The X-Ray Diffraction Analysis and Spectral Studies of Mixed Anionic (1:1) CdII3[(FeIII/CoIII)(CN)6]2·14H2O

✍ Scribed by D.F. Mullica; P.A.B. Colot; J.A. Kautz; R.J. Smith; E.L. Sappenfield

• Publisher: Elsevier Science
• Year: 1997
• Tongue: English
• Weight: 273 KB
• Volume: 129
• Category: Article
• ISSN: 0022-4596
• DOI: 10.1006/jssc.1996.7203

✦ Synopsis

Refinement of the crystallographic structure of (1 : 1) Cd II 3 [(Fe III /Co III ) (CN) 6 ] 2 • 14H 2 O (I) has been carried out by means of three-dimensional single-crystal X-ray diffractometry. This novel disordered mixed anionic complex crystallizes in the cubic space group Fm3 m (Z‫1؍‬ 1/3) with a 0 ‫)1(836.01؍‬ A s . Based on 166 unique reflections, the employed full-matrix least-squares method yielded a final reliability factor of R‫140.0؍‬ (R w ‫)740.0؍‬ and a goodness-of-fit value ( 2 ) of 1.79. Indexed power diffraction data are reported and evaluated according to the quantitative figures-of-merit F 21 ‫411؍‬ (0.007, 25) and M 20 ‫.9.451؍‬ A thermal gravimetric analysis revealed 14 water molecules per formula unit and the experimental density is 1.93(5) Mg m ؊3 [calc., 1.87(1) Mg m ؊3 ]. The divalent Cd atoms are linked to the (1 : 1) mixed metal atoms by linear cyanide bridging. The disordered structure I is isomorphous with the hydrated cobalticyanides of Mn and Cd. A hydrogen-bonding network is set up within cavities of the crystal lattice created by the molecular disorder. Selective geometric parameters as well as conoscopic and IR spectral results are presented.