Crystal structures of six miscellaneous products arising from the oxidation of precursors <i>R</i> ¹ <i>R</i> ² <i>R</i> ³P<i>E</i>Au<i>X</i> (<i>R</i> = <i>tert</i>-butyl or isopropyl; <i>E</i> = S or Se; <i>X</i> =

Compound <b>1</b>, (disulfane-1,2-di-yl)bis-(<i>tert</i>-butyl-diiso-propyl-phospho-nium) bis-[tetra-chlorido-aurate(III)], ( ^<i>t</i> Bu ^<i>i</i> Pr₂P)₂S₂·[AuCl₄]₂, contains the first structurally characterized dication of the form {(<i>R</i> ₃P)₂ <i>E</i>}₂ ²⁺. The ions are linked by S⋯Cl contacts and C-H_methine⋯Cl hydrogen bonds to form ribbons of residues parallel to the <i>a</i> axis. Compound <b>2</b> is bis-(di-<i>tert</i>-butyl-iso-propyl-phosphine sulfide-κ<i>S</i>)gold(I) triiodide/di-iodido-aurate(I)(0.905/0.095), [Au(C₁₁H₂₅PS)₂][AuI₂]_0.095(I₃)_0.905, or [( ^<i>t</i> Bu₂ ^<i>i</i> PrPS)₂Au]I₃ with 9.5% of the triiodide replaced by di-iodido-aurate(I). Chains of alternating anions and cations parallel to [110] are formed by two S⋯I contacts. Compound <b>3</b> is bis-(<i>tert</i>-butyl-diiso-propyl-phosphine sulfide-κ<i>S</i>)gold(I) triiodide/di-iodido-aurate(I)(0.875/0.125), [Au(C₁₀H₂₃PS)₂][AuI₂]_0.125(I₃)_0.875 or [( ^<i>t</i> Bu ^<i>i</i> Pr₂PS)₂Au]I₃ with 12.5% of the triiodide replaced by di-iodo-aurate(I). Chains parallel to [101] are formed by two S⋯I contacts. Compound <b>4</b>, bis-(di-<i>tert</i>-butyl-iso-propyl-phosphine sulfide-κ<i>S</i>)gold(I) hepta-iodide, [Au(C₁₁H₂₅PS)₂]I₇ or [( ^<i>t</i> Bu₂ ^<i>i</i> PrPS)₂Au]I₃·2I₂, is formally the bis-diiodine adduct of <b>3</b>, uncontaminated by di-iodido-aurate(I). The cations and anions display crystallographic twofold symmetry. The unbranched I₇ ^- groups, I-I⋯I-I-I⋯I-I, are bent at the third and fifth atoms. The anions are linked by two S⋯I contacts to form a layer structure parallel to the <i>bc</i> plane. In all three structures <b>2</b>-<b>4</b>, there are also weak C-H_methine⋯I contacts. Compound <b>5</b>, di-bromido-(di-<i>tert</i>-butyl-dithio-phosphato-κ² <i>S</i>,<i>S</i>')gold(III), [AuBr₂(C₈H₁₈PS₂)] or [AuBr₂( ^<i>t</i> Bu₂PS₂)], contains a four-membered chelate ring. It crystallizes with imposed mirror symmetry. An S⋯Br contact links the mol-ecules to form corrugated layers parallel to the <i>bc</i> plane. In compound <b>6</b>, di-<i>tert</i>-but-yl{[di-<i>tert</i>-but-yl(hy-droxy)phosphan-yl]diselan-yl}phosphine oxide tetra-bromido-aurate(III), (C₁₆H₃₇O₂P₂Se₂)[AuBr₄] or [( ^<i>t</i> Bu₂OPSe)₂H][AuBr₄], the cation has a central diselenide unit, and also displays an intra-cationic hydrogen bond O-H⋯O. Two Se⋯Br contacts link the residues to form zigzag chains parallel to [201]. The problem of determining whether an <i>E</i>⋯<i>X</i> contact (<i>E</i> = chalcogen, <i>X</i> = halogen) represents a halogen bond or a chalcogen bond is discussed.