Bis(methanol-1κO)tetra-μ-pyridazine-1:2κ4 N:N′;2:3κ4 N:N′-di-μ-thio­cyanato-1:2κ2 N:N;2:3κ2 N:N-tetrathio­cyanato-1κ2 N,3κ2 N-trinickel(II) methanol tetra­solvate

Susanne Wöhlert; Inke Jess; Christian Näther

doi:10.1107/S1600536812026864

. 2012 Jun 16;68(Pt 7):m940–m941. doi: 10.1107/S1600536812026864

Bis(methanol-1κO)tetra-μ-pyridazine-1:2κ⁴ N:N′;2:3κ⁴ N:N′-di-μ-thiocyanato-1:2κ² N:N;2:3κ² N:N-tetrathiocyanato-1κ² N,3κ² N-trinickel(II) methanol tetrasolvate

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

PMCID: PMC3393200 PMID: 22807768

Abstract

Reaction of an excess nickel(II) thiocyanate with pyridazine leads to single crystals of the title compound, [Ni₃(NCS)₆(N₂C₄H₄)₄(CH₃OH)₂]·4CH₃OH. The crystal structure consists of trimeric discrete complexes, in which two Ni^II cations are coordinated by two terminal and one μ-1,1 bridging thiocyanato anions, one methanol molecule and two bridging pyridazine ligands, whereas the central Ni^II atom is coordinated by two μ-1,1 bridging anions as well as four bridging pyridazine ligands. The asymmetric unit consists of two crystallographically independent Ni cations, one of which is located on a center of inversion, as well as three crystallographically independent thiocyanato anions, two pyridazine ligands and three independent methanol molecules in general positions. Two of the solvent molecules do not coordinate to the metal atoms and are located in cavities of the structure. The discrete complexes are linked by intermolecular O—H⋯O and O—H⋯S hydrogen bonding into layers parallel to the bc plane.

Related literature

For the background to this work and the synthesis of bridging thiocyanato coordination compounds, see: Boeckmann & Näther (2010 ▶, 2011 ▶); Wöhlert et al. (2011 ▶). For structures of related trinuclear complexes, see: Wriedt & Näther (2009 ▶); Yi et al. (2006 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Ni₃(NCS)₆(C₄H₄N₂)₄(CH₄O)₂]·4CH₄O
M _r = 1037.23
Orthorhombic,
a = 17.6689 (12) Å
b = 15.0760 (7) Å
c = 17.9479 (10) Å
V = 4780.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 200 K
0.13 × 0.09 × 0.07 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T _min = 0.746, T _max = 0.818
31891 measured reflections
4093 independent reflections
3190 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.106
S = 1.05
4093 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.52 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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812026864/hp2040sup1.cif

e-68-0m940-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026864/hp2040Isup2.hkl

e-68-0m940-Isup2.hkl^{(200.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ni1—N3	2.024 (3)
Ni1—N1	2.031 (3)
Ni1—O1	2.067 (3)
Ni1—N10	2.110 (3)
Ni1—N20	2.128 (3)
Ni1—N2	2.132 (3)
Ni2—N21	2.099 (3)
Ni2—N2	2.114 (3)
Ni2—N11	2.121 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2ⁱ	0.84	1.84	2.671 (4)	171
O2—H1O2⋯O3	0.84	1.91	2.691 (9)	155
O3—H1O3⋯S1	0.84	2.45	3.285 (6)	178

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Symmetry code: (i) 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 facility.

supplementary crystallographic information

Comment

The structure determination of the title compound was performed within a project on the synthesis of transition metal coordination compounds in which the metal centers are linked by bridging anionic ligands (Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011)). Within this project we reported on two modification of a trinuclear complex based on nickel(II) thiocyanate and pyridazine (Wriedt & Näther (2009)). In further investigations we have reacted nickel(II) thiocyanate with pyridazine in methanol which results in the formation of single-crystals of the title compound, which were characterized by single-crystal X-ray diffraction. The asymmetric unit of the title compound consists of two nickel(II) cations, one of them is located on a center of inversion, three thiocyanato anions, two pyridazine ligands and three methanol molecules all of them located in general position (Fig. 1). In the crystal structure two crystallographic independent nickel(II) cations are present. Ni1 is coordinated by two terminal N-bonded and one µ-1,1 bridging thiocyanato anions, one methanol molecule and two bridging pyridazine ligands in a slightly distorted octahedral geometry (Tab. 1). Ni2 is coordinated by two µ-1,1 bridging thiocyanato anions and four pyridazine ligands and the coordination environment can also be described as a sligthly distorted octahedron (Tab. 1). The nickel(II) cations are connected through µ-1,1 bridging thiocyanato anions and the two µ₂-N,N pyridazine ligands into trimeric units. The Ni—N distances are in range of 2.025 (3) Å to 2.133 (3) Å with angles between 86.53 (12) ° to 180 ° (Tab. 1). The intramolecular Ni···Ni distances amount to 3.3349 (4) Å. The crystal structure contains additional methanol molecules located in cavities of the structure which are not coordinated to the metal cations. These methanol molecules are linked by intermolecular O—H···O and O—H···S hydrogen bonding to the metal complexes forming layers which are parallel to the b-c plane (Fig. 2 and Tab. 2). It must be noted that according to a search in the CCDC database (CONQUEST Ver. 1 12.2010) (Allen, 2002) a trinuclear complex with cobalt(II) thiocyanate and pyridazine was reported by Yi et al. (2006).

Experimental

Nickel(II) thiocyanate (Ni(NCS)₂) and pyridazine were obtained from Alfa Aesar. All chemicals were used without further purification. 0.5 mmol (87.0 mg) and 0.125 mmol (9.1 µL) pyridazine were reacted in 0.5 ml methanol. Green single crystals of the title compound were obtained after two days.