Bridging Iodine Research Articles

Thermodynamic vs. Kinetic Control in Synthesis of O-Donor 2,5-Substituted Furan and 3,5-Substituted Pyrazole from Heteropropargyl Precursor.

Elaboration of a convenient route towards donor-substituted pyrazoles from heteropropargyl precursors is challenging due to a number of thermodynamically favorable side reactions (e.g., acetylene–allene isomerization and Glaser homocoupling). In this work, Sonogashira cross-coupling conditions of 4-tert-butylphenyl propargyl ether with benzoyl chloride followed by tandem Michael addition/cyclocondensation with hydrazine into 3,5-disubstituted pyrazole (kinetic control), as well as cycloisomerization conditions of ketoacetylene intermediate into 2,5-disubstituted furan (thermodynamic control), were established through a variation of the catalyst loading, solvent polarity, excess of triethylamine, and time of reaction. During the optimization of process parameters, a number of by-products represented by a monophosphine binuclear complex (PPh3PdI2)2 with two bridging iodine atoms and diyne were identified and isolated in the pure form. The quantum-chemical calculations and solution-state 1H/13C NMR spectroscopy suggested that the 5(3)-(4-tert-butylphenyloxy)methoxy-3(5)-phenyl-1H-pyrazole exists in the tautomeric equilibrium in a polar methanol solvent and that individual tautomers could be characterized in case aprotic solvents employed. The pyrazole features a unique tetramer motif in the crystal phase formed by alternating 3(5)-phenyl-1H-pyrazole tautomers, which was stabilized by N–H···N bonds and stacking interactions of pyrazole rings, whereas pyrazole dimers were identified in the gas phase.

Pyridinyl-triazole ligand systems for highly efficient CuI-catalyzed azide-alkyne cycloaddition

Pyridinyl-triazole ligand systems (including N2-2-pyridinyl 1,2,3-triazoles and N1/N2-substituted 2-(NH-1,2,3-triazol-4-yl)pyridines) were found to be superior ligands for CuI-catalyzed azide-alkyne cycloaddition (CuAAC) reactions. Low catalyst loadings, short reaction times, facile catalyst recyclability, ambient temperature, and open-flask conditions made this catalytic system very practical. The iodide anions could form iodine bridges to construct stable dinuclear Cu(I) complexes with these ligands, which was the key to achieve high catalytic activities. While CuBr and CuCl were not suitable for this ligand system because of the improper size of Br and Cl atoms for the formation of the corresponding dinuclear Cu(I) complexes.

Structure of a One-Dimensional Copper(I) Polymer with Iodine Bridges

A novel one-dimensional polymeric Cu(I) halide complex with iodine bridges between copper atoms and 2-phenylquinoline as an N-donor ligand is prepared. The complex is characterized by elemental analyses, IR spectroscopy, and crystallographic studies.The coordination geometry around copper may be described as distorted trigonal planar. The I-Cu-I, Cu-I-Cu, and N-Cu-I angles are 115.90(2)°, 116.37(2)°, and 124.80(8)°, respectively. The Cu-I distances range from 2.563(6) A to 2.569(6) A, and the Cu-N bond is 2.016(2) A, being in good agreement with that in the related structures.

Structure of a one-dimensional copper(I) polymer with iodine bridges

A novel one-dimensional polymeric Cu(I) halide complex with iodine bridges between copper atoms and 2-phenylquinoline as an N-donor ligand is prepared. The complex is characterized by elemental analyses, IR spectroscopy, and crystallographic studies.The coordination geometry around copper may be described as distorted trigonal planar. The I—Cu—I, Cu—I—Cu, and N—Cu—I angles are 115.90(2), 116.37(2), and 124.80(8)°, respectively. The Cu—I distances range from 2.563(6) to 2.569(6) Å, and the Cu—N bond is 2.016(2) Å, being in good agreement with that in the related structures.

Cu4I73−]n: A novel 1-D iodocuprate aggregate

A new cationic ligand, 1-methyl-3-(methylthio)pyrazin-1-ium iodide (MMTPI), has been designed and synthesized by regioselective alkylation of 2-methylthiopyrazine with MeI. Reaction of this ligand with CuI in a 3:4 molar ratio under mild conditions (MeCN, r.t.) produces new iodocuprate, [Cu4I7(MMTP)3]n, containing one-dimensional inorganic chains [Cu4I73−]n. The latter are constructed from the basket-shaped {[Cu3(μ3-I)](I)3(μ2-I)3} building blocks, which are linked by tetrahedral Cu atoms through bridging iodine atoms. The UV–Vis diffuse reflectance measurements reveal that the title iodocuprate possesses semiconductor behaviour with the band gap of 1.80 eV. The thermal stability and electronic structure of the iodocuprate are also discussed.

Coordination polymer of cadmium(II) iodide with tetramethylpyrazine

Compound [CdI2(Me4Pyz)] is synthesized by the reaction of CdI2 with tetramethylpyrazine (Me4Pyz, C8H12N2), and its structure is determined (CIF file CCDC 1538646). The crystals are monoclinic, space group C2/c, a = 14.732(3), b = 11.084(2), c = 7.792(2) A, s = 95.27(3)°, V = 1267.0(4) A, ?calcd = 2.634 g/cm3, Z = 4. Polymer chains [CdI2(Me4Pyz)]221e extended along the direction [001] are formed in the structure of the complex due to the bridging iodine atoms. The coordination polyhedron of the Cd2+ ion is a trigonal bipyramid with four bridging iodine atoms and one nitrogen atom of the organic ligand lying in the equatorial plane along with two iodine atoms. The distance between the cadmium atoms in the chain is 4.155 A.

A complex of cadmium(II) iodide with 4-cyanopyridine: Synthesis, crystal structure, and luminescent properties

The complex [CdI2(4-CNPy)2] (I) was obtained by a reaction of CdI2 with 4-cyanopyridine (4-CNPy, C6H4N2) and structurally characterized (CIF file CCDC no. 983377). The crystals of complex I are monoclinic, space group C2, a = 24.698(5) A, b = 4.127(1) A, c = 7.597(2) A, β = 96.05(1)°, V = 770.0(3) A3, ρcalcd = 2.477 g/cm3, Z = 2. In structure I, iodine atoms serve to unite complex molecules into the polymer chains [CdI2(4-CNPy)2]∞ along the direction [010]. The Cd(1) atom lying on a twofold axis has a slightly distorted octahedral environment made up of four bridging iodine atoms and two nitrogen atoms of two ligands 4-CNPy (Cd-Iav, 2.947(2) and Cd-N(1), 2.410(6) A). Within each chain, cadmium atoms are spaced apart at 4.13 A. Complex I exhibits photoluminescence.

On the structural diversity anions coordinate to the butterfly-shaped [(R2Sn)3O(OH)2]2+ cations and vice versa

The syntheses and crystal structures of [(t-Bu2Sn)3O(OH)2]CO3·3MeOH, 1a, [(t-Bu2Sn)3O(OH)2]CO3·3H2O·acetone, 1b, [(t-Bu2Sn)3O(OH)2][I]2·[(t-Bu2Sn(OH)I]2·2DMSO, 1c, and [(Cy2Sn)3O(OH)2][I]2·2DMSO, 2a, all containing the trinuclear [(R2Sn)3O(OH)2]2+ ion have been described. The butterfly shape of this cation is derived from two annulated, four-membered tin–oxygen rings with a central μ3-oxygen atom and trigonal-bipyramidally coordinated tin atom both belonging to both rings and two μ2-hydroxyl groups and two outer, four-fold coordinated tin atoms. In 1a and 1b, the carbonate anions interact with the outer tin atoms of the cations as bidentate chelating ligands in the classical syn–syn coordination mode, and vice versa. In this way, both outer tin atoms expand their coordination sphere from four to five, with the consequence that bond angles and lengths within the cation are determined by the axial and equatorial position of the oxygen atoms within the trigonal-bipyramidal coordination on all three tin atoms. 1c consists of two different building units, an up to now unknown hydroxide iodide of composition [(t-Bu2Sn(OH)I]2 with hydrogen-bonded DMSO molecules and a [(t-Bu2Sn)3O(OH)2]2+ cation with one coordinated and one isolated, via hydrogen bonds connected iodine ion. The hydroxide iodine is built up of two five-fold coordinated tin atoms linked via two hydroxyl groups with exocyclic iodine atoms occupying axial positions at the trigonal-biypramidally coordinated tin atoms. The unprecedented coordination of the iodine ion to the [(t-Bu2Sn)3O(OH)2]2+ cation takes place between both outer tin atoms, resulting in a five-fold, trigonal-bipyramidal coordination at these tin atoms, too. Structural parameters within the so-formed [(t-Bu2Sn)3O(OH)2I]+ complex are very similar to those of 1a and 1b, with the exception of a significant lengthening of the tin–oxygen bonds opposite to the bridging iodine atom. 2a represents the first example of the [(R2Sn)3O(OH)2]2+ cation without R = t-butyl, so far. In the solid, it consists of two crystallographic independent [(Cy2Sn)3O(OH)2][I]2 building units, each connected to two DMSO molecules via hydrogen bonds. Both building units are very similar with respect to their conformation. Each of the iodine anions coordinates with only one of the two outer tin atoms, one in an inwards, one in an outwards to the tin-oxygen framework directed position. These tin atoms are therefore also trigonal-bipyramidally coordinated as in 1a−1c, but because of steric reasons one of the trigonal-bipyramids has changed its orientation within the tin–oxygen framework, accompanied by enormous changes of bond lengths and angles therein.

Coordination molecular compounds of cadmium(II) iodide with dimethylpyridines

The reactions of CdI2 with dimethylpyridines (Me2Py is C7H9N) afford complexes CdI2(2,3-Me2Py)2] (I), [CdI2(2,6-Me2Py) (II), and CdI2(3,5-Me2Py)2 (III). The structures of compounds I and II are determined. The crystals of complex I are orthorhombic, space group Pbca, a = 7.930(1) A, b = 15.537(1) A, c = 29.943(1) A, V = 3689.1(5) A3, ρcalcd = 2.090 g/cm3, Z = 8. The crystals of complex II are monoclinic, space group C2/c, a = 14.784(1), b = 11.991(1), c = 17.711(1) A, β = 90.39(1)°, V = 1081.1(2) A3, ρcalcd = 2.908 g/cm3, Z = 4. The structure of compound I is built of discrete neutral complexes [CdI2(2,3-Me2Py)2]. The Cd polyhedron is a distorted tetrahedron (Cd-I 2.289–2.295, Cd-N 2.708–2.734 A, angles N(I)CdN(I) 103.1°-114.8°). Polymer chains [CdI2(2,6-Me2Py)]∞ extended along the direction [100] are observed due to the bridging iodine atoms in structure II. The Cd polyhedron is a trigonal bipyramid containing iodine atoms at the axial vertices (Cd-Iaks 3.040 A) and two iodine atoms and the nitrogen atom of the Me2Py ligand in the equatorial plane Me2Py (Cd-Ieq 2.840 A, Cd-N 2.309 A). The compounds in the solid state are photoluminescent.

Synthesis and structure of (tricarbollide)iodide iridium complex [(η-1-ButNH-1,7,9-C3B8H10)IrI2

Cyclooctadiene complex (η-1-ButNH-1,7,9-C3B8H10)Ir(cod) (1) was obtained by the reaction of [(7-ButNH-7,8,9-C3B8H10)]Tl with [(cod)IrCl]2 in the presence of TlPF6. The reaction of 1 with I2 gave diiodide [(η-1-ButNH-1,7,9-C3B8H10)IrI2]2 (2a). According to the X-ray diffraction data, complex 2a has a dimeric structure with two bridging iodine atoms.

Synthesis, crystal structures, and luminescence spectra of the coordination compounds of cadmium(II) iodide with hexamethylenetetramine

Coordination compounds [Cd1.5I3(HMTA) · H2O] (I) and [CdI2(HMTA) · H2O] (II) are synthesized by the reaction of CdI2 with hexamethylenetetramine (HMTA, C6H12N4) with the 1: 1 ratio in ethanol, and their structures are determined. The crystals of compound I are triclinic, space group P\( \bar 1 \), a = 8.027(1), b = 9.391(1), c = 10.382(1)A, α = 66.64(1)°, β = 86.18(1)°, γ = 73.63(1)°, V = 749.2(1) A3, ρcalcd = 3.136 g/cm3, Z = 2. The crystals of compound II are triclinic, space group P\( \bar 1 \), a =7.713(1), b = 8.192(1), c = 12.101(1)A, α = 80.32(1)°, β = 89.57(1)°, γ = 7.30(1)°, V = 725.0(1) A3, ρcalcd = 2.402 g/cm3, Z = 2. Structure I includes two types of cadmium complexes. The Cd(1) atom is coordinated through the octahedral mode by three pairs of the I, N(HMTA), and O(H2O) atoms. The coordination polyhedron of the Cd(2) atom is a distorted tetrahedron (three I atoms and one N atom). The structure contains infinite strips consisting of tetranuclear cyclic fragments joined by the Cd(1) atoms due to the bridging iodine and nitrogen atoms. In structure II, the Cd atom is coordinated through the tetrahedral mode by two iodide ions and the N(HMTA) and O(H2O) atoms. The interaction between the complexes occurs due to hydrogen bonds O-H…N to form supramolecular chains along the direction [010]. In each HMTA molecule, one of four nitrogen atoms is a proton acceptor in the hydrogen bonds, one nitrogen atom is coordinated, and two N atoms are terminal. Compound II in the solid state has photoluminescence with maxima at 443, 470, and 518 nm.

Synthesis and structure of cadmium complexes [Me3BuN] 2 + [CdI4]2−, [Ph3(PhCH2)P] 2 + [Cd2I6]2−, [Me3EtN] n + [CdI3] n − , and [Me3NH] n + [CdI3] n −

Complexes with cadmium-containing anions [Me3BuN]2+[CdI4]2− (I), [Ph3(PhCH2)P]2+[Cd2I6]2−(II), [Me3EtN]n+[CdI3]n−(III), and [Me3NH]n+[CdI3]n−(IV) were synthesized by reacting ammonium and phosphonium iodides with cadmium iodide. In the cations, N and P atoms have a distorted tetrahedral coordination, as Cd atom in the mononuclear [CdI4]2− anion of complex I, too. A centrosymmetric binuclear [Cd2I6]2− anion contains two terminal (t) CdI2 moieties linked to each other by two bridging (br) iodine atoms (Cd-Ibr is 2.8547(3) A; Cd-It are 2.7240(3) A and 2.7241(3) A). Anions of complexes III and IV are polymeric; CdI2 structural units (Cd-It are 2.711(3) A, in III and Cd-It are 2.7366(6) A, in IV) are associated via iodine atoms (Cd-Ibr are 2.853(3) A in III and Cd-Ibr are 2.8472(6) A, 2,8421(6) A in IV) to form polymer chains.

Bis(μ-di-2-pyridyl disulfide-κ3N,S:N′)di-μ3-iodido-di-μ2-iodido-tetracopper(I)

In the centrosymmetric tetra­nuclear title compound, [Cu4I4(C10H8N2S2)2], there are two different CuI atoms with tetra­hedral coordination geometries. One is chelated by a pyridine N atom and an S-donor from one di-2-pyridyl disulfide ligand and coordinated by two I atoms, while the second CuI atom is coordinated by a pyridine-N and three I atoms. Iodine bridges between the CuI atoms form a tetra­nuclear structure.

Synthesis and structure of bismuth complex [n-Bu4N] 2 + [Bi2I8 · 2 Me2S=O]2−

Bismuth complex [Bu4N]2+[Bi2I8 · 2Me2S=O]2−(I) was synthesized by reacting tetrabutylammonium iodide with bismuth iodide. In the cations, an N atom has a distorted tetrahedral coordination (CNC angles change in the range from 107.9(5)° to 111.9(5)°). In the centrosymmetric binuclear anion, octahedral bismuth atoms are bound to each other through the bridging (br) iodine atoms (Bi-Ibr, 3.2779(7) A and 3.3156(9) A), which are coplanar with four terminal (t) iodine atoms (Bi-It, 2.9392(7) A and 2.9534(8) A). Two remaining positions near the bismuth atom are occupied by an iodine atom (Bi-I, 3.0079(8) dimethyl sulfoxide (DMSO) molecule (Bi-O, 2.456(5) A).

Synthesis and structure of antimony iodide complexes: [Ph3MeP] + 2 [SbI5]2−, [Ph3MeP] + 3 [Sb3I12]3−·Me2C=O, [Ph3MeP] + 3 [Sb3I12]3−, and [Ph3MeP] + 3 [Sb2I9]3−

Complexes with antimony-containing anions, [Ph3MeP]+2[SbI5]2− (I), [Ph3MeP]+2[Sb3I12]3− (II), [Ph3MeP]+3[Sb3I12]3− · Me2C=O (III), and [Ph3MeP]+3[Sb2I9]3− (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI3 groups is bound to the central Sb atom through two μ2- and one μ3 iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms.

Synthesis and structure of tetra-p-tolylantimony complexes [(4-MeC6H4)4Sb] 2 + [Hg2I6]2−, [(4-MeC6H4)4Sb] 2 + [HgI4]2−, [(4-MeC6H4)4Sb] 3 + [Sb3I12]2−, and [(4-MeC6H4)4Sb]+[ReO4

Complexes [(4-MeC6H4)4Sb]2+[Hg2I6]2− (I), [(4-MeC6H4)4Sb]2+[HgI4]2− (II), [(4-MeC6H4)4Sb]3+[Sb3I12]2− (III), were synthesized by reactions of tetra-p-tolylantimony iodide with mercury iodide and antimony iodide, respectively. Tetra-p-tolylantimony perrhenate [(4-MeC6H4)4Sb]+[ReO4]− (IV) was prepared from tetra-p-tolylantimony chloride and sodium perrhenate in acetone. Crystal structures of complexes I, II, and IV were determined by X-ray crystallography. Mercury and rhenium atoms have tetrahedral coordinations in these complexes. The Hg-I and Re-O distances in the structures of I, II, and IV vary within 2.7719(13)–2.7908(12)A, 2.7028(3)–2.9163(3) A, and 1.693(3)–1.744(3) A, respectively. Antimony atoms in two crystallographically independent trinuclear centrosymmetric [Sb3I12]2− anions of complex III have an octahedral environment. Each terminal SbI3 fragment (Sb-It, 2.8265(9)–2.8333(10)A) is bound to the central atom through tree bridging iodine atoms (Sb(2)-Ibr, 3.2275(9)–3.3620(10)A). The distances between the central Sb atom and bridging iodine atoms are much shorter (Sb(1)-Ibr, 3.0153(6)–3.0316(6) A; Sb(3)-Ibr, 2.9926(6)–3.0074(6) A).

Synthesis and structure of mercury complexes [H4N] n + [HgI3] n − ,[Me3NH] n + [HgI3] n − ,[Me3NH] 2n + [Hg4I10] n 2− ,[Me4N] n + [HgI3] n − ,[Me3NBu] 2 + [Hg2I6]2−,[Bu4N] 2 + [Hg2I6]2−,[Ph3PAm] 2 + [Hg2I6]2−,[Me4N] 2n + [Hg4I10] n 2− ,[Me3NBu] 2n + [Hg4I10] n 2− , [Bu4N] 2n + [Hg4I10] n 2− , and

The reaction of ammonium and phosphonium iodides R3R′EI (E = N, P; R = H, Me, Bu, Ph; R′= H, Me, Bu, Am) with mercury iodide (I) (red polymorph) in acetone in 1: 1 and 1: 2 ratios (mol/mol) gave mercury complexes [H4N]n+[HgI3]n− (II), [Me3NH]n+[HgI3]n− (III), [Me3NH]2n+[Hg4I10]n2− (IV), [Me4N]n+[HgI3]n− (V), [Me3NBu]2+[Hg2I6]2− (VI), [Bu4N]2+[Hg2I6]2− (VII), [Ph3PAm]2+[Hg2I6]2− (VIII), [Me4N]2n+[Hg4I10]n2− (IX), [Me3NBu]2n+[Hg4I10]n2− (X), [Bu4N]2n+[Hg4I10]n2− (XI), and [Ph3PAm]2n+[Hg4I10]n2− (XII). According to X-ray diffraction data, crystals of I are composed of (HgI2)n polymeric layers in which each mercury atom having a tetrahedral environment (two IHgI angles equal to 103.16° and four angles of 112.72°) is bonded to four neighboring mercury atoms through iodine atoms (I-Hg, 2.818 A). In the tetrahedral cations of the complexes, the nitrogen and phosphorus atoms each have a distorted tetrahedral coordination. In the centrosymmetric binuclear [Hg2I6]2− anions, the mercury atoms having tetrahedral coordination lie in two almost perpendicular planes Hg2I6. In the polymeric anions of II and III, the HgI2 groups are linked to each other through bridging iodine atoms. The crystals of IV consist of tetrahedral trimethylammonium cations disordered over two positions and polymeric [Hg4I10]n−, anions in which the eight-membered Hg4I10 rings are connected to one another through bridging iodine atoms to form a polymeric ribbon.

Synthesis and structure of cadmium complexes [Ph3EtP] 2 + [Cd2I6]2− · Me2C=O, [Ph3(iso-Pr)P] 2 + [CdI4]2−, [Ph3(isoBu)P] 2n + [Cd2I6] n 2− , and [Ph4P] 2 + [Cd2I6]2−

Complexes with cadmium-containing anions [Ph3EtP]2+[Cd2I6]2− (I), [Ph3(iso-Pr)P]2+[CdI4]2− (II), [Ph3(iso-Bu)P]2n+[Cd2I6]n2− (III), and [Ph4P]2+[Cd2I6]2− (IV) were synthesized by the reaction of triphenylalkylphosphonium halides with cadmium iodide. The phosphorus atoms in the cations have a distorted tetrahedral coordination, as well as the cadmium atom in the mononuclear [CdI4]2− anion of complex II. The binuclear [Cd2I6]2− anions contain two terminal (t) CdI2 fragments linked to each other through two bridging (b) iodine atoms (Cd-Ib, 2.8626 and 2.8934 A in I, and 2.8652 and 2.8780 A in IV). The bond lengths Cd-It in I and IV are comparable (2.7245 and 2.7214 A in I and 2.7130 and 2.7252 A in IV). The anions of compound III are polymeric; the structural fragments [Cd2I6]2 (Cd-Ib, 2.8384 A; Cd-It, 2.6739 A) are associated by means of iodine atoms (I(1)…Cd(2A) 2.7973 A).

Phenyltellurium halide complexes of iron cyclopentadienyl dicarbonyl: Synthesis and molecular structures of CpFe(CO)2TePh, CpFe(CO)2TeBr2Ph, CpFe(CO)2TeBrPh(μ-Br)Br3TePh, and PhTeI3(C4H8O)

The bromination of CpFe(CO)2TePh (I) affords the monomeric complex CpFe(CO)2TePhBr2 (II) as the major product and crystals (III), being a cocrystallizate of complexes II and CpFe(CO)2TeBrPh(μ-Br)TePhBr3 (IIIA). Complex IIIA contains a PhTeBr3 molecule, which is weakly bound because of the lone electron pair (LEP) of the bridging bromine atom of molecule II. An analogous weak interaction with the LEP of oxygen in tetrahydrofuran (Te…O 2.893 A) is observed in the PhTeI3(THF) adduct (IV), which is a dimer with two bridging iodine atoms and can be obtained by the crystallization of PhTeI3 from THF. According to the X-ray diffraction data, the Fe-Te distances in compounds II and IIIA (on the average, 2.5 A) differ slightly and are similarly shortened by 0.2 A compared to the sum of the covalent radii of iron and tellurium. The secondary interactions Te…halide and Te…π system of the phenyl ligand are discussed.

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) A in compound II, 3.1961(3) and 3.3108(3) A in complex III), which are coplanar to four terminal (t) iodine atoms (Bi-It 2.9260(7) and 2.9953(6) A in complex II, 2.9206(3) and 2.9786(3) A in complex III). The two remaining positions at the bismuth atom are occupied by the iodine atom (Bi-It 2.8531(7) A in complex II, 2.8984(3) A in complex III) and O atom of the organic molecule (Bi-O 2.747(6) A in complex II, 2.507(3) A in complex III).