Molecular structure of fluoro derivatives of anionic pentacoordinated germanium. A new geometrical form for germanium

Abstract

Abstract The X-ray structures of tetraethylammonium bis(1,2-benzenediolato)fluorogermanate, [(C2H5)4N]+[(C6H4O2)2GeF]- (3), and the related monosolvate of methyltriphenylphosphonium bis(4methyl-1,2-benzenedithiolato)fluorogermanate, [(CH3)PPh3]+ [(C7H6S2)2GeF]-.CH3CN (4), lie along the Berry C 2t, coordinate connecting the idealized trigonal bipyramid with the rectangular pyramid. The structure of 3 is placed about 81% along this coordinate toward the rectangular pyramid and that for 4 is about 40% along this coordinate. 3 crystallizes in the monoclinic space group P21,/c with a = 12.886 (2) A, b = 14.870 (2) A, c = 10.912 (1) A, β = 100.29 (1)°, and Z = 4. 4 crystallizes in the monoclinic space group P21/n with a = 17.108 (6) A, b = 10.566 (3) A c = 20.630 (6) A, β = 114.01 (2)°, and Z = 4. The final conventional unweighted residuals were 0.035 and 0.058 for 3 and 4, respectively. The greater displacement of the pentacoordinated oxa compound 3 toward the RP is rationalized in terms of reduced electron-pa...