Synthesis and structure of triphenylbismuth bis(fluorobenzoates)

The reaction between triphenylbismuth, hydrogen peroxide, and 3,4,5-trifluorobenzoic or pentafluorobenzoic acid (molar ratio 1 : 1 : 2, respectively) in ether gave triphenylbismuth bis(3,4,5-trifluorobenzoate) (I) and triphenylbismuth bis(pentafluorobenzoate) (II) in 74 and 89% yields, respectively. The structures of compounds I and II were established by X-ray diffraction. The Bi atoms have a distorted trigonal-bipyramidal coordination with acylate groups in the axial positions. The OBiO angles are 170.2(2)degrees and 171.5(2)degrees in I and II, respectively. The Bi-C(Ph)(eq) bond lengths vary in the range of 2.187(6)-2.204(5) Angstrom, the Bi-O(acyl) lengths are 2.256(5) Angstrom in I, and 2.281(5) and 2.318(5) Angstrom in II. In the crystals I and II, the Bi and carbonyl O atoms are involved in intramolecular interactions (Bi (. . .) O(=C) 2.926(5)-3.176(5) Angstrom), which increase the equatorial CBiC angles on the side of these contacts to 136.2(3)degrees and 138.6(2)degrees in I and II, respectively.