Tris(tetraethylammonium) tris(μ₃-sulfido)bis[bromocopper(I)][dibromocopper(I)]oxomolybdate(VI) acetone solvate

Abstract

The title compound, (NEt4)3[(MoOS3)(CuBr)2(CuBr2)]·(CH3)2CO, contains a central pseudo‐tetrahedral MoOS32− unit with Cu atoms bridging all three S⋯S edges while the Mozdbnd;O bond remains terminal. The Mo, 3 Cu and three triply bridging S atoms occupy seven of the vertices of a distorted cube, the vertex opposite Mo being vacant. Two of the Cu atoms carry one terminal halogen atom each and have distorted trigonal planar coordination, while the third carries two and has distorted tetrahedral coordination. One of these two halogen atoms on the third Cu atom has a secondary interaction with one of the other Cu atoms, so it may be considered as semi‐bridging. Three of the four halogen sites show disorder as a result of minor substitution of Cl for Br, the semi‐bridging halogen atom being purely or essentially Br. This semi‐bridging type of halogen is unprecedented in MOS3Cu3Xn cluster anions.

Synthesis and structural characterization of mixed-metal complexes of CuI with MOS3 cores (M = Mo, W) and of an unusual polymeric AgI/mercaptoimidazole complex with five different AgI coordination environments

“…15 Our own interest in mixedmetal complexes of copper(I) and silver(I) with oxothiometalate a anions and heterocyclic thiones stems from our current research on coordination compounds of coinage metals with these ligands. [16][17][18][19] They show a fascinating variety of structures, both at the local chromophore and in the overall geometry; surprising results are sometimes obtained for the silver complexes, differing from their copper analogues, arising from the very soft character of silver(I) as a Lewis acid centre, which favours coordination by soft bases including sulfur-donating organic ligands and leads to coordination numbers ranging from two to six, and it is important to look for both comparisons and contrasts between related reactions and complexes of the two metals. 17, 18 We now report two additions to the family of mixed-metal complexes containing Cu I with the [MOS 3 ] 2core, and a polymeric mercaptoimidazole/AgI complex that was obtained unexpectedly during attempts to re-crystallize a related new WS 4 Ag 2 cluster complex with the softer [WS 4 ] 2core.…”

“…with three Cu-I bonds of equal length 2.933 A ˚. The three other structures are less symmetrical; ZELSEO 25 has an extra Brligand bridging two of the Cu atoms (both bonds 2.677 A ˚), and NANREZ 26 is similar with m 2 -I (2.942 A ˚), the third Cu ◊ ◊ ◊ X distance in each case being considerably longer (3.349 and 3.290 A ˚, respectively) and not considered to be a covalent bond; the situation in ETEMAR16 …”