Nature of the Pt chain distortion in the partially oxidized one-dimensional complex, K/sub 1/ /sub 75/Pt(CN)/sub 4/. 1. 5H/sub 2/O

Journal Article · Fri Oct 01 04:00:00 EDT 1976 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50164a029· OSTI ID:7321561

Reis, Jr, A H; Peterson, S W; Washecheck, D M; Miller, J S

The oxidation of potassium tetracyanoplatinate(II) in the absence of halide ions results in the formation of bronze needles of K/sub 1.75/Pt(CN)/sub 4/ . 1.5H/sub 2/O stoichiometry. The structure of this partially oxidized material consists of parallel one-dimensional noncollinear chains involving a commensurate repeat unit of 11.865 A. Thus the unit cell contents as deduced from single crystal x-ray data is formulated K/sub 7/(Pt(CN)/sub 4/)/sub 4/ . 6H/sub 2/O and is stoichiometric. This material crystallizes in the triclinic space group P anti 1 with a = 10.323 (14), b = 9.285 (13), c = 11.865 (17) A, ..cap alpha.. = 77.31 (3), ..beta.. = 114.85 (5), ..gamma.. = 73.84 (2)/sup 0/, and Z = 4. The structure was solved by a combination of Patterson, Fourier, and least-squares refinement techniques to an R/sub F/ = 0.050 for the 1840 observed reflections for which F/sub 0/ less than 3 sigma F/sub 0/. There are three inequivalent Pt atoms in the chain and two Pt--Pt bond distances of 2.967 (1) and 2.976 (1) A. The average twist angles of the cyanide ligands of the tetracyanoplatinate planes are 45.3 (5) and 49.8 (3.7/sup 0/). An extensive network of K/sup +/ ionic bonding and hydrogen bonded water molecules knit the material together orthogonal to the chain direction. The chain distortion is shown to be due to Coulombic forces acting between the tetracyanoplatinate anions, located in the asymmetric crystal sites at z = approximately /sup 1///sub 4/ and /sup 3///sub 4/, and the coordinated asymmetric K/sup +/ distribution. The crystallographic analysis leads to the formal oxidation state of +2.25 for Pt in this potassium deficient material and an odd number of electrons per unit cell.

• Research Organization: Argonne National Lab., IL
• OSTI ID: 7321561
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 15:10; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPLEXES
BOND ANGLE
BOND LENGTHS
COHERENT SCATTERING
COMPLEXES
CYANIDES
DIFFRACTION
HYDRATION
INTERATOMIC FORCES
PLATINUM COMPLEXES
POTASSIUM COMPLEXES
SCATTERING
SOLVATION
STEREOCHEMISTRY
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
WEISSENBERG METHOD
X-RAY DIFFRACTION