화학공학소재연구정보센터
Inorganic Chemistry, Vol.36, No.19, 4151-4155, 1997
Bonding forces in short hydrogen bonds. Crystal structure of Pd-II(dpgH)(2)
An analysis of the structures of 16 square-planar metal(II)-diglyoxime compounds was undertaken to determine the bonding forces which might alter the O...O distance observed for strong, low-barrier hydrogen bonds. This series of structures includes the X-ray diffraction structure of Pd-II(dpgH)(2) (dpg=diphenylglyoxime), with data collected at 158 K. This compound crystallizes in the space group Ibam with a=15.324(2) Angstrom, b=22.634(3) Angstrom, c=6.8811(7) Angstrom, V=2386.6(5) Angstrom(3), Z=4, and R=4.89% for the 1105 reflections with \F-0\>4 sigma(F) and 7.91% for all 1490 reflections. The observed Pd-N bond distances are 1.958(6) and 1.959(6) Angstrom. The distance between the two oxygen atoms that participate in the short hydrogen bond is 2.550(10) Angstrom; this distance is the shortest thus far reported for a palladium-diglyoxime compound. The hydrogen atom appears to be nearly centered, with refined O-H distances of 1.32(22) and 1.39(23) Angstrom in the O..H..O system; this interpretation of the hydrogen position is supported by nearly equivalent N-O distances in the strong-hydrogen-bond-containing moiety. Additionally, a search of the Cambridge Structure Database yielded 15 examples of square-planar metal-diglyoxime compounds of Ni(II), Pd(II), or Pt(II). Analysis of bonding forces in this series of compounds indicates that reduction of electron-electron repulsion between the oxygen atoms, either by delocalization of charge or by electron-withdrawing substituent groups, allows a closer approach of the oxygen atoms and a shorter hydrogen bend.