 × 0.07 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.912, T _max = 0.968
11086 measured reflections
2954 independent reflections
2446 reflections with I > 2σ(I)
R _int = 0.134

Refinement

R[F ² > 2σ(F ²)] = 0.073
wR(F ²) = 0.206
S = 1.07
2954 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −1.37 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021665/hy2314sup1.cif

e-66-0m781-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021665/hy2314Isup2.hkl

e-66-0m781-Isup2.hkl^{(145KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—N21	2.181 (4)
Mn1—N12ⁱ	2.277 (4)
Mn1—N11	2.300 (4)
Mn1—N1	2.312 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

MW thanks the Stiftung Stipendien-Fonds des Verbandes der Chemischen Industrie and the Studienstiftung des deutschen Volkes for a PhD scholarship. We gratefully acknowledge financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (Project 720/3-1). We thank Professor Dr Wolfgang Bensch for the opportunity to use his experimental facilities.

supplementary crystallographic information

Comment

Recently, we are interested in thermal decomposition reactions as an alternative tool for the discovering and preparation of new ligand-deficient coordination polymers with defined magnetic properties (Wriedt & Näther, 2009a,b; Wriedt et al., 2009a,b). In our ongoing investigation on the synthesis, structures and properties of such compounds we have reacted manganese(II) chloride, potassium thiocyanate and 4,4-bipyridine (bipy). In this reaction single crystals of the title compound were grown.

The title compound (Fig. 1) represents a two-dimensional layered coordination polymer, in which the Mn^II atom is coordinated by four bipy ligands and two thiocyanate anions in an octahedral coordination mode. The crystal structure is isotypic to its cobalt(II) analogue (Lu et al., 1997). In the crystal structure the metal atoms are bridged by the bipy ligands into layers with terminally N-bonded thicyanate anions. The layers are stacked perpendicular to the crystallographic c axis in order that the metal atoms in one layer sit above or below the squares formed by the metal atoms of the adjacent layers. By this arrangement voids are formed in which the diethyl ether molecules are located (Fig. 2). The MnN₆ octahedron is markedly distorted with four long Mn—N_bipy distances in the range of 2.277 (4) to 2.312 (4) Å and two short Mn—NCS distances of 2.181 (4) Å (Table 1). The angles arround the metal atoms range between 88.27 (8) to 91.73 (8) and 176.54 (16) to 180°. The pyridyl rings of the bipy ligands form dihedral angles of 51.2 (1) and 52.6 (1)°, respectively. The shortest intra- and interlayer Mn···Mn distances amount to 11.6391 (6) and 8.3198 (11) Å, respectively.

Experimental

MnCl₂ (117.0 mg, 0.93 mmol) and KNCS (180.8 mg, 1.86 mmol) obtained from Alfa Aesar were dissolved in a mixture of 10 ml water and 15 ml ethanol. This mixture was layered with a solution of 4,4-bipyridine (306.3 mg, 2 mmol) in 10 ml diethyl ether. After one day colourless block-shaped single crystals of the title compound were grown at the phase interface.