(Benzoxazole‐2‐thiol­ato‐S)(benzoxazole‐2‐thione‐S)­bis­(tri­phenylphosphine)copper(I)

The Cu atom in [Cu(C₇H₄NOS)(C₇H₅NOS)(C₁₈H₁₅P)₂] is tetrahedrally coordinated by a P₂S₂ donor set. One S atom is derived from neutral benzoxazole‐2‐thione and the other from the deprotonated form of the ligand. The two sulfur ligands are connected via an N—H?N interaction, leading to the formation of an eight‐membered ring.     

μ‐Bi­phenyl‐2,2′‐di­thiol­ato‐κ2S:S′‐bis­[(tri­phenyl­phosphine‐κP)­gold(I)]

The reaction of ClAuPPh₃ and 1,1′‐bi­phenyl‐2,2′‐di­thiol in the presence of tri­methyl­benzyl­ammonium chloride and K₂CO₃ in a tetra­hydro­furan/methanol solution gives the title complex, [Au₂(C₁₂H₈S₂)(C₁₈H₁₅P)₂]. The mol­ecule contains P—Au—S units which `cross' with torsion angles of ∼90° [P—Au—Au—P = 86.23 (5)° and S—Au—Au—S = 95.62 (5)°]. The intra‐ and intermolecular Au⋯Au distances [3.9064 (3) and 6.3797 (5) Å, respectively] are outside the range for typical Au⋯Au interactions. However, the Au atoms appear to be drawn together, leading to a significant bending of the P—Au—S angles [170.24 (5) and 169.52 (5)°].     

A new polymorph of (O‐ethyl dithio­carbonato‐κ2S,S′)­bis­(tri­phenylphosphine‐κP)silver(I)

A new triclinic polymorphic modification of the title compound, [Ag(C₃H₅OS₂)(C₁₈H₁₅P)₂], has been found and compared with the previously known orthorhombic modification [Tiekink (1988). Coord. Chem. 17 , 239–243]. The two polymorphs have the same molecular shape, viz. a distorted tetrahedral geometry, with a chelating di­thio­carbonate (xanthate) and two PPh₃ ligands bonded to the Ag atom. However, in this new polymorph, the xanthate ligand is bonded asymmetrically to the Ag atom, with Ag—S distances of 2.5489 (6) and 2.8055 (7) Å, while for the orthorhombic polymorph these distances are 2.686 (4) and 2.601 (4) Å. The Ag—P distances are similar in both structures.     

Carbonyl(5‐nitrotropolonato‐κ2O1,O2)(tri­phenyl­phosphine‐κP)­rhodium(I)

The molecule of the title complex, [Rh(5‐NO₂trop)(C₁₈H₁₅P)(CO)] (5‐­NO₂trop is 2‐hydroxy‐5‐nitrocyclo­hepta‐2,4,6‐trienone, C₇H₄NO₄), has a distorted square‐planar geometry. Strong intramolecular and weak intermolecular hydrogen bonding is observed, with H⋯O distances of the order of 2.25 and 2.55 Å, respectively. The Rh—CO, Rh—O (trans to CO), Rh—O (trans to P) and Rh—P bond distances are 1.775 (7), 2.072 (4), 2.068 (4) and 2.2397 (17) Å, respectively, the O—Rh—O angle is 77.09 (16)° and the bidentate O—C—C—O torsion angle is 1.5 (7)°.     

(4,6‐Dimercapto‐1,3,5‐triazine‐2‐thiol­ato‐S2)­tris­(tri­phenyl­phosphine‐P)gold(I) di­methyl­form­amide solvate

In the title compound, [Au(C₃H₂N₃S₃)(C₁₈H₁₅P)₃]·C₃H₇NO, the Au^I atom has a distorted tetrahedral geometry consisting of one uncoordinated di­methyl­form­amide mol­ecule, one tri­thio­cyanurate ligand and three PPh₃ ligands. The S—Au distance is 2.909 (2) Å, and the P—Au distances fall in the range 2.400 (14)–2.4074 (13) Å. The S—Au—P angles are 92.81 (6), 99.17 (6) and 104.21 (5)°, and the P—Au—P angles are 114.46 (5), 119.04 (5) and 119.66 (5)°.     

Bis[2,2′‐(phenyl­phosphinediyl)­dibenzene­thiol­ato‐κ3S,P,S′]germanium(IV)

Two tridentate phosphinethiol­ate ligands, [PhP(C₆H₄S‐2)₂]²⁻, coordinate to the Ge^IV centre in a facial manner yielding the title compound, [Ge(C₁₈H₁₃PS₂)₂], which exhibits a pseudo‐twofold symmetry with the two P‐atom donors in a cis configuration. The Ge centre has a distorted octahedral environment. Two phenyl rings, one from each of the phosphinethiol­ate ligands, are parallel to one another, indicating π–π interactions. The molecules are linked by weak C—H⋯π and C—H⋯S interactions.     

Chloro­(phenyl)(1H‐pyrazole‐κN2)(tri­phenyl­phosphine‐κP)­palladium(II)

In the title compound, [Pd(C₆H₅)Cl(C₃H₄N₂){P(C₆H₅)₃}], the phenyl and Cl ligands lie mutually trans. The compound is the first structurally characterized complex with four mono­dentate Cl, P, N and (non‐carbenoid) C ligands in a square‐planar four‐coordinate palladium(II) environment. The pyrazole ligand is coplanar with the latter array. The pyrazole NH group forms a bifurcated hydrogen bond to Cl, with an intra‐ and intermolecular component.     

Polymeric (μ2‐nitrato‐κ2O:O′)(μ2‐nitrato‐κ2O:O)(μ4‐pyridinium‐4‐thiol­ato‐κ4S:S:S:S)­disilver(I)

The title compound, [Ag₂(NO₃)₂(C₅H₅NS)]_n, was obtained from the reaction of silver nitrate with bis(4‐pyridyl) disufide (4‐PDS) in a mixture of ethanol and water, which suggests that the di­sulfide bond of 4‐PDS can be cleaved under mild conditions. The structure of the title compound is a two‐dimensional infinite array in which the asymmetric unit contains two Ag atoms, a pyridinium‐4‐thiol­ate mol­ecule and two nitrate groups. Each pyridinium‐4‐thiol­ate mol­ecule acts as a μ₄ bridge, linking four Ag atoms, with Ag—S bond distances of 2.4870 (19), 2.5791 (19), 2.5992 (19) and 2.848 (2) Å. The Ag⋯Ag distances lie in the range 2.889 (2)–3.049 (1) Å.     

Di­iodo(3,4,5,6‐tetrahydropyrimidin­ium‐2‐thiol­ato‐S)­mercury(II)

The reaction of 3,4,5,6‐tetrahydropyrimidine‐2‐thione (H₄py­mtH) with mercury(II) iodide in methanol in a 1:1 molar ratio resulted in the formation of single crystals of the title compound, [Hg(C₄H₈N₂S)I₂]. The Hg atom is coordinated by one S atom from H₄pymtH at 2.456 (2) Å and by two I atoms at distances of 2.6872 (7) and 2.7044 (6) Å, and has a characteristic deformed trigonal coordination geometry. The molecule has crystallographic m symmetry but the Hg atom is disordered above and below the mirror plane.     

Bis(μ‐cyst­amine‐κ4N,S:S′,N′)­bis­[(2‐amino­ethane­thiol­ato‐κ2N,S)­iridium(III)] tetrabromide dihydrate

In the complex cation of the title compound, [Ir₂(C₂H₆NS)₂(C₄H₁₂N₂S₂)₂]Br₄·2H₂O, which was obtained by rearrangement of [Re{Ir(aet)₃}₂]³⁺ (aet is 2‐amino­ethane­thiol­ate) in an aqueous solution, two approximately octahedral fac(S)‐[Ir(NH₂CH₂CH₂S)₃] units are linked by two coordinated di­sulfide bonds. The complex cation has a twofold axis, and the two non‐bridging thiol­ate S atoms in the complex are located on opposite sides of the two di­sulfide bonds. Considering the absolute configurations of the two octahedral units (Δ and Λ) and the four asymmetric di­sulfide S atoms (R and S), the complex consists of the Δ_RRΔ_RR and Λ_SSΛ_SS isomers, which combine to form the racemic compound.     

Tetrakis­(tetra­hydro­furan‐κO)­lithium mer‐tris­(carbazolyl‐κN)‐trans‐di­chloro(tetra­hydro­furan‐κO)­zirconate

In the title compound, [Li(C₄H₈O)₄][ZrCl₂(C₁₂H₈N)₃(C₄H₈O)], the environment of the Zr atom is pseudo‐octahedral, with the three carbazolyl ligands in a mer configuration. The counter‐ion of the zirconium complex is composed of an Li atom surrounded by four tetra­hydro­furan (THF) mol­ecules. The THF mol­ecule attached to the Zr atom is disordered over two sites, as are two of the THF mol­ecules in the lithium moiety. All bond distances and angles are consistent with those in complexes with similar structural entities. The Zr—N bond distances are 2.2185 (18) and 2.167 (3) Å.     

Di­iodo­bis(1‐methyl‐1,3‐imidazolium‐2‐thiol­ato‐S)­mercury(II)

The reaction of 1‐methyl‐1,3‐imidazole‐2‐thione (meimtH) with mercury(II) iodide in methanol in a 2:1 molar ratio resulted in the formation of single crystals of the title compound, [HgI₂(C₄H₆N₂S)₂]. The Hg atom is coordinated by two I [2.7809 (9) and 2.7999 (8) Å] and two thione S atoms [2.520 (3) and 2.576 (3) Å] with irregular tetrahedral coordination geometry. The NH groups of the imidazole ring take part in intra‐ and intermolecular hydrogen bonds with I atoms [N?I 3.596 (8) and 3.611 (9) Å, respectively] joining mol­ecules into infinite chains parallel to the z axis.     

Tetra­kis(penta­fluoro­benzene­thiol­ato‐κS)(triphenyl­phosphine‐κP)osmium(IV): a Z′ = 3 structure with a supra­molecular double‐stranded backbone

The title complex, [Os(C₆F₅S)₄(C₁₈H₁₅P)], crystallizes with three independent mol­ecules in the asymmetric unit. Two of these have very similar conformations, while in the third, the axial thiol­ate ligand has a rotation that differs by ca 21.5°. The coordination around the metal atom is trigonal bipyramidal and the supra­molecular structure involves an unusual double‐stranded backbone.     

cis‐Dinitrito(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ4N)­chromium(III) nitrite

In the title compound, [Cr(ONO)₂(cyclam)]NO₂ (cyclam is 1,4,8,11‐tetra­aza­cyclo­tetra­decane, C₁₀H₂₄N₂), the complex cation is located on a twofold symmetry axis. The central Cr atom has a distorted octahedral coordination, involving two Cr—O bonds, with the monodentate nitrite O atoms adopting a cis configuration, and four Cr—N bonds. The mean Cr—N and Cr—O distances are 2.0895 (14) and 1.9698 (14) Å.     

Tetra‐n‐butyl­ammonium tetrakis(penta­fluoro­benzenethiol­ato‐κS)­aurate(III)

The title compound, (C₁₆H₃₆N)[Au(C₆F₅S)₄], is the first example of a structurally characterized gold(III) complex with monodentate benzene­thiol­ate ligands. The Au atom lies on a fourfold axis and the AuS₄ group has square‐planar geometry. The anion shows a two‐dimensional linkage through π–π and C—F⋯π intermolecular interactions.     

Tri‐μ2‐chloro‐tetra­chloro‐μ3‐oxo‐hexakis­(tetra­hydro­furan‐κO)­dititanium(III)­samarium(III): a novel trinuclear Sm–Ti mixed species

In the title compound, [SmTi₂Cl₇O(C₄H₈O)₆], the metal ions are linked by a central μ₃‐oxo ion and by three μ₂‐chloro ions, giving a planar moiety containing a binary crystallographic axis. The coordination spheres are completed by terminal chloro ligands and tetra­hydro­furan mol­ecules, with resulting pentagonal bipyramidal and octahedral environments for the Sm and Ti atoms, respectively.     

Bis(μ‐pyridine‐2‐thiol­ato)‐κ4S:N;N:S‐bis­[(pyridine‐2‐thiol­ato‐κS)(2‐pyridyl­phen­yl‐κ2N,C2)platinum(III)](Pt—Pt): the non‐solvated and acetonitrile‐solvated forms

The title dinuclear platinum(III) complex, [Pt₂(C₁₁H₈N)₂(C₅H₄NS)₄], forms two crystal structures, viz. the non‐solvated and acetonitrile‐solvated (C₂H₃N) forms. For both forms, two (2‐pyridylphenyl)platinum units are bridged by two pyridine‐2‐thiol­ate (pyt) anions in a head‐to‐tail configuration, and the other two pyridine‐2‐thiol­ate anions occupy the axial position, coordinated through their S atoms. The most remarkable difference between the two forms is the orientation of the axial monodentate ligands. Those for the solvated form are located over the 2‐pyridylphenyl ligands, being related by a twofold axis which lies through the centre of the Pt—Pt bond, while the axial pyt ligands for the non‐solvated form are oriented irregularly, which is attributable to the dimeric arrangement in the crystal.     

(2,2′‐Bipyridyl‐κ2N,N′)­bis­(salicyl­ato‐κ2O,O′)­zinc(II)

The asymmetric unit of the title compound, [Zn(C₇H₅O₃)₂(C₁₀H₈N₂)], contains one monomeric zinc complex. The Zn atom is coordinated to one 2,2′‐bipyridyl ligand via both N atoms and to two salicyl­ate anions (Hsal⁻) in a bidentate chelating manner involving carboxyl­ate O‐atom coordination. The complex exhibits a distorted octahedral geometry about the Zn^II atom, with the `apical' positions occupied by one of the two N atoms of the bipyridyl ligand and an O atom from one Hsal<sup>−</sup> ligand; the Zn atom is 0.168 (1) Å out of the `basal' plane. Two intramolecular six‐membered hydrogen‐bonded rings are present, generated from interactions between the carboxyl and hydroxyl groups of the salicyl­ate ligands. The crystal packing is governed by weak C—H⋯O and C—H⋯π interactions.     

catena‐Poly­[bromo(ω‐thio­capro­lactam‐κS)­gold(I)](Au—Au)

The title compound, [AuBr(C₆H₁₁NS)]_n, formed through an Au^IIIAu^I reduction process, presents a polymeric structure including Au chains with alternating Au—Au distances of 3.0898 (8) and 3.1181 (8) Å. The coordination geometry is best described on the basis of linear [AuBr(C₆H₁₁NS)] mol­ecules, which are associated into a one‐dimensional polymer via a common aurophilic interaction.     

trans‐Bis(3,5‐di­aza‐1‐azonia‐7‐phosphaadamantane‐κP)­bis­(thiocyanato‐κS)­palladium(II) bis­(thio­cyanate)

The crystal structure of the title compound, trans‐[Pd(NCS)₂(C₆H₁₃N₃P)₂](NCS)₂, is one of the few pal­ladium(II) complexes containing two protonated water‐soluble 1,3,5‐tri­aza‐7‐phos­pha­adamantane (PTA) ligands re­ported to date. The compound displays a distorted square‐planar geometry, with the Pd atom on an inversion centre and with the S atoms of the thio­cyanate counter‐ions occupying the axial positions above and below the equatorial plane described by the phosphine and thio­cyanate ligands. Geometric parameters for the formal coordination polyhedron include a Pd—P distance of 2.2940 (8) Å, a Pd—S distance of 2.3509 (8) Å and a P—Pd—S angle of 89.45 (3)°. The effective cone angle for the PTA ligands was calculated as 114.5°.