Synthesis and structure features of triphenylbismuth dicarboxylates

The interaction of triphenylbismuth with chloroacetic acid and pentafluorobenzoic acid in the presence of tert -butyl hydroperoxide or hydrogen peroxide in ether has led totriphenylbismuth bis (chloroacetate) (1) and triphenylbismuth bis (2,3,4,5,6-pentafluorobenzoate) (2). The X-ray diffraction pattern for the crystal 1has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (MoKα-radiation, λ = 0.71073 Å, graphite monochromator), the results are [C22H19O4Cl2Bi, M 627.25, the triclinic syngony, the symmetry group P -1; cell parameters: a = 8.891(5), b = 10.401(5), c = 12.452(5) Å; α = 86.38(2) degrees, β = 73.97(2) degrees., γ = 87.15(3) degrees.; V = 1104.0(9) Å3; the crystal size is 0.41×0.28×0.1 mm; intervals of reflection indexes are -15 ≤ h ≤ 15, -17 ≤ k ≤ 17, -21 ≤ l ≤ 21; total reflections 76809; independent reflections 11945; Rint 0.0525; GOOF 1.041; R1 = 0.0330, wR2 = 0.0665; residual electron density 1.30/-2.28 e/Å3], and 2 [C32H15O4F10Bi, M 862.42, the triclinic syngony, the symmetry group P-1; cell parameters: a = 12.168(8), b = 12.260(8), c = 12.720(8) Å; α = 72.43(3) degrees, β = 63.39(3) degrees, γ = 61.46(2) degrees.; V = 1481.0(16) Å3; the crystal size is 0.37×0.2×0.1 mm; intervals of reflection indexes are -16 ≤ h ≤ 16, -16 ≤ k ≤ 16, -16 ≤ l ≤ 16; total reflections 51260; independent reflections 7342; Rint 0.0416; GOOF 1.047; R1 = 0.0251, wR2 = 0.0524; residual electron density 0.84/-0.91 e/Å3]the bismuth atoms have a distorted trigonal-bipyramidal coordination. The OBiO axial angles are 173.07(7) degrees and 172.24(8) degrees; the sums of the CBiC angles in the equatorial plane are 359.93 degrees and 359.92 degrees. The Bi-O bond lengths are 2.303(2), 2.323(2) Å, and 2.272(3), 2.315(3) Å .The intervals of variation in the Bi-C equatorial bond lengths are 2.190(3)-2.214(3)Å and 2.194(3)-2.206(3)Å. Structures 1 and 2 contain intermolecular contacts between the bismuth atoms and the oxygen atoms of the carboxylate groups. The Bi···O=С distances equal 2.904(3), 2.908(3) Å (1), and 2.947(4), 3.167(4) Å (2), which is less than the sum of the Van der Waals radii of bismuth and oxygen (3.59 Å). The Cl∙∙∙Cl intermolecular contacts (3.43 Å) and H∙∙∙O (2.43, 2.57 Å) are present in crystal 1; while only H∙∙∙O (2.50 Å) is presentin crystal 2. Complete tables of coordinates of atoms, bond lengths and valence angles for the structure are deposited at the Cambridge Structural Data Bank (No. 1991198 (1); No. 2042930 (2); deposit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).