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Z. Naturforsch. 2014,
69b, 1315 – 1320
doi:10.5560/ZNB.2014-4067
Amine Complexes of Gold, Part 8: Two Pyridine Derivatives of Gold(i) Thiocyanate
Aminkomplexe des Golds, Teil 8: Zwei Pyridinderivate des Gold(i)-thiocyanats [1]
Institut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Postfach 3329, D-38023 Braunschweig, Germany
Reprint requests to Prof. Dr. P. G. Jones. E-mail:
p.jones@tu-bs.de
Received March 20, 2014 / published online December 19, 2014
Herrn Professor Hubert Schmidbaur zum 80. Geburtstag gewidmet
The reaction between (tht)AuCl (tht = tetrahydrothiophene) and KSCN leads to a mixture possibly consisting of gold(I) thiocyanate and [Au(tht)2]+ [Au(SCN)2]−. This can be treated with pyridine to give the ionic derivative [Au(py)2]+ [Au(SCN)2]− (1), for which the structures of two polymorphs were determined. Orthorhombic polymorph 1a (space group Pbcn, Z = 4) consists of infinite chains of alternating cations and anions with all gold atoms lying on a twofold axis, whereas triclinic polymorph 1b (space group P1̅, Z = 2) contains isolated tetranuclear units cation···anion···anion···cation with inversion symmetry. In both patterns the gold atoms are linked by short aurophilic contacts. Attempts to recrystallize 1b from dichloromethane-diethyl ether led to small quantities of tetrapyridinium bis(dithiocyanatogold(i)) sulfate (2), (pyH)4[Au(SCN)2]2(SO4), which was identified by crystal structure analysis. The cations are associated with the sulfate ions by classical hydrogen bonds; aurophilic interactions between the anions lead to dimers, which further associate to chains by Au···S contacts.
Key words: Gold, Thiocyanate, Amine, Secondary Interactions, Polymorphs