Crystal and molecular structure of ferricenium tetrachlorobismuthate

Abstract

Ferricenium tetrachlorobismuthate, (C 5 H 5) 2 FeBiC1 4 , crystallizes in the monoclinic space group P2 1 /c with a = 10.998(5)A, b = 17.449(4)~, c = 7.569(4)A, B = 98.46(5)~. There are four molecules in the unit cell. Reflection intensities were measured by the 8-28 scan method with a Picker FACS-1 automated diffractometer, MoKa radiation, and a graphite. 2 (2) monochromator. For 1374 data with F >3o F ; R 1 = 0.030, and R 2 = 0.037. The Bi atom is coordinated by 6 chloride ions in an irregular octahedral array; two pairs of Cl ions form halogen bridges with neighboring Bi ions resulting in an infinite chain of edge sharing octahedra. There are 6 independent Bi-Cl bond distances: 2.50(1)~ and 2.52(1)~, to nonbridging chlorines, and 2.70(1)~, 2.75(l)A, 2.95(l)A and 3.10(l)A to bridging chlorines. The bridging Cl-Bi-Cl bond angles are 80.3° and 83.9°; the ten non-bridging Cl-Bi-Cl bond angles range from 85.9° to 99.3°. The axial Cl-Bi-Cl bond angles are 166.0°, 174.5°, and 175.9°.-ii-The ferricenium cations stack between the polymer chains with cyclopentadiene rings in the eclipsed conformation, unlike the pure ferrocene molecule which shows staggered rings. The average CC distance in the rings is 1.40(2)~, the distance between ring centers is 3.40(2)~ and the Fe-ring center distance is 1.70(2)~. • '}• 60~~767-1-' C1 (2')-Bi-C1 (3) •. 87.9 (1) C1 (2')-Bi-C1 (4) 166.0(1) C 1 (3)-B i-Cl(4)

Ferrocenium Tetrachloroantimonate

“…The Fe-to-ring-centre distances are 1.7062 (4)(C1-C5) and 1.7054 (4)/~, (C6-C10). The molecular packing in the title compound is in line with other related structures such as ferrocenium tetrachlorobismuthate and pyridinium tetrachloroantimonate (Mammano et al, 1977;Porter & Jacobson, 1970). In general, the Group 15 halogen anion MX£ forms an infinite chain of octahedra with the cations packed into the spaces between these chains.…”

“…Although ferrocene is readily oxidized to the ferrocenium cation by Group 15 trihalides such as PC13, AsCI3, SbC13 and BiC13, the products can be quite complicated due to the presence of highly aggregated halogeno-Group 15 anions (Landers et al, 1976;Mammano, Zalkin, Landers & Rheingold, 1977). Therefore, it can be generalized that the oxidation products of such reactions can have different compositions depending on the molar ratio of metal halide to ferrocene used, and also on the type of solvent.…”

“…Recrystallization of ferrocenium salts from water or organic solvents is normally very difficult and hence relatively few detailed X-ray structures of ferrocenium salts have been reported. Our literature search on ferrocenium Group 15 halides indicated that so far only the structures of ferrocenium tetrachlorobismuthate, (Mammano et al, 1977;Churchill, Landers & Rheingold, 1981;Rheingold, Landers, Dahlstrom & Zubieta, 1979). Even though a product from SbC13 with an empirical formula analogous to that of ferrocenium tetrachlorobismuthate was found, no structural details of the compound were reported (Cowell, Ledwith, White & Wood, 1970) and hence the X-ray structure analysis of the title compound, (I), was undertaken.…”

Structure of ferrocenium hexafluorophosphate

“…Until 1983 all reported structures of ferrocenium ions showed an eclipsed conformation for the r/5-C5H5 (Cp) rings: (Cp2Fe)(picrate) (Petterson, 1966), (Cp2Fe)(CC13CO2H)3 (Schleuter & Gray, 1971), (Cp2Fe)(BiC14) (Mammano, Zalkin, Landers & Rheingold, 1977), [(Cp2Fe)2(SbaCl120)]2.2C6H6 (Rheingold, Landers, Dahlstrom & Zubieta, 1979), (Cp2Fe)2(As4ClloO2) (Churchill, Landers & Rheingold, 1981), (Cp2Fe)(FeC14) (Paulus & Sch/ifer, 1978). The structure of (Cp2Fe)I 3 (Bernstein & Herbstein, 1968) was so disordered that no structural details concerning the ferrocenium ion could be obtained.…”

A functionalized pyridinyl ligand containing binuclear biferrocene

“…The average distance from the iron atom to the center of Cp rings is 1.640(1) Å . Inspection of this Fe Ã/Cp distance shows that this value is closer to the value of 1.65 Å found for ferrocene [14] than to the value of 1.70 Å found for the ferrocenium ion [15]. The dihedral angle between the two least-squares planes of the Cp rings for a given ferrocenyl moiety is 1.528, while the two Cp rings bonded to each iron ion are nearly eclipsed, with an average staggering angle of 9.098.…”