Crystal structures of sixteen phosphane chalcogenide complexes of gold(I) chloride, bromide and iodide.
Acta Crystallogr E Crystallogr Commun
; 80(Pt 1): 34-49, 2024 Jan 01.
Article
em En
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| ID: mdl-38312159
ABSTRACT
The structures of 16 phosphane chalcogenide complexes of gold(I) halides, with the general formula R 1 3- nR 2 nPEAuX (R 1 = t-butyl; R 2 = isopropyl; n = 0 to 3; E = S or Se; X = Cl, Br or I), are presented. The eight possible chlorido derivatives are 1a, n = 3, E = S; 2a, n = 2, E = S; 3a, n = 1, E = S; 4a, n = 0, E = S; 5a, n = 3, E = Se; 6a, n = 2, E = Se; 7a, n = 1, E = Se; and 8a, n = 0, E = Se, and the corresponding bromido derivatives are 1b-8b in the same order. However, 2a and 2b were badly disordered and 8a was not obtained. The iodido derivatives are 2c, 6c and 7c (numbered as for the series a and b). All structures are solvent-free and all have Z' = 1 except for 6b and 6c (Z' = 2). All mol-ecules show the expected linear geometry at gold and approximately tetra-hedral angles P-E-Au. The presence of bulky ligands forces some short intra-molecular contacts, in particular Hâ¯Au and Hâ¯E. The Au-E bond lengths have a slight but consistent tendency to be longer when trans to a softer X ligand, and vice versa. The five compounds 1a, 5a, 6a, 1b and 5b form an isotypic set, despite the different alkyl groups in 6a. Compounds 3a/3b, 4b/8b and 6b/6c form isotypic pairs. The crystal packing can be analysed in terms of various types of secondary inter-actions, of which the most frequent are 'weak' hydrogen bonds from methine hydrogen atoms to the halogenido ligands. For the structure type 1a, Hâ¯X and Hâ¯E contacts combine to form a layer structure. For 3a/3b, the packing is almost featureless, but can be described in terms of a double-layer structure involving borderline Hâ¯Cl/Br and Hâ¯S contacts. In 4a and 4b/8b, which lack methine groups, Cmeth-yl-Hâ¯X contacts combine to form layer structures. In 7a/7b, short C-Hâ¯X inter-actions form chains of mol-ecules that are further linked by association of short Auâ¯Se contacts to form a layer structure. The packing of compound 6b/6c can conveniently be analysed for each independent mol-ecule separately, because they occupy different regions of the cell. Mol-ecule 1 forms chains in which the mol-ecules are linked by a Cmethineâ¯Au contact. The mol-ecules 2 associate via a short Seâ¯Se contact and a short Hâ¯X contact to form a layer structure. The packing of compound 2c can be described in terms of two short Cmethine-Hâ¯I contacts, which combine to form a corrugated ribbon structure. Compound 7c is the only compound in this paper to feature Auâ¯Au contacts, which lead to twofold-symmetric dimers. Apart from this, the packing is almost featureless, consisting of layers with only translation symmetry except for two very borderline Auâ¯H contacts.
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MEDLINE
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En
Revista:
Acta Crystallogr E Crystallogr Commun
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Alemanha
País de publicação:
ENGLAND
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ESCOCIA
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GB
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GREAT BRITAIN
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INGLATERRA
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REINO UNIDO
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SCOTLAND
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UK
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UNITED KINGDOM