A new configuration of the one‐dimensional anionic Mo/S/Ag polymer, {[Ce(dmac)₇MeOH][Mo₃S₁₂Ag₃]}_n(dmac is N,N‐dimethylacetamide)

Publisher： John Wiley & Sons Inc

E-ISSN： 1600-5368|63|7|m1987-m1988

ISSN： 1600-5368

Source： Acta Crystallographica Section E, Vol.63, Iss.7, 2007-07, pp. : m1987-m1988

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Abstract

The self‐assembly of tetrathiomolybdate, silver iodide and cerium nitrate in N,N‐dimethylacetamide (dmac) and methanol resulted in a one‐dimensional anionic Mo/S/Ag polymer, catena‐poly[heptakis(N,N‐dimethylacetamide‐κO)(methanol‐κO)cerium(III) [di‐μ₃‐sulfido‐octa‐μ₂‐sulfido‐disulfidotrisilver(I)trimolybdenum(VI)]], {[Ce(C₄H₉NO)₇(CH₄O)][Mo₃S₁₂Ag₃]}_n. The polymeric anion {[Mo₃S₁₂Ag₃]_n}³ⁿ⁻ assumes a new configuration of a saw‐tooth chain with the lengths of the sides in a 1:2 ratio. Such a configuration is intermediate between the polymeric anions in two reported compounds, viz. {[Ca(DMF)₆][Mo₂S₈Ag₂]}_n and {[Ca(DMSO)₆]₂[W₄S₁₆Ag₄]}_n (DMF is dimethylformamide and DMSO is dimethyl sulfoxide). The metal atoms in the chain are nearly coplanar. The central Ce in the solvent‐coordinated cation has distorted square‐antiprismatic coordination. Of the seven N,N‐dimethylacetamide (dmac) molecules present, one is found to be disordered over two sites, with occupancy factors of 0.63 and 0.37. The overall structure can be viewed as consisting of staggered layers parallel to (010), which are formed by anionic chains propagating along the a axis and cations distributed in the spaces between the anionic chains. No notable interactions are found between cations and polymeric anions except for electrostatic attractions.