Isomeric forms of the organometallic-inorganic hybrid polymer [Cp*2Mo2P2Se3(CuI)3(CH3CN)]n

Isomeric forms of the organometallic-inorganic hybrid polymer [Cp*₂Mo₂P₂Se₃(CuI)₃(CH₃CN)]_n

M. Dušek

Institute of Physics ASCR, v.v.i., Na Slovance 2, 18221 Praha 8, Czech Republic

dusek@fzu.cz

Recently, there was an article [1] published about synthesis and characterization of a tripledecker molecule [Cp*₂Mo₂P₂Se₃], Cp* = C₅Me₅), and its use as a molecular building block in the formation of copper(I) halide polymers. Reaction of the tripledecker molecule (see Fig. 1) with copper(I) halides provides polymers of diverse dimensionalities depending on competing coordination properties of P and Se atoms.

The reaction of the tripledecker molecule with CuI in CH₃CN gave a mixture of bright-red plates and dark prisms, both with a composition Cp*₂Mo₂P₂Se₃(CuI)₃(CH₃CN)]_n, in a temperature-dependent ratio. While structure of bright-red plates could be solved by classical methods as a two-dimensional polymer, the structures of the dark-red prisms was modulated. The modulation of tripledecker molecule is of harmonic nature. On the other hand, discontinuous modulation function are needed for the inorganic part whene a cage from Cu and I atoms (Fig. 2) alternates between two positions. In three-dimensional description this lead to disorder, which is resolved using crenel modulation function.

The presentation demonstrates way how to solve and refine this kind of structure. The steps with program Jana2006 [2] will be explained together with necessary underlying theory to the extent needed for understanding the presented procedures. Finally, still unsolved problems connected with solution of the title structure, will be discussed.

Figure 1. The tripledecker molecule. P yellow, Se red, Mo orange, C gray, hydrogen omitted.

Figure 2. Two positions of the Cu-I cage observed as disorder in the average structure.

1. M. Bodensteiner, M. Dusek, M.M. Kubicki, M. Pronold, M. Scheer, J. Wachter, M. Zabel, Eur. J. Inorg. Chem., 2010, (2010), 5298.

2. V. Petricek, M. Dusek, L. Palatinus, Jana2006. The crystallographic computing system. Institute of Physics, Praha, Czech Republic. http://jana.fzu.cz