Poly[bis­(methanol-κO)tris­(μ-pyrimidine-κ2 N:N′)tetra­kis(thio­cyanato-κN)dinickel(II)]

Mario Wriedt; Sina Sellmer; Inke Jess; Christian Näther

doi:10.1107/S1600536809005674

. 2009 Mar 6;65(Pt 4):m361–m362. doi: 10.1107/S1600536809005674

Poly[bis(methanol-κO)tris(μ-pyrimidine-κ² N:N′)tetrakis(thiocyanato-κN)dinickel(II)]

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

PMCID: PMC2968860 PMID: 21582319

Abstract

In the crystal structure of the title compound, [Ni₂(NCS)₄(C₄H₄N₂)₃(CH₃OH)₂]_n, each nickel(II) cation is coordinated by three N-bonded pyrimidine ligands, two N-bonded thiocyanate anions and one O-bonded methanol molecule in a distorted octahedral environment. The asymmetric unit consists of one nickel cation, two thiocyanate anions and one methanol molecule in general positions, as well as one pyrimidine ligand located around a twofold rotation axis. The crystal structure consists of μ-N:N′ pyrimidine-bridged zigzag-like nickel thiocyanate chains; these are further linked by μ-N:N-bridging pyrimidine ligands into layers which are stacked perpendicular to the b axis. The layers are connected via weak O—H⋯S hydrogen bonding.

Related literature

For related pyrimidine structures, see: Lloret et al. (1998 ▶); Näther et al. (2007 ▶); Näther & Greve (2003 ▶). For general background, see: Wriedt et al. (2008 ▶) and literature cited therein.

Experimental

Crystal data

[Ni₂(NCS)₄(C₄H₄N₂)₃(CH₄O)₂]
M _r = 654.10
Orthorhombic,
a = 20.0624 (4) Å
b = 32.5018 (6) Å
c = 8.0268 (2) Å
V = 5233.99 (19) Å³
Z = 8
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 80 K
0.19 × 0.09 × 0.03 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T _min = 0.813, T _max = 0.936
26228 measured reflections
3743 independent reflections
3659 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.020
wR(F ²) = 0.048
S = 1.09
3743 reflections
170 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ▶), 1746 Friedel pairs
Flack parameter: 0.092 (7)

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2008 ▶; 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: XCIF in SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005674/si2156sup1.cif

e-65-0m361-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005674/si2156Isup2.hkl

e-65-0m361-Isup2.hkl^{(183.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Ni1—N31	2.0334 (14)
Ni1—N21	2.0376 (13)
Ni1—O41	2.1053 (12)
Ni1—N11	2.1118 (13)
Ni1—N2ⁱ	2.1200 (13)
Ni1—N1	2.1244 (13)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O41—H1O4⋯S21ⁱⁱ	0.80 (3)	2.50 (3)	3.2474 (14)	154 (2)

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Symmetry code: (ii) 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 we thank Professor Dr Wolfgang Bensch for the opportunity to use of his experimental facility.

supplementary crystallographic information

Comment

Recently, we have shown that new ligand deficient coordination polymers with interesting magnetic properties can be prepared by thermal decomposition of suitable ligand rich precursor compounds (Näther & Greve, 2003; Wriedt et al., 2008; and Näther et al., 2007). In our ongoing investigation on the synthesis, structures and properties of new coordination polymers based on paramagnetic metal pseudohalides and N-donor ligands (Lloret et al. 1998), we have reacted nickel(II) thiocyanate with pyrimidine in methanol. In this reaction single crystals of the title compound has been formed.

The 2:3 title compound [Ni(SCN)₂(pyrimidine)₃*2MeOH]_n (Fig. 1) represents a two-dimensional coordination polymer, which consists of µ-1,3-(N,N) pyrimidine bridged zigzag like nickel thiocyanates chains, which are further linked by µ-1,3-(N,N) bridged pyrimidine ligands into layers (Fig. 2 and 3). Within each layer the nickel cations are bridged by three µ-1,3-(N,N') pyrimidine ligands and are further terminal coordinated by two N-bonded thiocyanate anions and one O-bonded methanol molecule. Thus, each nickel cation is octahedrally coordinated. The asymmetric unit consists of one nickel cation, two thiocyanate anions and one methanol molecule in general position as well as one pyrimidine ligand located around a twofold rotation axis. The Ni—NCS distances amount to 2.0334 (14) and 2.0376 (13) Å and the Ni—N_pyrimidine distances range from 2.1118 (13) to 2.1244 (13) Å as well as the angles around the iron cations range between 86.62 (5) and 177.66 (5)° (Tab. 1). The shortest intra- and interchain Ni···Ni distances amount to 5.9470 (1) and 8.4023 (1) Å, respectively.

Experimental

Ni(SCN)₂, pyrimidine and methanol were obtained from Alfa Aesar. 0.125 mmol (21.5 mg) Ni(SCN)₂, 0.25 mmol (20.0 mg) pyrimidine and 0.5 ml methanol were transfered in a closed test-tube. The mixture was heated at 120 °C for three days. After cooling green needle-shaped single crystals of the title compound were obtained in a heterogenous mixture.