V. B. Logvinova

COMPLEXES OF BISMUTH(III) WITH AMINOPOLYCARBOXYLIC ACIDS. CRYSTAL STRUCTURES OF GUANIDINIUM AQUA(ETHYLENEDIAMINETETRAACETATO)BISMUTHATE(lll) AND AMINOGUANIDINIUM ETHYLENEDIAMINETETRAACETATOBISMUTHATE(III)

In the crystal structure of guaninidium aqua(ethylenedi9minetetraacetato)bismuthate(III), the ethylenediaminetetraacetato tetraanion chelates to the bismuth atom through its two amino and four carboxyl oxygen atoms. A carboxylate bridge [Bi-0 = 2.694(4) A] links adjacent water-coordinated [Bi-Owater = 2.673(4) A] ethylenediaminetetraacetatobismuthate(III) anions into a helical linear chain. The bismuth atom is eight-coordinate in a square-antiprismatic environment. The bismuth atom shows dodecahedral coordination in aminoguanidinium ethylenediaminetetraacetatobismuthate(III). The crystal structure features a short carboxyl bridge [Bi-O = 2.657(4) A] that links the bismuthate anions into a dinuclear entity; adjacent entities are linked by a long carbonyl bridge [Bi-0 = 2.931(4) A] into a linear chain. In both ethylenediaminetetraacetatobismuthates(III), the lone-pair of electrons is stereochemical^ inert.

Monomeric complex [HfF5(H2O)2]− anion in the crystal structure of 4-amino-1,2,4-triazolium pentafluorohafnate trihydrate: Synthesis and X-ray study

For the first time, hybrid organic-inorganic 4-amino-1,2,4-triazolium fluorohafnate of the composition (C2H5N4)[HfF5(H2O)2]·H2O is synthesized and its crystal structure is determined. The formation of a new type of a fluoride monomeric pentagonal bipyramid complex [HfF5(H2O)2]− anion with five F atoms and two H2O molecules is revealed.

New structure types of polymeric chain anions in the crystal structures of complex zirconium fluorides

The crystal structures of complex zirconium fluorides (C2H5N4)2Zr2F10·H2O and (H3O)3(NEt4)2Zr4F21·3H2O synthesized for the first time are determined. The formation of new structure types of polymeric chain complex anions is found in them. Two crystallographically independent zigzag-like polymeric chains ∞(ZrF5)− composed of pentagonal bipyramidal polyhedra of Zr atoms sharing F-F edges form a polymeric chain complex anion in the (C2H5N4)2Zr2F10·H2O structure. The polymeric chain complex anion in the (H3O)3(NEt4)2Zr4F21·3H2O structure is formed of tetranuclear -Zr(1)F7-Zr(2)F8-Zr(3)F8-Zr(4)F7- moieties in which Zr(2)F8 and Zr(3)F8 polyhedra are linked by a common thiangular face and Zr(1)F7 and Zr(4)F7 polyhedra are bonded to Zr(2)F8 and Zr(3)F8 polyhedra by common edges. In the polymeric chain of the complex [Zr4F21]5− anion the tetranuclear fragments share edges. The structural fragments of the compounds are combined in three-dimensional units by a branched system of N-H⋯O, N-H⋯F, and O-H⋯F hydrogen bonds.

CRYSTAL STRUCTURE OF MONOCLINIC MODIFICATIONS OF ZIRCONIUM AND HAFNIUM TETRAFLUORIDE TRIHYDRATES

The monoclinic modification of ZrF4·3H2O, isostructural to HfF4·3H2O, is synthesized and structurally studied for the first time. Unlike the triclinic modification of ZrF4·3H2O with a dimeric structure, the synthesized compound has a polymer structure formed from infinite chains composed of ZrF6(H2O)2 groups sharing F…F edges. The crystal structure of HfF4·3H2O, previously determined by the photo method, is refined. The refined data on the geometric characteristics of the coordination polyhedron of the Hf atom and the system of hydrogen bonds in the structure are obtained.

Crystal structures of layered zirconium pentafluorides of methylammonium, glycinium, and β-alanine

For the first time, new hybrid organic-inorganic layered zirconium pentafluorides of methylammonium, glycinium, and β-alanine with the composition (CH3NH3)ZrF5·0.5H2O, (H3NCH2COOH)ZrF5·2H2O, and (H3N(CH2)2COOH)ZrF5 are synthesized and their structures are analyzed. In the studied compounds, CN of the Zr atom is 8, and its coordination polyhedron represents a dodecahedron sharing its 6 vertex with three neighboring Zr polyhedra. The Zr dodecahedra are joined with each other in planar netlike anion layers of the composition ∞2[ZrF5]−. The anion layers are hydrogen bonded into a three-dimensional structure by H2O cations and molecules.

Synthesis and Study of Hybrid Organic-Inorganic Glycinium Fluorozirconates

Hybrid organic-inorganic zirconium fluoride complexes, (GlyH)ZrF5, (GlyH)ZrF5 · 2H2O, and (GlyH)2ZrF6, have been synthesized for the first time. They were studied by X-ray powder diffraction and thermal analysis, as well as IR and Raman spectroscopy. The structure of the fluorozirconates was inferred from IR and Raman spectroscopic data.

Crystal structure of rubidium and cesium tetrafluoroindate(III) dihydrates

The crystal structures of isostructural fluoride complexes of indium(III) M[InF4(H2O)2] (M = Rb, Cs) crystallizing in the monoclinic system, space group I2/a, are studied. The structures of M[InF4(H2O)2] (M = Rb, Cs) are formed of isolated centrosymmetric complex [InF4(H2O)2]– anions with the trans-position of coordinated H2O molecules and Rb+, respectively Cs+, cations. The In atom in the complex [InF4(H2O)2]– anion is surrounded by four F atoms and two oxygen atoms of coordinated H2O molecules, forming the coordination polyhedron as a slightly distorted octahedron. Via a system of hydrogen O–H⋯F bonds the polyhedra of In atoms are arranged in a three-dimensional framework with the cations located in its channels.

Mixed-ligand fluorooxalate complex compounds of indium(III) M2[InF3(C2O4)H2O] (M = K, Rb): Synthesis and crystal structure

Isostructural fluorooxalate complex compounds of indium(III) M2[InF3(C2O4)H2O] (M = K, Rb), being the first representatives of a new class of mixed-ligand fluoro-containing complex compounds of indium(III) are synthesized and structurally studied for the first time. The crystal structures of M2[InF3(C2O4)H2O] (M = K, Rb) are formed of K+ cations (Rb+ respectively) and complex [InF3(C2O4)H2O]2– anions. The indium atom in the complex anion is surrounded by four F atoms, two of which are bridging, the oxygen atom of the coordinated H2O molecule, and two oxygen atoms of the bis-bidentate (tetradentate) oxalate group. The coordination polyhedron of the indium atom (CN 7) is a pentagonal bipyramid. Via alternating double bridging F atoms and tetradentate bridging C2O4 group, the In(III) atom polyhedra are arranged in polymers chains. Via hydrogen O–H⋯F bonds the chains are organized in layers. Between the layers, the K+ or Rb+ cations are located, which strengthen the crystal structure.

Structure of polymorphs of complex zirconium and hafnium fluorides with the 4-amino-1,2,4-triazolium cation: (C2H5N4)2MF6 (M = Zr, Hf, ZrxHf1–x)

New hybrid organic-inorganic complex zirconium and hafnium fluorides with the 4-amino-1,2,4-triazolium cation (C2H5N4)2MF6 (M = Zr, Hf, ZrxHf1–x), which crystallize in two polymorphs (monoclinic (P21/n, Z = 4) and triclinic (P