Maciej Bujak

CRYSTAL AND MOLECULAR STRUCTURE OF BIS(N,N-DIMETHYLETHYLENEDIAMMONIUM) HEXADECACHLOROTETRAANTIMONATE(III) [(CH3)2NH(CH2)2NH3]2[Sb4Cl16] AT 295 AND 95 K. A STRUCTURALLY NOVEL [Sb4Cl16]4- ANION

The crystals of a new chloroantimonate(III) with Ν,Ν-dimethylethylenediammonium cation, [(CH3)2NH(CH2)2NH3]2[Sb4Cli6] were obtained by the reaction of antimony trichloride and N,Ndimethylethylenediamine in an aqueous solution of hydrochloric acid. The crystal and molecular structure of this salt was determined at 295 and 95 K. It consists of [(CH3)2NH(CH2)2NH3] cations and structurally novel isolated [Sb4Cli6] anions. The [Sb4Cli6] units are built of four [SbCl5] square pyramids connected with each other by corners. The polyhedra are linked in such a way that the coordination sphere of each antimony(III) atom is composed of three terminal and two bridging chloride atoms. The square pyramids show high variations in their Sb-Cl bond lengths and Cl-Sb-Cl angles. The largest difference of bond lengths 0.744(4) Ä, was found, in the room temperature structure, between Sb-Cl bonds to the terminal axial and bridging equatorial chloride atoms. The Ν,Ν-dimethylethylenediammonium cations are located in cavities formed by the inorganic anions. They are connected to anions by N-H...C1 and C-H...C1 hydrogen bonds. At 95 Κ the N...C1 and C...C1 distances range from 3.168(4) to 3.609(4) Ä. The influence of temperature and the geometry of hydrogen bonds on the distortion of [SbCl5] square pyramids is discussed. The main distortions are connected with Sb-Cl bond lengths and Cl-Sb-Cl angles involving bridging chloride atoms.

Crystal and molecular structure of 1,2,4-triazolium chloride and its salt with antimony trichloride - bis(1,2,4-triazolium) pentachloroantimonate(III)-1,2,4-triazolium chloride

The structures of 1,2,4-triazolium chloride (C2H4N3)Cl and its derivative with antimony trichloride - (C2H4N3)2[SbCl5] · (C2H4N3)Cl containing unsubstituted 1,2,4-triazolium cations were determined. (C2H4N3)Cl crystallizes in the monoclinic system, space group P21/n with the unit cell dimensions at 86 K: a = 9.425(2), b = 8.557(2), c = 11.158(2)Å , β = 95.87(3)°; V = 895.2(3)Å3, Z=8, dc = 1.566, dm = 1.56(2) g·cm-3.At roomtemperature, crystals of (C2H4N3)2- [SbCl5] · (C2H4N3)Cl are orthorhombic, space group P212121, a = 8.318(2), b = 11.381(2), c = 19.931(4) Å, V = 1886.8(7) Å3, Z = 4, dc = 1.917, dm = 1.91(2) g·cm-3. In both crystals the 1,2,4-triazole rings are planar. The anionic sublattice of (C2H4N3)2[SbCl5]·(C2H4N3)Cl consists of polymeric [SbCl5]n 2- zig-zag chains composed of distorted [SbCl6]3- octahedra connected via their vertices and the single Cl- anions. The cavities between the inorganic chains are filled by 1,2,4-triazolium cations. The nature of the distortion of the [SbCl6]3- polyhedra has been studied by examining correlations between the Sb-Cl bond lengths and the strength of hydrogen bonds, which join the anionic sublattice and the organic cations. This study confirms that the deformation of the [SbCl6]3- octahedra is caused by hydrogen bonds.

Synthesis, structural and spectroscopic characterization of the α, ω-diam-monioalkane hexabromorhodates(III) [H3N(CH2)xNH3]2[H502] [RhBr6]Br2 (x = 3, 4): IR spectra of [H5O2]+ ions with weak solid state interactions

The reaction of rhodium(III) chloride trihydrate with 1,3-diaminopropane and 1,4-diaminobutane in concentrated hydrobromic acid results in the formation of the bis(α,ω-diammonioalkane) diaquahydrogen(1+) hexabromorhodate(III) dibromides [H3N(CH2)xNH3]2[H5O2][RhBr6]Br2 (x = 3, 4). Dark red single crystals were obtained by diffusion-controlled crystallization at room temperature. Both compounds crystallize in space group type P1̄ and their structures are closely related. In view of crystal engineering they are inorganic-organic hybrid materials built up from octahedral [RhBr6]3−, simple Br− and flexible chain-like [H3N(CH2)xNH3]2+ ions with the [H5O2]+ and further Br− ions incorporated and thus might be considered as addition compounds [H3N(CH2)xNH3]2[RhBr6]Br ∙ [H5O2]Br. Cationic and anionic moieties in the crystal are held together by a complex system of N-H∙∙∙Br and O-H∙∙∙Br hydrogen bonds. Geometric features of O-H∙∙∙Br hydrogen bonding as well as the pronounced disorder of the [H5O2]+ ions in the diammoniopropane salt indicate the weak association of these species in the solids. Weak association of the ions is also documented by difference ATR-FT-IR spectra of the compounds and related diammonioalkane dibromides that show the stretching modes of the terminal O-H bonds above 3300 cm−1. Further characteristic bands are recognized at ca. 1635 (s), 985 (vs), and 670 (m) cm−1.

Crystal structure of 2,2’-bipyridindiium (2,2’-bipyridyl-κ2N,N’)- tetrabromidorhodate(III) bromide, (C10H10N2)[RhBr4(C10H8N2)]Br, C20H18Br5N4Rh

Abstract C20H18Br5N4Rh, monoclinic, P21/c (no. 14), a = 19.0663(3) Å, b = 9.9988(1) Å, c = 13.5741(2) Å, β = 108.993(2)°, V = 2446.9 Å3, Z = 4, Rgt(F) = 0.0247, wRref(F2) = 0.0563, T = 295 K.

Crystal structure of the layered inorganic-organic hybrid material bis(trans-cyclohexane-1,4-diammonium) hexabromidorhodate(III) bromide monohydrate, C12H34Br7N4ORh

Abstract C12H34Br7N4ORh, monoclinic, P21/c (no. 14), a = 11.3677(5) Å, b = 11.4644(5) Å, c = 19.0407(9) Å, β = 92.443(4)°, V = 2479.2 Å3, Z = 4, Rgt(F) = 0.0290, wRref(F2) = 0.0578, T = 295 K.