I. V. Egorova

Synthesis and structure of bismuth complexes [Ph3MeP]2+[BiI3.5Br1.5(C5H5N)]2− · C5H5N, [Ph4Bi]4+[Bi4I16]4− · 2Me2C=O, and [Ph3(iso-Am)P]4+[Bi8I28]4− · 2Me2C=O

Complexes [Ph3MeP]2+[BiI3.5Br1.5(C5H5N)]2− · C5H5N(I), [Ph4Bi]4+[Bi4I16]4− · 2Me2C=O (II), and [Ph3(iso-Am)P]4+[Bi8I28]4− · 2Me2C=O (III) were synthesized by reactions of bismuth iodide with triphenylmethylphosphonium bromide, triphenylbismuthonium sulfosalicylate, and triphenylisoamylphosphonium iodide, respectively. The crystal structures of complexes I–III were determined by X-ray crystallography. The complexes contain, in addition to cations and solvent molecules, mono-, tetra-, and octanuclear anions, in which bismuth atoms are in octahedral coordination.

Synthesis and Structure of the bismuth complex [Ph3PrP] 4 + [Bi4I16]4−

The complex [Ph3P]4+[Bi4I16]4− · 2 Me2C=O (I) was synthesized by the reaction of triphenyl(propyl)phosphonium iodide with bismuth iodide in acetone. The crystal structure of complex I was determined by X-ray crystallography. It contains, in addition to solvent molecules, two types of crystallographically independent tetrahedral tetraphenyl(propyl)phosphonium cations and tetranuclear anions [Bi4I16]4− in a chair conformation with the bismuth atoms being in an octahedral coordination. The Bi-I distances in the anion vary within 2.8768(4)–3.2524(4) Å.

Bismuth compounds [Ph3BuP]+I−, [Ph3BuP]2+[Bi2I8 · 2Me2C=O]2−, and [Ph3BuP]2+[Bi2I8 · 2Me2S=O]2−: Syntheses and crystal structures

The complexes [Ph3BuP]2+[Bi2I8 · 2Me2C=O]2− (II) and [Ph3BuP]2+[Bi2I8 · 2Me2S=O]2− (III) are synthesized by the reactions of triphenyl(n-butyl)phosphonium iodide (I) with bismuth iodide in acetone and dimethyl sulfoxide. In the cations of complexes I–III, the P atoms have a distorted tetrahedral coordination (CPC angles 106.3(2)°–112.0(3)°). The butyl group in cation I is disordered over two positions. In the binuclear centrosymmetric anions of structures II and III, the octahedrally coordinated bismuth atoms are linked in pairs by two bridging (br) iodine atoms (Bi-Ibr 3.1508(7) and 3.2824(8) Å in compound II, 3.1961(3) and 3.3108(3) Å in complex III), which are coplanar to four terminal (t) iodine atoms (Bi-It 2.9260(7) and 2.9953(6) Å in complex II, 2.9206(3) and 2.9786(3) Å in complex III). The two remaining positions at the bismuth atom are occupied by the iodine atom (Bi-It 2.8531(7) Å in complex II, 2.8984(3) Å in complex III) and O atom of the organic molecule (Bi-O 2.747(6) Å in complex II, 2.507(3) Å in complex III).

Structures of triphenylbismuth dicarboxylates

Tripheylbismuth bis(trichloroacetate) (I), triphenylbismuth bis(chloroacetate) (II), and triphenylbismuth bis(bromoacetate) (III) were synthesized by the reaction of triphenylbismuth with carboxylic acid. The Bi atoms of the synthesized compounds have a distorted trigonal-bipyramidal coordination with phenyl ligands in equatorial positions. The Bi-C bond lengths lie within intervals 2.194(2)–2.201(2), 2.193(8)–2.223(7), 2.191(4)–2.220(3) Å, the distances Bi-O and Bi···O(=C) are equal 2.308(2), 2.315(2), and 2.896(2), 2.931(2); 2.289(6), 2.302(6), and 2.891(6), 2.910(6); 2.295(3), 2.312(3), and 2.893(3), 2.920(3) Å in I, II, and III, respectively. Molecules of triphenylbismuth dicarboxylates show linear dependence between the maximum equatorial angle CBiC (on the side of a contact) and intramolecular distance Bi···O(=C).

Synthesis of bismuth complexes from bismuth iodide and ammonium and phosphonium salts

The complexes [Et2NH2]3+[BiCl6]3− (I), [NH4]+[BiI4(C5H5N)2]−·2C5H5N (II), [Ph3MeP]2+[BiI5]2− (III), [Ph3MeP]2+[BiI5(C5H5N)]2−·C5H5N (IV), [Ph3MeP]3+[Bi3I12]3− (V), [Ph3(i-Pr)P]3+[Bi3I12]3−·2Me2C=O (VI), [Ph3BuP]2+[Bi2I8·2Me2C=O]2− (VII), and [Ph3BuP]2+[Bi2I8·2Me2S=O]2− (VIII) were obtained by reactions of bismuth iodide with ammonium and phosphonium iodides in acetone, pyridine, or dimethyl sulfoxide.

Synthesis and structure of bismuth-containing complexes [Ph3PMe] 2 + [BiI5]2− and [Ph3PMe] 2 + [BiI5 · C5H5N]2− · C5H5N

The complexes [Ph3PMe]2+[BiI5]2− (I) and [Ph3PMe]2+ [BiI5 · C 5H5N]2− · C 5H5N (II) were synthesized by the reaction of bismuth triiodide with triphenylmethylphosphonium iodide, and their structures were determined by X-ray diffraction analysis. The P atom in cation I has slightly distorted tetragonal coordination polyhedron (the CPC angles 109.42(4)° and 109.52(4)°, the bond lengths P-CPh 1.779(2), P-CMe 1.793(1) Å. The Bi atom in the anion of complex I has an ideal trigonal-bipyramidal coordination polyhedron (Bi-Ieq 3.0031(4), Bi-Ieq 3.0485(5) Å). The crystal of complex II consists of the anions [BiI5 · C 5H5N]2−, solvated pyridine molecules, and two types of crystallographically independent tetrahedral triphenylmethylphosphonium cations (the angles CPC 106.9(1)°–111.7(1)°, the distances P-CPh 1.785(3)–1.792(3), P-CMe 1.793(3), 1.786(3) Å). The Bi atoms in the anion of complex II have a distorted octahedral coordination polyhedron (Bi-I 3.0878(4)–3.1240(3), Bi-N(1) 2.628(3) Å).

Reaction of Tetraphenylantimony Bromide with o-Tolylbismuth Bis(2,5-dimethylbenzenesulfonate). The Formation of Tetranuclear Anion [Bi4Br16]4–

The [Ph4Sb]4[Bi4Br16] complex was synthesized via reaction of tetraphenylantimony bromide with o-tolylbismuth bis(2,5-dimethylbenzenesulfonate) and studied using X-ray diffraction analysis. This compound has ionic structure and consists of tetraphenylstibonium cations and a four-charge tetranuclear anion [Bi4Br16]4– formed by two pairs of edge-sharing ВiBr6 octahedra. The Sb–C bond lengths are equal to 2.05(1)–2.10(1) Å, the Bi–Br distances lie within the 2.649(2)–3.246(2) Å range, and the Sb(1)···Br(7) distance is equal to 3.934(2) Å.

Synthesis and structure of bismuth complexes [Ph3(n-Pr)P] 2 + [Bi2I8 · 2Me2S=O]2−, [Ph3(iso-Bu)P] 2 + [Bi2I8 · 2Me2S=O]2−, [Ph3(n-Bu)P] 2 + [Bi2I8 · 2Me2S=O] 2−, and [Ph3(n-Am)P] 2 + [Bi2I8 · 2Me2S=O]2−

The complexes [Ph3(n-Pr)P]2+[Bi2I8 · 2Me2S=O]2− (I), [Ph3(iso-Bu)P]2+[Bi2I8 · 2Me2S=O]2− (II), [Ph3(n-Bu)P]2+[Bi2I8 · 2Me2S=O]2− (III), and [Ph3(n-Am)P]2+[Bi2I8 · 2Me2S=O] 2− (IV) are synthesized by reactions of triphenylalkylphosphonium iodide with bismuth iodide in dimethyl sulfoxide. In all complexes, the P atoms in cations have a distorted tetrahedral coordination (the CPC angles vary from 106.4(8)° to 114.8(2)°). In the dihedral centrosymmetric anions, the octahedral bismuth atoms are bound to each other by two bridging (br) iodine atoms (Bi-Ibr 3.167(1), 3.273(1) Å (I); 3.1557(2), 3.2589(2) Å (II); 3.1961(3), 3.3108(3) Å (III); 3.1913(4), 3.3161(4) Å (IV)), which are coplanar to four terminal (t) iodine atoms (Bi-It 2.956(1), 2.989(1) Å (I); 2.9557(2), 2.9872(2) Å (II); 2.9206(3), 2.9706(3) Å ( III ); 2.9328(4), 2.9890(4) Å (IV)). Two remaining positions at the bismuth atoms are occupied by the iodine atom (Bi-I 2.987(1) Å (I); 3.0051(2) Å (II); 2.8984(3) Å (III); 2.9046(4) Å (IV)) and the dimethyl sulfoxide molecule (Bi-O 2.458(12) Å (I); 2.430(2) Å (II); 2.507(3) Å (III); 2.544(4) Å (IV)).

Synthesis and structure of triphenylbismuth bis(2-phenylaminobenzoate)

Interaction of triphenylbismuth with phenylanthranilic acid in the presence of hydrogen peroxide yields triphenylbismuth bis(2-phenylaminobenzoate), in which bismuth atoms have a distorted trigonal bipyramidal coordination with phenyl ligands in equatorial positions. The bond lengths (Å) are as follows: Bi-C, 2.193(5), 2.200(4), and 2.200(4); Bi-O, 2.252(4) and 2.300(4). Intramolecular hydrogen bonds N-H⋯O(=C) (H⋯O, 1.91, 1.97 Å; N⋯O, 2.634(9), 2.667(9) Å) and donor-acceptor interactions Bi⋯O(=C) (2.790(5) and 2.838(5) Å) exist in the molecule.

Synthesis and structure of phenylbismuth bis(chloroacetate)

Crystals of phenylbismuth bis(chloroacetate) were synthesized by the reaction of triphenylbismuth with chloroacetic acid. Tridentate chelate-bridging chloroacetate ligands are bonded to neighboring molecules through the O atoms to form polymer chains. The Bi-O distances are equal to 2.36(1), 2.55(1), 2.78(1) and 2.30(1), 2.67(1), 2.85(2) Å. the length of the Bi-C bond is 2.26(2) Å.