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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

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic50182a010· OSTI ID:6683814
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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), Journal Name: Inorg. Chem.; (United States) Vol. 17:4; ISSN INOCA
Country of Publication:
United States
Language:
English

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Structural studies of precursor and partially oxidized conducting complexes. XIII. A neutron diffraction and x-ray diffuse scattering study of the dimerized platinum chain in rubidium tetracyanoplatinate chloride (2:1:0. 3) trihydrate, Rb/sub 2/(Pt(CN)/sub 4/)Cl/sub 0/ /sub 3/. 3. 0H/sub 2/O
Journal Article · Fri Mar 31 23:00:00 EST 1978 · Inorg. Chem.; (United States) · OSTI ID:6683861
Structural studies of precursor and partially oxidized conducting complexes. 20. A reduction in platinum-chain dimerization in rubidium tetracyanoplatinate chloride (2:1:0. 3) trihydrate, Rb/sub 2/(Pt(CN)/sub 4/)Cl/sub 0/ /sub 3/. 3. 0 H/sub 2/O, at 110 K as revealed by a neutron diffraction study
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
AMMONIUM COMPOUNDS
BOND LENGTHS
CHEMICAL BONDS
CHEMICAL PREPARATION
CHLORINE COMPLEXES
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
CYANIDES
DIFFRACTION
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
HYDRATES
LEAST SQUARE FIT
LOW TEMPERATURE
MAXIMUM-LIKELIHOOD FIT
MOLECULAR STRUCTURE
NEUTRON DIFFRACTION
NUMERICAL SOLUTION
PHYSICAL PROPERTIES
PLATINUM COMPLEXES
PRECURSOR
SCATTERING
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION