d8⋯d10 RhI⋯AuI interactions in Rh 2,6-xylylisocyanide complexes with [Au(CN)2]−: bond analysis and crystal effects

Abstract

The well-known [RhL₄]_n(anion)_n structures, with Rh^I⋯Rh^I d⁸⋯d⁸ interactions, are replaced by others with Rh^I⋯Au^I d⁸⋯d¹⁰ interactions such as [{RhL₄}{Au(CN)₂}] (L = 2,6-xylylisocyanide) or [{RhL₄}{Au(CN)₂}{RhL₄}{Au₂(CN)₃}·4(CHCl₃)]_∞ when the anion is [Au(CN)₂]⁻. Orbital (Rh⋯Au), coulombic, and inter-unit π–π aryl stacking interactions stabilize these crystal structures.