Jack M. Williams, K. Keefer, D. M. Washecheck
Oct 1, 1976
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0
Influential Citations
26
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Journal
Inorganic Chemistry
Abstract
The complete molecular structure of quasi-one-dimensional, partially oxidized potassium tetracyanoplatinate (1.75:1) sesquihydrate, K/sub 1/./sub 75/(Pt(CN)/sub 4/).1.5H/sub 2/O, has been determined by a single-crystal neutron diffraction study. The potassium deficient tetracyanoplatinate, K(def)TCP hereafter, crystallizes with four formula units in the triclinic unit cell C/sup 1//sub i/-Pl, with cell constants a = 10.360 (17) A, b = 9.303 (15) A, c = 11.832 (19) A, ..cap alpha.. = 77.57 (9)/sup 0/, ..beta.. = 114.74 (5)/sup 0/, and ..gamma.. = 73.64 (7)/sup 0/. A total of 5037 observed data were averaged to yield 3969 independent reflections (3276 data with F/sub 0//sup 2/ > sigmaF/sub 0//sup 2/). The structure was solved from the neutron Patterson map and refinement using full-matrix least-squares techniques has led to an agreement factor of R(F/sub 0//sup 2/) = 0.058. The agreement factor for 3276 data with F/sub 0//sup 2/ > sigmaF/sub 0//sup 2/ is R(F/sub 0//sup 2/) = 0.054. The structure comprises an unusual ''zig-zag'' metal atom chain containing three crystallographically independent Pt atoms with a Pt(1)-Pt(2)-Pt(3) bond angle of 173.25 (3)/sup 0/. Inversion centers occur at Pt(1) and Pt(3). The most surprising finding is that the two independent metal atom separations are equal (2.961 (1) and 2.965 (1)more » A), though not required to be so by symmetry, just as in the case of K/sub 2/(Pt(CN)/sub 4/)Br/sub 0/./sub 3/.3H/sub 2/O where they are 2.888 (6) A and 2.892 (6) A.« less