Tetrakis[2-(2-Pyridyl)Pyridinium] Tetra-μ\u3csub\u3e3\u3c/sub\u3e-Iodo-Hexa-μ\u3csub\u3e2\u3c/sub\u3e-Iodo-Dodecaiodohexabismuthate and Bis[Tris(2,2\u27-Bipyridine)Ruthenium(II)] Di-μ\u3csub\u3e4\u3c/sub\u3e-Iodo-Octa-μ\u3csub\u3e2\u3c/sub\u3e-Iodo-Dodecaiodohexabismuthate

Crystals of the title compounds were grown solvothermally in an ethanol-water solvent mixture using ruthenium triiodide, 2,2\u27-bipyridine and bismuth triiodide as starting materials. Tetrakis[2-(2-pyridyl)pyridinium] tetra-3-iodo-hexa-2-iodo-dodecaiodohexabismuthate, (C10H9N2)4[Bi6I22], crystallizes in the triclinic space group P 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\u27-bipyridinium cations. The minor product of the reaction is bis[tris(2,2\u27-bipyridine)ruthenium(II)] di-4-iodo-octa-2-iodo-dodecaiodohexabismuthate, [Ru(C10H8N2)3]2[Bi6I22], which also crystallizes in the triclinic space group P. For this compound, the asymmetric unit consists of one full [Ru(2,2\u27-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. Formula: (C10H9N2)4[Bi6I22] and [Ru(C10H8N2)3][Bi6I22

The Synthesis and Crystal Structure of [BiI\u3csub\u3e2\u3c/sub\u3e(tpy)\u3csub\u3e2\u3c/sub\u3e][Bi\u3csub\u3e2\u3c/sub\u3eI\u3csub\u3e7\u3c/sub\u3e(tpy)]: A New Metal Halide Material

[BiI2(tpy)2][Bi2I7(tpy)] (1) (tpy = 2,2′:6′2′′-terpyridine), a new compound containing a discrete bismuth halide anion, has been synthesized solvothermally and characterized by single crystal X-ray diffraction. The solvothermal reaction between BiI3, Zn(NO3)2 · 6H2O, and 2,2′:6′2′′-terpyridine in an ethanol/water solvent mixture resulted in the title compound. The anion and cation of this compound both contain bismuth, iodide ligands, and the organic ligand. The anion is composed of two face-sharing bismuth polyhedra, one of which is coordinated in a tridentate fashion to a disordered tpy ligand; and the remaining coordination sites at each Bi center are occupied by iodide ligands. The cation of the compound is a distorted, eight-coordinate polyhedron with a bismuth center, two iodide ligands, and six nitrogen atoms from two, tridentate tpy ligands. [BiI2(tpy)2][Bi2I7(tpy)] crystallizes in the triclinic space group P 1¯¯¯ with the following lattice parameters: a = 10.0744(5) Å, b = 16.6115(8) Å, c = 18.5333(9) Å, α = 102.6490(10)°, β = 101.0850(10)°, and γ = 93.9160(10)°

Syntheses and Crystal Structures of New Chain-Containing Iodometallate Compounds: [H1,10-phen](H\u3csub\u3e2\u3c/sub\u3eO)\u3csub\u3e1.41\u3c/sub\u3e[AgI\u3csub\u3e2\u3c/sub\u3e], [H1,10-phen](H\u3csub\u3e2\u3c/sub\u3eO)\u3csub\u3e1.42\u3c/sub\u3e[CuI\u3csub\u3e2\u3c/sub\u3e]; [Co(tpy)\u3csub\u3e2\u3c/sub\u3e][Bi\u3csub\u3e2\u3c/sub\u3eI\u3csub\u3e8\u3c/sub\u3e], [Fe(tpy)\u3csub\u3e2\u3c/sub\u3e][Bi\u3csub\u3e2\u3c/sub\u3eI\u3csub\u3e8\u3c/sub\u3e]; [Co(1,10-phen)\u3csub\u3e3\u3c/sub\u3e][Pb\u3csub\u3e3\u3c/sub\u3eI\u3csub\u3e8\u3c/sub\u3e]·H\u3csub\u3e2\u3c/sub\u3eO, and [Fe(1,10-phen)\u3csub\u3e3\u3c/sub\u3e][Pb\u3csub\u3e3\u3c/sub\u3eI\u3csub\u3e8\u3c/sub\u3e]·\u3csub\u3e0.5\u3c/sub\u3e(H\u3csub\u3e2\u3c/sub\u3eO)

Three pairs of novel, isostructural polymeric iodometallate compounds, [H1,10-phen](H2O)1.41[AgI2] (1) ([H1,10-phen]+ = [1,10-phenanthrolinium]+), [H1,10-phen](H2O)1.42[CuI2] (2), [Co(tpy)2][Bi2I8] (3) (tpy = 2,2′:6′2″-terpyridine), [Fe(tpy)2][Bi2I8] (4), [Co(1,10-phen)3][Pb3I8]·H2O (5) (1,10-phen = 1,10-phenanthroline), and [Fe(1,10-phen)3][Pb3I8]·0.5(H2O) (6) have been synthesized solvothermally and characterized by single crystal X-ray diffraction. Compounds 1 and 2 are isostructural and crystallize in the orthorhombic space group Cmma with lattice parameters of a = 6.7063(7) Å, b = 17.6051(18) Å, c = 12.7088(13) Å and a = 6.5770(3) Å, b = 17.5245(8) Å, c = 12.5515(6) Å, respectively. The polymeric anionic chains in 1 and 2 are formed by edge-sharing MI4 (M = Ag, Cu) tetrahedra. Compounds 3 and 4 are isostructural and crystallize in the monoclinic space group P21/n with lattice parameters of a = 16.5085(7) Å, b = 16.0392(7) Å, c = 16.5115(7) Å, β = 97.4710(10)° and a = 16.4478(6) Å, b = 16.0645(6) Å, c = 16.4498(6) Å, β = 97.4490(10)°, respectively. Both structures contain the first observed, face-sharing [Bi2I8]2−anion cluster that is linked via corner sharing into infinite zig-zag anionic chains. Compounds 5 and 6 are isostructural and crystallize in the triclinic space group P1¯ with lattice parameters of a = 11.8798(5) Å, b = 15.2805(7) Å, c = 16.1889(7) Å, α = 63.9240(10)°, β = 74.0420(10)°, γ = 73.2540(10)° and a = 11.7889(5) Å, b = 15.3224(6) Å, c = 16.2584(6) Å, α = 64.1920(10)°, β = 73.5600(10)°, and γ = 73.7120(10)°, respectively. Compounds 5 and 6contain infinite [Pb3I8]2− chains in which the three crystallographically unique Pb2+ ions are found in sets of three trans face-sharing octahedra. These face-sharing trimers are observed in pairs that share three edges, and the pairs are further connected into 1-D chains by edge sharing with neighboring 2 × 3 units

Layered Heterometallic Iodoplumbate Containing a Novel Pb\u3csub\u3e3\u3c/sub\u3eCu\u3csub\u3e6\u3c/sub\u3eI\u3csub\u3e16\u3c/sub\u3e Net: Structure and Optical Properties

A new heterometallic iodoplumbate was synthesized solvothermally. The complex, [Co(phen)3]2[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

Structural Diversity and Thermochromic Properties of Iodobismuthate Materials Containing d-Metal Coordination Cations: Observation of a High Symmetry [Bi\u3csub\u3e3\u3c/sub\u3eI\u3csub\u3e11\u3c/sub\u3e]\u3csup\u3e2-\u3c/sup\u3e Anion and of Isolated I\u3csup\u3e−\u3c/sup\u3e Anions

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][Bi3I11] (1), [Fe(1,10-phen)3][Bi3I11] (2), and [Zn(1,10-phen)3][Bi3I11] (3) are isostructural. They crystallize in the monoclinic space group P21/n and contain the unprecedented iodobismuthate anion, [Bi3I11]2−, which exhibits near D3h symmetry and has an unusual arrangement of three cis face-sharing BiI6 octahedra. [Co(TMPhen)3]2[Bi2I9][I] (4), which crystallizes in the trigonal space group P-31c, and [Co(tpy)2]2[Bi2I9][I] (5) and [Zn(tpy)2]2[Bi2I9][I] (6), which are isostructural and crystallize in the monoclinic space group C2/c, contain the discrete binuclear [Bi2I9]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 BiI3 are thermochromic; the origin of this behavior is spectroscopically and crystallographically investigated

Structural Diversity and Thermochromic Properties of Iodobismuthate Materials Containing d-Metal Coordination Cations: Observation of a High Symmetry [Bi3I11]2− Anion and of Isolated I− Anions

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][Bi3I11] (1), [Fe(1,10-phen)3][Bi3I11] (2), and [Zn(1,10-phen)3][Bi3I11] (3) are isostructural. They crystallize in the monoclinic space group P21/n and contain the unprecedented iodobismuthate anion, [Bi3I11]2−, which exhibits near D3h symmetry and has an unusual arrangement of three cis face-sharing BiI6 octahedra. [Co(TMPhen)3]2[Bi2I9][I] (4), which crystallizes in the trigonal space group P-31c, and [Co(tpy)2]2[Bi2I9][I] (5) and [Zn(tpy)2]2[Bi2I9][I] (6), which are isostructural and crystallize in the monoclinic space group C2/c, contain the discrete binuclear [Bi2I9]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 BiI3 are thermochromic; the origin of this behavior is spectroscopically and crystallographically investigated