M. Konno, Shinaki Hyodo, S. Iijima
Aug 1, 1982
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0
Influential Citations
31
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Journal
Bulletin of the Chemical Society of Japan
Abstract
The crystal structure of 1′,1'″-dipropylbiferrocenium (PrFcFcPr)+I3−, which shows averaged-valence irons at 298 K and trapped-valence irons at 110 K, was determined by X-ray diffraction. The crystal at 298 K is triclinic, space group P\bar1, a=8.5148(8), b=8.5482(5), and c=10.9032(13) A, α=89.546(9), β=115.582(9), and γ=108.488(7)°, U=671.10(9) A3, and Z=1. The crystal at 110 K is triclinic, space group P1, a=8.431(2), b=8.478(2), and c=10.816(3) A, α=88.58(3), β=117.39(2), and γ=108.65(2)°, U=643.4(3) A3, and Z=1. Structures were refined to R=0.042 at 298 K and R=0.050 at 110 K. At 298 K cation (PrFcFcPr)+ sits on the symmetry center and the two Fc units are crystallographically equivalent, whereas at 110 K the symmetry center is lost and ferrocene-like and ferrocenium-like Fc units are distinguished. A three-dimensional hydrogen-bond network is clearly found between the cation and iodine atoms at 110 K, in contrast to the result at 298 K. Infrared spectra of 1′,1'″-diethyl- and 1′,1'″-dipropylbiferrocen...