Reactions of triphenylantimony with pentafluoropropionic acid and pentafluorophenol in the presence of cumil hydroperoxide

Reactions of triphenylantimony with pentafluoropropionic acid and pentafluorophenol in the presence of cumyl hydroperoxide (molar ratio 1:2:1) result in formation of triphenylantimony bis(pentafluoropropionate) Ph3Sb[OC(O)CF2CF3]2 (1) and triphenylantimony bis(pentafluorophenolate) Ph3Sb(OC6F5)2 (2), respectively. The structures of compounds have been established by X-ray diffraction analysis (XRD). According to the XRD data, crystals 1 consist of two types of crystallographically independent molecules [C48H30F20O8Sb2, M 1358.22; monoclinic syngony, symmetry group P21/n; cell parameters: a = 13.732(8), b = 19.599(7), c = 20.500(10) Å; β = 101.23(2); V = 5412(4) Å3; Z = 4; calc = 1.667 g/cm3; = 1.116 mm1; 2 5.0657 deg.; total reflections 159335; independent reflections 13706; number of refined parameters 741; Rint = 0.0813; GOOF 1.146; R1 = 0.0730, wR2 = 0.1925; residual electron density (max/min): 1.23/0.89 e/Å3], 2 [C30H15F10O2Sb, M 719.17; triclinic syngony, symmetry group P-1; cell parameters: a = 10.0334(4), b = 10.8464(4), c = 15.1351(6) Å; = 76.156(2), β = 70.938(2), = 64.2450(10); V = 1392.93(10) Å3, Z = 2; calc = 1.715 g/cm3; = 1.085 mm 1; 2 6.15856.998 deg; total reflections 17472; independent reflections 6633; number of refined parameters 377; Rint = 0.0244; GOOF 1.077; R1 = 0.0398, wR2 = 0.0914; residual electron density (max/min): 0.64/0.60 e/Å3]. In trigonal bipyramidal molecules with the oxygen atoms in axial positions, the Sb−C distances are 2.071(4)−2.100(6) Å for 1 and 2.088(4)−2.095(4) Å for 2; the OSbO bond angles take values of 177.53(17)° (1A), 176.81(18)° (1B), and 179.37(9)° (2). The Sb−O distances in 1 (2.109(4)2.121(5) Å) are somewhat higher than in 2 [2.083(2) and 2.092(3) Å]. The intramolecular Sb∙∙∙O contacts in 1 between the central metal atom and the carbonyl oxygen atoms are 3.198(5), 3.244(6) Å for 1A and 3.170(5), 3.207(6) Å for 1B, which is less than the sum of the van der Waals radii of the partner atoms (3.7 Å). Complete tables of atomic coordinates, bond lengths and bond angles for the structures have been deposited with the Cambridge Crystallographic Data Centre (No. 2066544 (1), No. 2179019 (2), deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).