Mixed metal cations crystal structure

One typical way to improve the catalyst system was directed at the multi-component bismuth molybdate catalyst having scheelite structure (85), where metal cations other than molybdenum and bismuth usually have ionic radii larger than 0.9 A. It is important that the a-phase of bismuth molybdate has a distorted scheelite structure. Thus, metal molybdates of third and fourth metal elements having scheelite structure easily form mixed-metal scheelite crystals or solid solution with the a-phase of bismuth molybdates. Thus, the catalyst structure of the scheelite-type multicomponent bismuth molybdate is rather simple and composed of a single phase or double phases including many lattice vacancies. On the other hand, another type of multi-component bismuth molybdate is composed mainly of the metal cation additives having ionic radii smaller than 0.8 A. Different from the scheelite-type multicomponent bismuth molybdates, the latter catalyst system is never composed of a simple phase but is made up of many kinds of different crys-... 

To control the extent of intermixing and stoichiometry of the cation species, there have been a number of investigations to synthesize stoichiometric mixed-metal precursors with structures similar to the perovskite crystal structure. The motivation behind these efforts is that stoichiometric precursors with structures similar to the desired crystaUine phase should undergo crystallization at lower heat treatment temperatures. Most attempts in this area, however, have resulted in mixed-metal species with a cation stoichiometry different than perovskite." " The formation of such compounds indicates the importance of thermodynamic sinks in the synthesis of mixed-metal precmsors. ... 

Most of the salts based on decamethylmetallocenium radical cations and on planar metal bisdichalcogenate radical anions reported so far present crystal structures with mixed linear chain basic motives. The only known exception is [Fe(Cp )2][Ni (mnt)2], which exhibits another type of crystal structure based on a D+ [A2]2 D+ repeat unit [28]. In the case of this compound the magnetic behavior is dominated by the intradimer antiferromagnetic interactions. 

In some instances, this approach has proven successful, with comparatively low crystallization temperatures being observed. For example, Eichorst and Payne in the synthesis of LiNb03 noted crystallization temperatures of 400-500 °C for a mixed-metal alkoxide precursor.111 In other instances, these attempts have proven less successful. Numerous attempts have been made to synthesize Pb-Zr and Pb-Ti precursors, each with the 1 1 cation stoichiometry of the desired PbZr03 and PbTi03 compounds.83,84 Unfortunately, 1 1 stoichiometric ratio compounds have not always been obtained, with crystalline compounds of other stoichiometries precipitating from the solution, as illustrated in Fig. 2.11.83 This figure shows the crystal structure of PbTi2[p(4)—... 

Hg(CNO)2 is decomposed by heat (equation 8).4 It crystallizes in the orthorhombic form and contains linearly coordinated mercury.21 It reacts with alkali metal fulminate solutions to form the highly explosive compounds M2Hg(CNO)4 (M = K, Rb, Cs) with larger cations such as Ph4As+ more stable complexes are formed.219,220 Besides the homogeneous anionic mercury(II) fulminato complexes there are a few mixed species with unknown structures, e.g. Na Hg(CNO)2X (X = Cl, Br) or Na2S203-2Hg(CNO).221... 

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