Crystal structures of six miscellaneous products arising from the oxidation of precursors R (1) R (2) R (3)PEAuX (R = tert-butyl or isopropyl; E = S or Se; X = Cl, Br or I).

Compound 1, (disulfane-1,2-di-yl)bis-(tert-butyl-diiso-propyl-phospho-nium) bis-[tetra-chlorido-aurate(III)], ( (t) Bu (i) Pr(2)P)(2)S(2)·[AuCl(4)](2), contains the first structurally characterized dication of the form {(R (3)P)(2) E}(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 a axis. Compound 2 is bis-(di-tert-butyl-iso-propyl-phosphine sulfide-κS)gold(I) triiodide/di-iodido-aurate(I)(0.905/0.095), [Au(C(11)H(25)PS)(2)][AuI(2)](0.095)(I(3))(0.905), or [( (t) Bu(2) (i) PrPS)(2)Au]I(3) 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 3 is bis-(tert-butyl-diiso-propyl-phosphine sulfide-κS)gold(I) triiodide/di-iodido-aurate(I)(0.875/0.125), [Au(C(10)H(23)PS)(2)][AuI(2)](0.125)(I(3))(0.875) or [( (t) Bu (i) Pr(2)PS)(2)Au]I(3) with 12.5% of the triiodide replaced by di-iodo-aurate(I). Chains parallel to [101] are formed by two S⋯I contacts. Compound 4, bis-(di-tert-butyl-iso-propyl-phosphine sulfide-κS)gold(I) hepta-iodide, [Au(C(11)H(25)PS)(2)]I(7) or [( (t) Bu(2) (i) PrPS)(2)Au]I(3)·2I(2), is formally the bis-diiodine adduct of 3, uncontaminated by di-iodido-aurate(I). The cations and anions display crystallographic twofold symmetry. The unbranched I(7) (-) 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 bc plane. In all three structures 2-4, there are also weak C-H(methine)⋯I contacts. Compound 5, di-bromido-(di-tert-butyl-dithio-phosphato-κ(2) S,S')gold(III), [AuBr(2)(C(8)H(18)PS(2))] or [AuBr(2)( (t) Bu(2)PS(2))], 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 bc plane. In compound 6, di-tert-but-yl{[di-tert-but-yl(hy-droxy)phosphan-yl]diselan-yl}phosphine oxide tetra-bromido-aurate(III), (C(16)H(37)O(2)P(2)Se(2))[AuBr(4)] or [( (t) Bu(2)OPSe)(2)H][AuBr(4)], 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 E⋯X contact (E = chalcogen, X = halogen) represents a halogen bond or a chalcogen bond is discussed.