Solving simple organometallic structures solely from X-ray powder diffraction data: the case of polymeric [{Ru(CO)4}n]

Abstract

The crystal and molecular structure of [{Ru(CO)₄}_n] has been determined solely from X-ray powder diffraction data using standard laboratory equipment and refined with a (modified) Rietveld procedure. The compound crystallizes in the orthorhombic space group Ibam, with a= 14.147(4), b= 7.060(2) and c= 5.720(1)Å, Z= 4; the final refinement (19 variables) converged to R_p, R_wp and R_Bragg of 0.077, 0.102 and 0.025, respectively, for 4001 data collected at room temperature in the 5–85°(2θ) range. The structure, which consists of a polymeric stack of staggered trans-D_4h Ru(CO)₄ fragments separated by a Ru–Ru contact of 2.860(1)Å, is the first polymeric binary metal carbonyl compound so far characterized. Strain and particle-size broadening effects have been observed, and the microstructural properties of the compound are discussed.