ABSTRACT
Six new inorganic-organic salts, all containing iodobismuthate anions and d-metal coordination cations, were synthesized solvothermally from reactions of bismuth iodide, a transition metal (M) nitrate salt (M = Co, Fe or Zn), and a heterocyclic, chelating organic ligand: 1,10-phenanthroline (1,10-phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (TMphen), or 2,2':6',2''-terpyridine (tpy). All six compounds were structurally analyzed by single crystal X-ray diffraction, including variable temperature crystallographic analysis to monitor for structural changes. Furthermore, those containing novel anions and achieved in high yield were additionally characterized by solid-state UV visible spectroscopy at room temperature. [Co(1,10-phen)(3)][Bi(3)I(11)] (1), [Fe(1,10-phen)(3)][Bi(3)I(11)] (2), and [Zn(1,10-phen)(3)][Bi(3)I(11)] (3) are isostructural. They crystallize in the monoclinic space group P2(1)/n and contain the unprecedented iodobismuthate anion, [Bi(3)I(11)](2-), which exhibits near D(3h) symmetry and has an unusual arrangement of three cis face-sharing BiI(6) octahedra. [Co(TMPhen)(3)](2)[Bi(2)I(9)][I] (4), which crystallizes in the trigonal space group P-31c, and [Co(tpy)(2)](2)[Bi(2)I(9)][I] (5) and [Zn(tpy)(2)](2)[Bi(2)I(9)][I] (6), which are isostructural and crystallize in the monoclinic space group C2/c, contain the discrete binuclear [Bi(2)I(9)](3-) anion, common in previously reported iodobismuthate compounds. In addition they contain unusual isolated I(-) anions, which are rarely encountered in iodobismuthate phases. Compounds 1-6 show constitutional similarities while utilizing different organic ligands and illustrate the sensitive dependence of reaction conditions on the identity of the halometalate anion formed. Additionally, all six compounds and the starting material BiI(3) are thermochromic; the origin of this behavior is spectroscopically and crystallographically investigated.
ABSTRACT
A new heterometallic iodoplumbate was synthesized solvothermally. The complex, [Co(phen)3][Pb3Cu6I16].C2H5OH, contains a novel Pb3Cu6I16 net made up of linked Pb3I11 and Cu6I11 clusters. The clusters form a BN-type layer, where the Pb3I11 and Cu6I11 clusters take the place of B and N. The layers, which are separated by [Co(phen)3]2+ cations, contain cavities in which ethanol molecules are located.
ABSTRACT
Crystals of the title compounds were grown solvothermally in an ethanol-water solvent mixture using ruthenium triiodide, 2,2'-bipyridine and bismuth triiodide as starting materials. Tetrakis[2-(2-pyridyl)pyridinium] tetra-mu3-iodo-hexa-mu2-iodo-dodecaiodohexabismuthate, (C10H9N2)4[Bi6I22], crystallizes in the triclinic space group P-1 and is the major reaction product. The asymmetric unit of this compound consists of half a centrosymmetric [Bi6I22]4- anion and two independent 2,2'-bipyridinium cations. The minor product of the reaction is bis[tris(2,2'-bipyridine)ruthenium(II)] di-mu4-iodo-octa-mu2-iodo-dodecaiodohexabismuthate, [Ru(C10H8N2)3]2[Bi6I22], which also crystallizes in the triclinic space group P-1. For this compound, the asymmetric unit consists of one full [Ru(2,2'-bipyridine)3]2+ cation and half a centrosymmetric [Bi6I22]4- anion. Although both compounds contain a centrosymmetric [Bi6I22]4- anion, the polyhedral arrangement of the distorted BiI6 octahedra in the two compounds is quite different, and the anion of the latter compound has not previously been observed in iodobismuthate chemistry.
