Structural diversity in thallium chemistry, IV. Further examples of solid state bromothallate(III) derivatives obtained by employing certain classes of alkyl diammonium cations

Structural Diversity in Thallium Chemistry. Part V

“…Whilst a rich diversity among chlorothallate(III) anions has previously been established [2 ± 9], less has been known with reference to bromothallate(III) anions, with most examples generally being limited to the [TlBr 4 ] À ion, and, to a lesser degree, the [TlBr 6 ] 3À ion [2]. Our recent efforts, however, have expanded this horizon, and, so far, we have reported the isolation of bromothallate(III) salts containing such diverse species as discrete [TlBr 5 ] 2À anions in both regular [1] [10] and highly distorted, axially stretched trigonal bipyramidal forms [11], cis-bromobridged chains composed of [TlBr 5 ] 2À units such that the Tl-atom is hexacoordinate [1], and mixed salts containing various combinations of unassociated anionic moieties like [TlBr 4 ] À Br À [1] [11], [TlBr 4 ] À [TlBr 6 ] 3À [1] [10], and [TlBr 4 ] À [TlBr 6 ] 3À 4 Br À [1].…”

“…For the corresponding bromothallate(III) systems, evidence of halo-bridging in the solid state has been observed only in the room-temperature a-phase of Cs 3 Tl 2 Br 9 [15] and in the N-methylpropane-1,3-diammonium pentabromothallate(III) salt [1], both of which contain, among other species, cis-bromo-bridged [TlBr 5 ] 2À chains made up of corner-shared [TlBr 6 ] 3À octahedra. As a continuation of our investigations, we began using a range of mono-and disubstituted pyridinium cations on the basis that both the chloro-and the bromothallate(III) salts acquired with the unsubstituted pyridinium cation were found to possess the [Tl 2 X 9 ] 3À stoichiometry, although in neither case was a discrete binuclear [Tl 2 X 9 ] 3À unit obtained.…”

Synthesis and Structural Characterization of N,N´- Dipropyl-N,N,N´,N´-tetramethyl-1,2- ethylenediammonium Dichloride and Dibromide

“…Since the symmetry is broken only by the two atom pairs (Cl1/O2 and Cl2/O1) it is possible that, this symmetry break is not detected by CHECKCIF. The bond lengths and angles of the cations are within their normal ranges and can be compared to the corresponding values of {Me 2 BuN(CH 2 ) 2 NMe 2 Bu} 2+ [13] and {Me 2 EtN(CH 2 ) 2 NMe 2 Et} 2+ [10,12]. The packing in 1 · 2H 2 O consists of layers of cations, as shown in Fig.…”

“…Some illustrative examples of such structures contain polyiodidoargentate [2 -5], polyiodidoplumbate [6 -9], and single-strand polytetratelluride [10] anions. The units [SnI 3 ] 3− [11,12], 0932-0776 / 11 / 0700-0755 $ 06.00 c 2011 Verlag der Zeitschrift für Naturforschung, Tübingen · http://znaturforsch.com [SnI 4 ] 2− [12], and [TlBr 5 ] − [13] appear as discrete anions in the solid state, but secondary bonding interactions link them into polynuclear networks.…”

Crystal structure and phase transition in the compound [C6H5CH2NH(CH3)2]TlCl4

“…However a relatively small number of organic-cation thallium complexes has been characterized [5][6][7]. Thallium complexes exhibit a wide range of coordination numbers and geometries (tetrahedral [6,8,9], square pyramidal [9,10], trigonal bipyramid [5,8], octahedral [8,10] and the empirical formula of the complex is not always a reliable indicator for its structure. Some of these compounds exhibit structural phase transitions and interesting physical properties such as ferroelectricity and ionic conduction [11,12].…”