A second polymorph of 1,1,4,4-tetramethylpiperazinium pentabromothallate(III)

Linden, Anthony; Petridis, Alexander; James, B. D.

doi:10.1107/s0108270101019746

Cited by 9 publications

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References 6 publications

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“…3.77 ä) found in the structures of the piperazinium and 2,2'bipyridinium pentabromothallate(III) salts [11], and those in the more regular [TlBr 5 ] 2À species found in the 1,1,4,4-tetramethylpiperazinium, N,N'-diethyltriethylenediammonium and N,N'-diethyl-N,N,N',N'-tetramethylethylene-1,2-diammonium salts in which the longest axial TlÀBr bonds are in the range 2.73 to 2.92 ä [1] [10] [32]. Accordingly, the trigonal bipyramidal geometry of 3 is less distorted than in the structures displaying the very long Tl ¥¥¥ Br interactions and the Br(1)-atom may be described as undergoing −secondary× bonding [33] with the Tl-atom.…”

Section: Results and Discussion ± 31 Tris(pyridinium)bis[tetrabrommentioning

confidence: 99%

Structural Diversity in Thallium Chemistry. Part V

Linden

Petridis

James

2003

Helvetica Chimica Acta

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From thallium(III) bromide solution, the unsubstituted pyridinium cation yields a complex (1) with the [Tl 2 Br 9 ] 3À anionic stoichiometry. The Raman spectrum and single-crystal X-ray crystallographic analysis showed that the salt contains independent [TlBr 4 ] À and bromide anions. A variety of mono-and disubstituted pyridinium cations were also employed in similar syntheses. The 2-bromopyridinium cation gave a salt 2 with [TlBr 5 ] 2À stoichiometry, but the crystal structure revealed very weakly interacting [TlBr 4 ] À and bromide anions with a Tl ¥¥¥ Br À distance of 4.1545(6) ä. The 2-(ammoniomethyl)pyridinium and 2-amino-4-methylpyridinium cations yielded complexes containing [TlBr 5 ] 2À (3) and [TlBr 4 ] À (4) species, respectively, which were confirmed by Raman spectroscopy and X-ray crystallographic analyses. For 3, the [TlBr 5 ] 2À anion has a highly distorted trigonal bipyramidal conformation with one long axial Tl ¥¥¥ Br bond of 3.400(2) ä. Microanalytical results in conjunction with Raman spectra from a further five salts confirmed that they all contain the simple [TlBr 4 ] À anion. NÀH ¥¥¥ Br Hydrogen bonds clearly influence the nature of the anionic species obtained in these systems.

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Section: Results and Discussion ± 31 Tris(pyridinium)bis[tetrabrommentioning

confidence: 99%

Structural Diversity in Thallium Chemistry. Part V

Linden

Petridis

James

2003

Helvetica Chimica Acta

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“…3.77 has been found in the structures of the piperazinium (XXI) and 2,2'-bipyridinium (XXII) salts [5], and a slightly shorter Tl ··· Br distance of 3.40 is present in the [TlBr 5 ] 2À anion of the 2-(ammoniomethyl)pyridinium (XXIII) salt [1]. These contrast with the more regular trigonal bipyramidal [TlBr 5 ] 2À species (longest TlÀBr 2.73 -2.92 ) found in the structures of the N,N'diethyl-N,N,N',N'-tetramethylethylene-1,2-diammonium (XXIV) [2] and N,N'-diethyltriethylenediammonium (diethyl-DABCO; XXV) salts [4] and in both polymorphs of the 1,1,4,4-tetramethylpiperazinium (XXVI) compound [4] [6]. Table 7).…”

Section: Results Andmentioning

confidence: 97%

“…This H-bonding pattern can be described by the graph set motif [32] of C 1 2 (7). Interestingly, although no chiral moieties are present, 3 crystallizes in a polar space group, as did the complex from cation XXV [4], and the absolute structure has been determined by refinement of the absolute structure parameter [15] [16], which converged to a value of À 0.016 (6).…”

Section: Results Andmentioning

confidence: 99%

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Structural Diversity in Thallium Chemistry. Part VI

Linden

Petridis

James

2009

Helvetica Chimica Acta

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New bromothallate(III) complexes have been synthesized using eleven organoammonium cations related to others employed previously. The crystal structure determinations of eight of these have been performed. The diethylenetriammonium cation yields the first compound containing [TlBr 6 ] 3À as the only anionic species, while the N,N,N',N'',N''-pentamethyldiethylenetriammonium cation gave a mixed salt containing discrete [TlBr 4 ] À and Br À ions, in which the [TlBr 4 ] À unit does not participate in hydrogen bonding. In the pyrazolinium mixed salt, both the [TlBr 4 ] À and Br À ions are hydrogen-bonded to cations and disposed in an arrangement similar to a [Tl 2 Br 9 ] 3À unit. The triethylenediammonium dication gives a compound in which a highly distorted trigonal bipyramidal [TlBr 5 ] 2À system is present, while the 1benzylpiperazinium compound also shows a very weak [TlBr 4 ] À and Br À interaction. Six other monovalent cations provided [TlBr 4 ] À derivatives that were characterized either crystallographically or via their Raman spectra. In a comprehensive structural summary, the various interactions between cations and bromothallate(III) anionic groupings, giving rise to the structural diversity described in this and previous reports, are discussed in terms of the cation charge, quaternization and steric influence, NÀH ··· Br hydrogen bonding, and secondary bonds present in the compounds.

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“…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].…”

Section: Introductionmentioning

confidence: 99%

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

Abdi¹,

Hadrich

Zouari³

2008

Cryst. Res. Technol.

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The N-N dimethyl benzylammonium tetrachlorothallate (III) [C 6 H 5 CH 2 NH(CH 3 ) 2 ]TlCl 4 crystallizes in the monoclinic system P2 1 /n at room temperature with the following unit cell dimensions: a = 7.725 (3) -tetrahedra alternate with planes of [C 6 H 5 CH 2 NH(CH 3 ) 2 ] + cations. The cohesion of the atomic arrangement is ensured by hydrogen bonds N-H…Cl. Differential scanning calorimetric and optical birefringence measurements reveals a phase transition at T = 339K. Raman spectroscopic study and dielectric measurements were performed to discuss the mechanism of the phase transition.

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A second polymorph of 1,1,4,4-tetramethylpiperazinium pentabromothallate(III)

Cited by 9 publications

References 6 publications

Structural Diversity in Thallium Chemistry. Part V

Structural Diversity in Thallium Chemistry. Part V

Structural Diversity in Thallium Chemistry. Part VI

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

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A second polymorph of 1,1,4,4-tetramethylpiperazinium pentabromothallate(III)

Cited by 9 publications

References 6 publications

Structural Diversity in Thallium Chemistry. Part V

Structural Diversity in Thallium Chemistry. Part V

Structural Diversity in Thallium Chemistry. Part VI

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

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