Neil R. Brooks

Dichloro­bis[1-methyl­imidazoline-2(3H)-thione]cadmium(II)

In the title complex, [CdCl2(C4H6N2S)2], the Cd atom has a distorted tetraxadhedral coordination geometry, with two Cl− and two monodentate neutral thione ligands bonded through S. There are intraxadmolecular N—H⋯Cl and interxadmolecular N—H⋯S hydrogen bonds, generating centrosymmetric dimers.

A second tetragonal polymorph of bis­(tetra-n-butyl­ammonium) tetrakis­[chloro(μ3-sulfido)­copper(I)]­molybdate(VI)

The title compound, bisxad(tetra-n-butylxadammonium) tetraxadchloroxadtetra-μ3-sulfidotetracopper(I)molybdenum(VI), (C16H36N)2[MoS4(CuCl)4], has been obtained in a second polymorphic form. The anion, in which four of the six S⋯S edges of the central MoS4 tetrahedron are bridged by CuCl neutral molecular units to give a planar pentanuclear MoCu4 framework, is disordered on a crystallographic fourfold rotation axis, requiring equal occupancy of two sets of four positions for the S atoms. There is additional disorder as a result of 8.2u2005(2)% substitution of Cl by Br, arising from tetra-n-butylxadammonium bromide used in the synthesis. Copper has distorted trigonal planar coordination, involving two μ3-S atoms and a terminal halogen atom. The two independent cations lie on positions of symmetry overline 4.

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

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 Mo=O bond remains terminal. The Mo, 3u2005Cu 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.

Tetraethylammonium [1-methyl­imidazole-2(3H)-thione]copper(I)-di-μ-sulfido-dioxotungstate(VI)

In the title complex, tetrethylammonium [1-methylxadimidazole-2(3H)-thione-2κS]xaddioxo-1κ2O-di-μ-sulfido-1:2κ4S:S-copxadper(I)xadtungstate(VI), (C8H20N)[WCuO2S2(Hmimt)], where Hmimt is 1-methylxadimidazole-2(3H)-thione (C4H6N2S), the W and Cu atoms have tetrahedral and trigonal planar coordination, respectively. Two sulfide ligands bridge the two metal centres; tungsten is additionally coordinated by two terminal oxo ligands and copper by the exocyclic S atom of Hmimt. The bridged W⋯Cu distance is 2.670u2005(3)u2005A. Anions are linked into chains by N—H⋯O hydrogen bonds between Hmimt and oxo ligands.

Bis­(tetra-n-butyl­ammonium) tetrakis­[chloro(μ3-sulfido)copper(I)]­tungstate(VI): a second polymorph

The title compound, (C16H36N)2[WS4(CuCl)4], has been obtained in a second polymorphic form. The anion, in which four of the six S⋯S edges of the central WS4 tetrahedron are bridged by CuCl neutral molecular units to give a planar pentanuclear WCu4 framework, is disordered on a crystallographic fourfold rotation axis, requiring equal occupancy of two sets of four positions for the S atoms. Copper has distorted trigonal planar coordination, involving two μ3-S atoms and a terminal Cl atom. The two independent cations lie on positions of symmetry overline 4.

Bis­(tetraethyl­ammonium) μ‐tetra­thio­molybdato(VI)‐bis­[chloro­copper(I)]

The title compound, (Et4N)2[MoS4(CuCl)2], consists of tetraethylxadammonium cations of expected geometry, and trinuclear anions in which two opposite edges of an MoS42− tetrahedron are bridged by CuCl units. The bridging of Mo and Cu centres by all four S atoms hardly affects the tetrahedral coordination of Mo and leads to a distorted trigonal planar coordination geometry for Cu, with both chloro ligands terminal.

Synthesis and crystal structures of bis(N-phenyl-3,5-dinitrothiobenzamidato)mercury(II) and bis(N-phenyl-4-nitrothiobenzamidato)mercury(II)

The crystal structures of bis(N-phenyl-3,5-dinitrothiobenzamidato)mercury(II) (1) and bis(N-phenyl-4-nitrothiobenzamidato)mercury(II) (2) have been determined by single-crystal X-ray diffraction. Both the complexes crystallize in centrosymmetric monoclinic space groups with crystallographic inversion symmetry. The S–Hg–S linkage is thus precisely linear in each case. Significant secondary interactions include intramolecular π coordination by phenyl groups, aromatic ring stacking in the case of 1 only, and a number of intramolecular and intermolecular C–H ⋅ ⋅ ⋅ X contacts (X = O, N, S) influencing the molecular conformation and crystal packing.

Bis[N-(4-nitrophenyl)thiobenzamidato]mercury(II).

The molecule of the title compound, [Hg(C(13)H(9)N(2)O(2)S)(2)], has approximate twofold rotation symmetry, with the Hg atom in an essentially linear two-coordinate HgS(2) environment supported by secondary pi interactions with the nitrophenyl rings of both ligands. The ligands are in the imine-thiolate rather than the amine-thione tautomeric form.