✦ LIBER ✦
Tentative partial oxidation of the nickel(II) potassium-dithiooxalato complex: Existence of iodine an adduct K2Ni(S2C2O2)2I in solution and crystal structure of a new polymorphic form of K2Ni(S2C2O2)2 (‘black’ form)
✍ Scribed by A. Gleizes; F. Clery; M.F. Bruniquel; P. Cassoux
- Publisher
- Elsevier Science
- Year
- 1979
- Tongue
- English
- Weight
- 709 KB
- Volume
- 37
- Category
- Article
- ISSN
- 0020-1693
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✦ Synopsis
Tentative partial oxidation of 'red' nickel(R) potassiumdithiooxalate K2Ni(S2C,0,), by iodine results in a K2Ni(S&0,)J adduct. This adduct was identified in solution but could not be isolated in the solid state. Operating with KzCrzO, surprisingly leads to a polymorphic 'black' form of KaNi(S,C,-O& which is also obtained as by-product of the rapid decomposition of the iodine adduct. The X-ray structure of the new 'black' form has been solved (P2Jn; Z = 2; a = 11.0369(10) A, b = 4.1911(3) A, c = 12.7221(17) A, (3 = 111.784(9)"). Full-matrix least-squares refinement of 70 variables gave a final value of the conventional R index (on F) of 0.022 for 1420 reflections having F", > 3a (Fz). Planar Ni(S,CzO,), units stack along the b direction (Ni-Ni = 4.19 A) which is not the case in the 'red'form. Crystallographic relationship between both 'red'
and 'black ' species is discussed.