Structural studies of precursor and partially oxidized conducting complexes. XV. A combined neutron and x-ray diffraction study of ammonium tetracyanoplatinate chloride trihydrate, (NH/sub 4/)/sub 2/(Pt(CN)/sub 4/)Cl/sub 0/ /sub 3/. 3H/sub 2/O
The main structural findings reported here, which bear on the diminished electrical conductivity of (NH/sub 4/)/sub 2/(Pt(CN)/sub 4/)Cl/sub 0/./sub 3/ . 3H/sub 2/O compared to prototype K/sup 2/(Pt(CN)/sub 4/)Br/sub 0/./sub 3/ . 3H/sub 2/O, are that while the intrachain Pt-Pt spacings are shorter and are of equal length (2.88(1)A) in the K+ salt, they are longer and are of different length (2.910(5) and 2.930(5)A x rays) in the NH/sub 4//sup +/ salt. Thus the formation of alternately long and short Pt-Pt separations (dimerization) in NH/sub 4/CP(Cl) is likely one of the most important factors contributing to its electrical conduction properties. A factor which supports hypothesis is that in RbCP(Cl), the Pt-Pt distances are also of unequal length (2.924(8) and 2.877(8)A), and Rb CP(Cl) has lower room temperature conductivity than KCP(Br). The complete explanation for the structure-conductivity relationships in those POTCP complexes is obviously much more complicated, because although a Rb/sup +/ ion has nearly the same cation radius as NH/sub 4//sup +/ and RbCP(Cl) and NH/sub 4/CP(Cl) are isostructural, the low-temperature electrical conductivity (NH/sub 4/CP(Cl)<< RbCP(Cl)) is vastly different.
- Research Organization:
- Argonne National Lab., IL
- OSTI ID:
- 6683814
- Journal Information:
- Inorg. Chem.; (United States), Vol. 17:4
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMMONIUM COMPOUNDS
CHEMICAL PREPARATION
STRUCTURAL CHEMICAL ANALYSIS
CHLORINE COMPLEXES
CYANIDES
PLATINUM COMPLEXES
BOND LENGTHS
CHEMICAL BONDS
CRYSTAL STRUCTURE
ELECTRIC CONDUCTIVITY
HYDRATES
LEAST SQUARE FIT
LOW TEMPERATURE
MOLECULAR STRUCTURE
NEUTRON DIFFRACTION
PRECURSOR
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
ELECTRICAL PROPERTIES
MAXIMUM-LIKELIHOOD FIT
NUMERICAL SOLUTION
PHYSICAL PROPERTIES
SCATTERING
SYNTHESIS
400201* - Chemical & Physicochemical Properties