catena-Poly[[[bis­(methanol-κO)bis­(seleno­cyanato-κN)manganese(II)]-μ-1,2-bis­(pyridin-4-yl)ethane-κ2 N:N′] 1,2-bis­(pyridin-4-yl)ethane monosolvate]

Susanne Wöhlert; Inke Jess; Christian Näther

doi:10.1107/S1600536813007150

. 2013 Mar 20;69(Pt 4):m223. doi: 10.1107/S1600536813007150

catena-Poly[[[bis(methanol-κO)bis(selenocyanato-κN)manganese(II)]-μ-1,2-bis(pyridin-4-yl)ethane-κ² N:N′] 1,2-bis(pyridin-4-yl)ethane monosolvate]

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

PMCID: PMC3629498 PMID: 23634016

Abstract

The reaction of manganese selenocyanate with 1,2-bis(pyridin-4-yl)ethane (bpa) leads to the title compound, {[Mn(NCSe)₂(C₁₂H₁₂N₂)(CH₃OH)₂]·C₁₂H₁₂N₂}_n. The Mn^II cation is coordinated by two N-bonded selenocyanate anions, two bpa ligands and two O-bonded methanol molecules, within a slightly distorted octahedral geometry. The Mn^II cations and the non-coordinating N-donor ligands are located on centers of inversion while the coordinating N-donor co-ligands are located on a twofold rotation axis. In the crystal, the Mn^II cations are linked into chains along the c-axis direction by the bpa ligands. The chains are further connected via a non-coordinating bpa ligand into layers parallel to (3-10) via O—H⋯N hydrogen-bonding interactions.

Related literature

For background to this work and the structures of related compounds, see: Boeckmann & Näther (2010 ▶, 2012 ▶), Wöhlert et al. (2012 ▶), Wöhlert & Näther (2012a ▶,b ▶).

Experimental

Crystal data

[Mn(NCSe)₂(C₁₂H₁₂N₂)(CH₄O)₂]·C₁₂H₁₂N₂
M _r = 697.46
Monoclinic,
a = 19.184 (1) Å
b = 9.7854 (4) Å
c = 17.3468 (9) Å
β = 108.624 (4)°
V = 3085.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.82 mm⁻¹
T = 293 K
0.14 × 0.11 × 0.06 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T _min = 0.493, T _max = 0.748
10827 measured reflections
2998 independent reflections
2556 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.094
S = 1.06
2998 reflections
179 parameters
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.58 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: XCIF in SHELXTL.

Supplementary Material

Click here for additional data file.^{(23.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813007150/bt6898sup1.cif

e-69-0m223-sup1.cif^{(23.1KB, cif)}

Click here for additional data file.^{(147.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007150/bt6898Isup2.hkl

e-69-0m223-Isup2.hkl^{(147.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mn1—N1	2.180 (3)
Mn1—O1	2.211 (2)
Mn1—N10	2.322 (2)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N20	0.82	1.92	2.731 (3)	173

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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 Wolfgang Bensch for access to his experimental facility.

supplementary crystallographic information

Comment

Recently, we have reported on the synthesis and characterization of thiocyanate coordination polymers with monodentate and bidentate neutral co-ligands like e.g. pyridine, pyridazine or 1,2-bis(pyridin-4-yl)ethylene (Boeckmann & Näther, 2010, 2012; Wöhlert & Näther, 2012a; Wöhlert & Näther, 2012b). Within this project we investigated the influence of the neutral co-ligand on the structural, thermal and magnetic properties of such compounds. In further work we also investigated the influence of the anionic ligand. In this context we have reported a new coordination polymer based on cobalt(II) selenocyanate and 1,2-bis(pyridin-4-yl)ethylene, in which the cobalt(II) cations are connected by the selenocyanato anions into chains that are further linked into layers by the neutral N-donor co-ligand (Wöhlert et al., 2012). In the present investigation we tried to prepare similar compounds with manganese(II) selenocyanate and 1,2-bis(pyridin-4-yl)ethane (bpa), which results in the formation of single-crystals of the title compound.

The asymmetric unit of the title compound [Mn(NCSe)₂(C₁₂H₁₂N₂)(CH₃OH)₂]_n^.nC₁₂H₁₂N₂ solvate consists of a manganese(II) cation and one non-coordinating bpa ligand which are located on a center of inversion, one coordinating bpa ligand on a 2-fold rotation axis and one selenocyanate anion and one methanol molecule in general positions (Fig. 1). In the crystal structure each manganese(II) cation is coordinated by two terminal N-bonded selenocyanate anions, two O-bonded methanol molecules and two N-bonded bpa ligands within slightly distorted octahedra. The MnN₄O₂ distances ranges from 2.180 (3) Å to 2.322 (2) Å with angles around the manganese(II) cation between 88.87 (9) ° to 91.13 (9) ° and of 180 ° (Tab. 1). The manganese(II) cations are linked by the bpa ligands into chains which elongate in the direction of the crystallographic c-axis (Fig. 2). These chains are further linked into layers parallel to the (3 -1 0) plane by non-coordinated bpa molecules via O–H–N hydrogen bonding (Fig. 3).

Experimental

MnCl₂x2H₂O, KNCSe and 1,2-bis(pyridin-4-yl)ethane were obtained from Alfa Aesar. All chemicals were used without further purification. 0.15 mmol (24 mg) MnCl₂x2H₂O and 0.2 mmol (28 mg) KNCSe were reacted with 0.6 mmol (109 mg) 1,2-bis(pyridin-4-yl)ethane in 1 ml methanol. Light-red single crystals of the title compound were obtained after one week.