Synthesis and structure of bismuth complexes [Ph4P]+2[Bi2I8(m2-Et2SO-O)]2- and [Ph4P]+2trans-[Bi2I8(dmso-O)2]2-

The interaction of bismuth (III) iodide with tetraphenylphosphonium iodide in dimethylsulfoxide and diethylsolfoxide have synthesized bismuth complexes [Ph4P]+2[Bi2I8(m2-Et2SO- O )]2- (1) и [Ph4P]+2 trans -[Bi2I8(dmso- O )2]2- (2). They have been structurally characterized. The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (Mo Kα -radiation, λ = 0.71073 Å, graphite monochromator) of crystals 1 [C26H24O0.5SI4BiP, M 1124.06, the monoclinic syngony, the symmetry group С2/с; cell parameters: а = 27.563(15) Å, b = 9.140(7) Å, с =28.978(17) Å; α = 90.00 degrees, β =119.069(17) degrees, γ = 90.00 degrees; V = 6381(7) Å3; the crystal size 0.43×0.35×0.19 mm; intervals of reflection indexes are -41 ≤ h ≤ 41, -13 ≤ k ≤ 13, -43 ≤ l ≤ 42; total reflections 124163; independent reflections 11658; Rint 0.0708; GOOF 1.025; R 1 = 0.0852, wR 2 = 0.1380; residual electron density -3.19/2.61 e/Å3] [C28H32O2PS2BiI4, M 1212.21; the triclinic syngony, the symmetry group Р-1; cell parameters: а = 9.409(10) Å, b = 14.149(16) Å, с =15.745(15) Å; α = 113.85 degrees, β =92.50(4) degrees, γ = 104.05 degrees; V = 1836(3) Å3; the crystal size 0.64×0.43×0.4 mm; intervals of reflection indexes are -15 ≤ h ≤ 15, -23 ≤ k ≤ 24, -25 ≤ l ≤ 26; total reflections 117427; independent reflections 18300; Rint 0.0927; GOOF 1.006; R 1 = 0.1366, wR 2 = 0.1369; residual electron density -2.99/2.59 e/Å3] the phosphor atoms have a distorted tetrahedral coordination (the CPC angles are 107.7(3)-112.8(4)° (1), 107.2(3)-111.2(3)° (2); the Р-С bond lengths are 1.771(7)-1.823(8) Å (1), 1.786(6)-1.804(5) Å (2)). The equatorial angles IBiI are 86.22(3)-92.87(3)° (1), 80.43(8)-95.86(8)° (2), the axial angles OBiI are 162.71(11)° (1), и 174.34(11)° (2); the equatorial Bi-I bond lengths are 2.8882(14)-3.2829(18) Å (1), 2.928(2)-3.364(3) Å (2), the axial Bi-I bond lengths are 2.9156(17) Å (1), 2.928(2) Å (2), the axial Bi-O bond lengths are 2.747(5)Å (1), 2.572(5) Å (2). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1969793, 1969795; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).