Unique coordination of pyrazine in T[Ni(CN) 4]·2pyz with T=Mn, Zn, Cd

The materials under study, T[Ni(CN) 4]·2pyz with T=Mn, Zn, Cd, were prepared by separation of T[Ni(CN) 4] layers in citrate aqueous solution to allow the intercalation of the pyrazine molecules. The obtained solids were characterized from chemical analyses, X-ray diffraction, infrared, Raman, thermo...

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Bibliographic Details
Published in:Journal of solid state chemistry 2009, Vol.182 (4), p.757-766
Main Authors: Lemus-Santana, A.A., Rodríguez-Hernández, J., del Castillo, L.F., Basterrechea, M., Reguera, E.
Format: Article
Language:English
Subjects:
AQUEOUS SOLUTIONS
AZINES
CADMIUM COMPLEXES
CHEMICAL ANALYSIS
CLATHRATES
COHERENT SCATTERING
COMPLEXES
Condensed matter: structure, mechanical and thermal properties
Crystal chemistry
CRYSTAL STRUCTURE
DIFFRACTION
DISPERSIONS
Exact sciences and technology
GRAVIMETRIC ANALYSIS
HEATING
HETEROCYCLIC COMPOUNDS
HOMOGENEOUS MIXTURES
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Layered compounds
MANGANESE COMPLEXES
MIXTURES
NICKEL COMPLEXES
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
Physics
Pillared solids
PYRAZINES
QUANTITATIVE CHEMICAL ANALYSIS
SCATTERING
Solid surfaces and solid-solid interfaces
SOLUTIONS
Structural studies
Structure of solids and liquids
crystallography
Structure of specific crystalline solids
Surfaces and interfaces
thin films and whiskers (structure and nonelectronic properties)
TEMPERATURE RANGE
TEMPERATURE RANGE 0273-0400 K
THERMAL ANALYSIS
THERMAL GRAVIMETRIC ANALYSIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION
ZINC COMPLEXES
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Description
Summary:The materials under study, T[Ni(CN) 4]·2pyz with T=Mn, Zn, Cd, were prepared by separation of T[Ni(CN) 4] layers in citrate aqueous solution to allow the intercalation of the pyrazine molecules. The obtained solids were characterized from chemical analyses, X-ray diffraction, infrared, Raman, thermogravimetry, UV–Vis, magnetic and adsorption data. Their crystal structure was solved from ab initio using direct methods and then refined by the Rietveld method. A unique coordination for pyrazine to metal centers at neighboring layers was observed. The pyrazine molecule is found forming a bridge between Ni and T atoms, quite different from the proposed structures for T=Fe, Ni where it remains coordinated to two T atoms to form a vertical pillar between neighboring layers. The coordination of pyrazine to both Ni and T atoms minimizes the material free volume and leads to form a hydrophobic framework. On heating the solids remain stable up to 140 °C. No CO 2 and H 2 adsorption was observed in the small free spaces of their frameworks. Framework for T[Ni(CN) 4]·2pyz with T=Mn, Zn, Cd.
ISSN:0022-4596
1095-726X
DOI:10.1016/j.jssc.2008.12.028