Tetrakis(pyrazine-κ<i>N</i>)bis(thiocyanato-κ<i>N</i>)zinc(II)

Liu, T.; Xie, Ziyu

doi:10.1107/s1600536807028735

Cited by 3 publications

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References 3 publications

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“…However, these compounds are easily accessible by thermal decomposition of their ligand-rich 1:2 precursor compounds. Moreover discrete ligand-rich 1:4 complexes were prepared like [Mn(NCS) 2 (pyrazine) 4 ] and [Zn(NCS) 2 (pyrazine) 4 ] in the pyrazine system.…”

Section: Introductionmentioning

confidence: 99%

Thermal Decomposition Reactions as Tool for the Synthesis of New Metal Thiocyanate Diazine Coordination Polymers with Cooperative Magnetic Phenomena

2009

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Reaction of nickel thiocyanate with pyrimidine at room temperature leads to the formation of the new ligand-rich 1:2 (1:2 = ratio between metal and ligand) compound [Ni(NCS)(2)(pyrimidine)(2)](n) (2) which is isotypic to [Co(NCS)(2)(pyrimidine)(2)](n) (1) reported recently. In the crystal structure, the Ni(2+) ions are coordinated by four N atoms of pyrimidine ligands, which connect the metal centers into layers, and two N atoms of terminal bonded thiocyanato anions within slightly distorted octahedra. If the synthesis is performed under solvothermal conditions and an excess of the metal thiocyanate is used, single crystals of the ligand-deficient 1:1 compound [Ni(NCS)(2)(pyrimidine)](n) (4) are obtained. Investigations on the synthesis of this compound show that it is always contaminated with large amounts of the corresponding ligand-rich 1:2 compound 2. In the crystal structure, the Ni(2+) ions are coordinated by two N atoms of pyrimidine ligands, which connect the metal centers into chains, and two N atoms as well as two S atoms of mu-1,3 bridged thiocyanato anions, which conntect these chains into layers, within a slightly distorted octahedral geometry. On heating compounds 1 and 2 transform quantitatively into the ligand-deficient 1:1 Ni compound 4 and its isotypic Co compound 3. If nickel and cobalt thiocyanate are reacted with an excess of pyrimidine in a solvent-free reaction, discrete ligand-rich 1:4 complexes of composition [M(NCS)(2)(pyrimidine)(4)] (M = Co 5 and Ni 6) are obtained, which could be determined by single crystal structure analysis. In their crystal structure the metal ions are coordinated by four terminal bonded pyrimidine ligands and two terminal N-bonded thiocyanato anions. For the ligand-rich 1:2 and ligand-deficient 1:1 compounds magnetic measurements were performed, which reveal different magnetic properties: The 1:2 compounds show a ferromagnetic and the 1:1 compounds an antiferromagnetic ordering at lower temperatures.

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Section: Introductionmentioning

confidence: 99%

Thermal Decomposition Reactions as Tool for the Synthesis of New Metal Thiocyanate Diazine Coordination Polymers with Cooperative Magnetic Phenomena

2009

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Synthesis, Crystal Structures, and Thermal Properties of New Zinc(II) Thiocyanato Coordination Compounds

Bhosekar

Boeckmann

Jeß

et al. 2010

Zeitschrift anorg allge chemie

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Reaction of zinc(II) thiocyanate with pyrazine, pyrimidine, pyridazine, and pyridine leads to the formation of new zinc(II) thiocyanato coordination compounds. In bis(isothiocyanato‐N)‐bis(μ2‐pyrazine‐N,N) zinc(II) (1) and bis(isothiocyanato‐N)‐bis(μ2‐pyrimidine‐N,N) zinc(II) (2) the zinc atoms are coordinated by four nitrogen atoms of the diazine ligands and two nitrogen atoms of the isothiocyanato anions within slightly distorted octahedra. The zinc atoms are connected by the diazine ligands into layers, which are further linked by weak intermolecular S···S interactions in 1 and by weak intermolecular C–H···S hydrogen bonding in 2. In bis(isothiocyanato‐N)‐bis(pyridazine‐N) (3) discrete complexes are found, in which the zinc atoms are coordinated by two nitrogen atoms of the isothiocyanato ligands and two nitrogen atoms of the pyridazine ligands. The crystal structure of bis(isothiocyanato‐N)‐tetrakis(pyridine‐N) (4) is known and consists of discrete complexes, in which the zinc atoms are octahedrally coordinated by two thiocyanato anions and four pyridine molecules. Investigations using simultaneous differential thermoanalysis and thermogravimetry, X‐ray powder diffraction and IR spectroscopy prove that on heating, the ligand‐rich compounds 1, 2, and 3 decompose without the formation of ligand‐deficient intermediate phases. In contrast, compound 4 looses the pyridine ligands in two different steps, leading to the formation of the literature known ligand‐deficient compound bis(isothiocyanato‐N)‐bis(pyridine‐N) (5) as an intermediate. The crystal structure of compound 5 consists of tetrahedrally coordinated zinc atoms which are surrounded by two isothiocyanato anions and two pyridine ligands. The structures and the thermal reactivity are discussed and compared with this of related transition metal isothiocyanates with pyrazine, pyrimidine, pyridazine, and pyridine.

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