Poly[[tetra­kis­(μ-1,2-di-4-pyridyl­ethyl­ene-κ2 N:N′)tetra­kis­(seleno­cyanato-κN)dimanganese(II)] 1,2-di-4-pyridyl­ethyl­ene disolvate]

Susanne Wöhlert; Inke Jess; Christian Näther

doi:10.1107/S1600536811016199

. 2011 May 7;67(Pt 6):m693–m694. doi: 10.1107/S1600536811016199

Poly[[tetrakis(μ-1,2-di-4-pyridylethylene-κ² N:N′)tetrakis(selenocyanato-κN)dimanganese(II)] 1,2-di-4-pyridylethylene disolvate]

Susanne Wöhlert ^a,^*, Inke Jess ^a, Christian Näther ^a

PMCID: PMC3120600 PMID: 21754598

Abstract

The crystal structure of the title compound, {[Mn(NCSe)₂(C₁₂H₁₀N₂)₂]·C₁₂H₁₀N₂}_2n, consists of two crystallographically independent Mn cations, four selenocyanate anions, four 1,2-di-pyridylethylene (bpe) ligands (two of which are located on centers of inversion) and two bpe solvent molecules. Each manganese(II) cation is coordinated by two terminally N-bonded selenocyanate anions and four bpe ligands within a slightly distorted octahedron. The manganese(II) cations are linked by the bpe ligands into chains that are further connected by these ligands into layers. These layers are stacked, forming cavities in which additional bpe solvent molecules are embedded.

Related literature

For background to this work, see: Boeckmann & Näther (2010 ▶); Wriedt et al. (2009 ▶); Wriedt & Näther (2010 ▶). For a description of the Cambridge Crystallographic Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Mn₂(NCSe)₄(C₁₂H₁₀N₂)₄]·2C₁₂H₁₀N₂
M _r = 1623.12
Monoclinic,
a = 14.3102 (3) Å
b = 13.9933 (2) Å
c = 36.0614 (6) Å
β = 91.211 (2)°
V = 7219.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.42 mm⁻¹
T = 293 K
0.19 × 0.13 × 0.08 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008) ▶ T _min = 0.689, T _max = 0.853
68086 measured reflections
12826 independent reflections
10467 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.124
S = 1.10
12826 reflections
883 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.78 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 ▶); software used to prepare material for publication: XP in SHELXTLand DIAMOND (Brandenburg, 2011 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016199/bt5535sup1.cif

e-67-0m693-sup1.cif^{(39KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811016199/bt5535Isup2.hkl

e-67-0m693-Isup2.hkl^{(627KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn2—N16	2.172 (4)
Mn2—N17	2.185 (3)
Mn2—N41	2.317 (3)
Mn2—N121	2.322 (3)
Mn2—N22	2.325 (3)
Mn1—N14	2.176 (3)
Mn1—N13	2.183 (4)
Mn1—N21	2.324 (3)
Mn1—N1	2.338 (3)
Mn1—N81	2.339 (3)

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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 Bensch for access to his experimental facilities.

supplementary crystallographic information

Comment

In our recent work on the synthesis, structures and properties of new coordination polymers based on paramagnetic transition metals, thiocyanato or selenocyanato anions and N-donor ligands we have shown that ligand-deficient compounds can be prepared by thermal decomposition reactions (Wriedt et al., 2009, Boeckmann & Näther, 2010 and Wriedt & Näther, 2010). Within this project we tried to prepare new ligand-rich precursor compounds based on manganese(II) selenocyanato and the N-donor ligand 1,2-bis(4-pyridyl)-ethylene (bpe) which resulted in the formation of the title compound that were identified by single crystal X-ray diffraction.

In the crystal structure of the title compound each managnese(II) cation is coordinated by two terminally N-bonded selenocyanato anions and four bridging bpe ligands (Fig. 1). The MnN₆ octahedra are slightly distorted with distances in the range of 2.172 (4) Å to 2.339 (3) Å. The angles around the metal cations are in the range of 86.94 (12) ° to 179.89 (16) °. The manganese(II) cations are linked by the bpe ligands into chains that are further connected into layers by additional coligands (Fig. 2). The layers are stacked in order that cavities are formed, in which non-coordinated bpe molecules are located (Fig. 3). The Mn—Mn distances within the chains are in range of 13.9666 (8) Å to 13.9933 (8) Å.

It must be noted that according to a search in the CCDC database (ConQuest Ver.1.12.2010; Allen, 2002) compounds based on manganese(II) selenocyanate and 1,2-bis(4-pyridyl)-ethylene are unknown.

Experimental

Manganese chloride tetrahydrate (MnCl₂ × 4H₂O) and 1,2-bis(4-pyridyl)-ethylene (bpe) were obtained from sigma aldrich. Potassium selenocyanate (KNCSe) and acetonitrile (MeCN) were obtained from alfa aesar. All chemicals were used without further purification. 0.15 mmol (25.4 mg) MnCl₂ x 4H₂O, 0.3 mmol (43 mg) KNCSe and 0.6 mmol (107.5 mg) bpe were reacted with 1 ml MeCN in a closed test-tube at 120 ° C for three days. On cooling orange block-shaped single crystals of the title compound were obtained.