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The Unprecedented [S₄ N₂ O₁₀ ]^2- Anion in the Molecular Gold Complexes [Au₂ Br₂ (S₄ N₂ O₁₀ )₂ ] and [Au₂ Cl₂ (S₄ N₂ O₁₀ )₂ ](S₂ O₅ Cl₂ ).

ABSTRACT: The reaction of hexachlorophosphazene, P₃ N₃ Cl₆ , with SO₃ and the gold halides AuCl₃ and AuBr₃ , respectively, leads to the new cyclic anionic tetramer, [S₄ N₂ O₁₀ ]^2- , which is coordinated to Au³⁺ in the dimeric complexes [Au₂ X₂ (S₄ N₂ O₁₀ )₂ ] (X=Cl, Br). The [S₄ N₂ O₁₀ ]^2- anion can be seen as the condensation product of two sulfate anions, [SO₄ ]^2- _, and two amidosulfate anions, [NH₂ SO₃ ]^- .

SUBMITTER: Rennebaum T

PROVIDER: S-EPMC9825932 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

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The Unprecedented [S4 N2 O10 ]2- Anion in the Molecular Gold Complexes [Au2 Br2 (S4 N2 O10 )2 ] and [Au2 Cl2 (S4 N2 O10 )2 ](S2 O5 Cl2 ).

Rennebaum Tobias T van Gerven David D Wickleder Mathias S MS

Chemistry (Weinheim an der Bergstrasse, Germany) 20220919 65

The reaction of hexachlorophosphazene, P3 N3 Cl6 , with SO3 and the gold halides AuCl3 and AuBr3 , respectively, leads to the new cyclic anionic tetramer, [S4 N2 O10 ]2- , which is coordinated to Au3+ in the dimeric complexes [Au2 X2 (S4 N2 O10 )2 ] (X=Cl, Br). The [S4 N2 O10 ]<s ...[more]

PMID: 35975981

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Project description:The structures of seven gold(III) halide derivatives of general formula LAuX 3 (L = methyl-pyridines or di-methyl-pyridines, X = Cl or Br) are presented: tri-chlorido-(2-methyl-pyridine)-gold(III), [AuCl3(C6H7N)], 1 (as two polymorphs 1a and 1b); tri-bromido-(2-methyl-pyridine)-gold(III), [AuBr3(C6H7N)], 2; tri-bromido-(3-methyl-pyridine)-gold(III), [AuBr3(C6H7N)], 3; tri-bromido-(2,4-di-meth-yl-pyridine)-gold(III), [AuBr3(C7H9N)], 4; tri-chlorido-(3,5-di-methylpyridine)-gold(III), [AuCl3(C7H9N)], 5; tri-bromido-(3,5-di-methyl-pyridine)-gold(III), [AuBr3(C7H9N)], 6, and tri-chlorido-(2,6-di-methyl-pyridine)-gold(III), [AuCl3(C7H9N)], 7. Additionally, the structure of 8, the 1:1 adduct of 2 and 6, [AuBr3(C6H7N)]·[AuBr3(C7H9N)], is included. All the structures crystallize solvent-free, and all have Z' = 1 except for 5 and 7, which display crystallographic twofold rotation symmetry, and 4, which has Z' = 2. 1a and 2 are isotypic. The coordination geometry at the gold(III) atoms is, as expected, square-planar. Four of the crystals (1a, 1b, 2 and 8) were non-merohedral twins, and these structures were refined using the 'HKLF 5' method. The largest inter-planar angles between the pyridine ring and the coordination plane are observed for those structures with a 2-methyl substituent of the pyridine ring. The Au-N bonds are consistently longer trans to Br (average 2.059 Å) than trans to Cl (average 2.036 Å). In the crystal packing, a frequent feature is the offset-stacked and approximately rectangular dimeric moiety (Au-X)2, with anti-parallel Au-X bonds linked by Au⋯X contacts at the vacant positions axial to the coordination plane. The dimers are connected by further secondary inter-actions (Au⋯X or X⋯X contacts, 'weak' C-H⋯X hydrogen bonds) to form chain, double chain ('ladder') or layer structures, and in several cases linked again in the third dimension. Only 1b and 7 contain no offset dimers; these structures instead involve C-H⋯Cl hydrogen bonds combined with Cl⋯Cl contacts (1b) or Cl⋯π contacts (7). The packing patterns of seven further complexes LAuX 3 involving simple pyridines (taken from the Cambridge Structural Database) are compared with those of 1-8.

Dataset Information

The Unprecedented [S₄ N₂ O₁₀ ]^2- Anion in the Molecular Gold Complexes [Au₂ Br₂ (S₄ N₂ O₁₀ )₂ ] and [Au₂ Cl₂ (S₄ N₂ O₁₀ )₂ ](S₂ O₅ Cl₂ ).

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