Dicarbonyldi‐μ‐chloro‐cis,cis‐η4‐1,5‐cyclo­octa­dienedirhodium(I)

The title compound, dicarbonyl‐1κ²C‐di‐μ‐chloro‐1:2κ⁴Cl‐[cis,cis‐2(η⁴)‐1,5‐cyclo­octa­diene]­di­rhodium(I), [Rh₂Cl₂(C₈H₁₂)(CO)₂], consists of a di­chloro‐bridged dimer of rhodium, with a non‐bonded Rh?Rh distance of 3.284 (2) Å. One Rh atom is coordinated to two carbonyl ligands, while the other Rh atom is coordinated to the cyclo­octa­diene moiety.     

Tetrakis(μ‐benzothiazole‐2‐thiolato)‐1:2κ4N:S2;1:2κ4S2:N‐dichloro‐1κCl,2κCl‐dirhenium(III)(Re—Re) dichloromethane solvate: a bridged complex with a long Re—Re quadruple bond

The title compound, [Re₂(C₇H₄NS₂)₄Cl₂]·CH₂Cl₂, consists of dirhenium mol­ecules with bridging N,S‐benzo­thia­zole‐2‐thiol­ate ligands, axial Cl^? ligands and intramolecular hydrogen bonding. These mol­ecules adopt somewhat staggered conformations, with a long Re—Re quadruple bond distance of 2.2716 (3) Å.     

trans‐Carbonyliodotris(triphenylstibine‐κSb)rhodium(I)

The crystal structure of the title compound, [RhI(C₁₈H₁₅Sb)₃(CO)], represents a rare example of a crystallographically characterized five‐coordinate Rh^I–SbPh₃ complex. The compound crystallizes with the I—Rh—CO core on a threefold rotation axis, with three crystallographically equivalent tri­phenyl­stibine ligands. Selected geometric parameters are: Rh—I = 2.7159 (8), Rh—Sb = 2.5962 (4), Rh—C_CO = 1.825 (6) and C_CO—O 1.153 (6) Å, and Sb—Rh—I = 89.374 (10) and Sb—Rh—C_CO = 90.626 (10)°. The cone angle of the SbPh₃ ligand was determined as 137°, according to the Tolman model.     

7‐{Di­phenyl­[(tri­phenyl­phos­phine)­aurio]­phos­phine(1+)‐P}‐8‐methyl‐7,8‐dicarba‐nido‐undecaborate(1–) dichloro­methane hemi­solvate

The title compound, 7‐[(Ph₂P)Au(PPh₃)]‐8‐(CH₃)‐7,8‐nido‐C₂B₉H₁₀]·­0.5CH₂Cl₂ or [Au(C₁₅H₂₃B₉P)­(C₁₈H₁₅P)]·­0.5CH₂Cl₂, is the first reported gold derivative of the ligand [7‐­(Ph₂P)‐8‐(CH₃)‐7,8‐nido‐C₂B₉H₁₀]^?. It has a mono­nuclear structure with the gold centre in an essentially linear coordination [P—Au—P 174.041 (15)°]. The open C₂B₃ face contains one H atom that is strongly bonded to the central B atom and semi‐bridging to a neighbouring B atom [B—H distances 1.070 (16) and 1.45 (3) Å].     

Compositional disorder in trans‐[RhBr0.26Cl0.74H(PMe3)4][B(1,2‐O2C6Br4)]·CH2Cl2

The structure of trans‐(bromo/­chloro)­hy­drido­tetra­kis­(tri‐me­thyl­phos­phine)­rhod­ium(III) bis­(tetra­bromo­pyro­catechol‐ato‐O,O′)­borate dichloromethane solvate, [RhCl_0·74Br_0·26H‐(C₃­H₉­P)₄]­(C₁₂­BBr₈­O₄)·­CH₂Cl₂, is reported. The Rh^III com­plex shows bromine/chlorine compositional disorder with a trans arrangement of the hydride and halide ligands. The anion has approximate D_2d symmetry, with a central spiro‐B atom distorted from regular tetrahedral geometry by the small chelating O—B—O angles.     

Tetra‐μ‐chloro‐1:2κ4Cl;1:3κ4Cl‐bis(4,4′‐di­methyl‐2,2′‐bi­pyridine)‐2κ2N,3κ2N‐lithium(I)­dipalladium(II) tetrakis­(penta­fluoro­phenyl)­borate di­chloro­methane 1.196‐solvate

In the crystal structure of the title compound, [LiPd₂Cl₄(C₁₂H₁₂N₂)₂](C₂₄F₂₀B)·1.196CD₂Cl₂ or [{(Me₂bipy)PdCl₂}₂(μ‐Li)]⁺·B(C₆F₅)₄⁻·1.196CD₂Cl₂ (Me₂bipy is 4,4′‐di­methyl‐2,2′‐bi­pyridine), an Li⁺ cation is stabilized by complexation with two (Me₂bipy)PdCl₂ units through weak Li—Cl interactions. This compound is thus a rare example of a complex that exhibits an arrested Cl⁻ abstraction.     

catena‐Poly[[[tetrakis(μ‐acetato‐κ2O:O′)dirhodium(II)]‐μ‐[1,3‐bis(dimethylamino)propan‐2‐ol‐κ2N:N′]] tetrahydrofuran hemisolvate]

In the structure of the title compound, {[Rh₂(C₂H₃O₂)₄(C₇H₁₈N₂O)]·0.5C₄H₈O}_n or {[Rh₂(O₂CMe)₄(Hbdmap)]·0.5C₄H₈O}_n, where Hbdmap is 1,3‐bis­(dimethyl­amino)propan‐2‐ol, each Hbdmap ligand is coordinated to two [Rh₂(O₂CMe)₄] units by two N atoms, resulting in a polymeric chain structure. The observed coordination mode of the Hbdmap mol­ecule is unprecedented.     

Pt2II and Pt2III dimers containing a Pt2(2,2′‐bipyridine)2(μ‐N,N‐dimethyl­guanidinato)2 unit

The syntheses and crystal structures of the title Pt₂^II and Pt₂^III dimers doubly bridged with N,N‐dimethyl­guanidinate ligands, namely bis­(μ‐N,N‐dimethyl­guanidinato)bis­[(2,2′‐bipyridine)platinum(II)](Pt—Pt) bis­(hexa­fluoro­phosphate) acetonitrile disolvate, [Pt₂^II(C₃H₈N₃)₂(C₁₀H₈N₂)₂](PF₆)₂·2CH₃CN, (I), and guanidinium bis­(μ‐N,N‐dimethyl­guanidinato)bis­[(2,2′‐bipyridine)sulfatoplatinum(III)](Pt—Pt) bis­(hexa­fluoro­phosphate) nitrate hexa­hydrate, (C₃H₁₀N₃)[Pt^III₂(C₃H₈N₃)₂(SO₄)₂(C₁₀H₈N₂)₂]NO₃·6H₂O, (II), are reported. The oxidation of the Pt₂^II dimer into the Pt₂^III dimer results in a marked shortening of the Pt—Pt distance from 2.8512 (6) to 2.5656 (4) Å. The change is mainly compensated for by the change in the dihedral angle between the two Pt coordination planes upon oxidation, from 21.9 (2) to 16.9 (3)°. We attribute the relatively strong one‐dimensional stack of dimers achieved in the Pt₂^II compound in part to the strong Pt^II⋯C(bpy) associations (bpy is 2,2′‐bipyridine) in the crystal structure [Pt⋯C = 3.416 (10) and 3.361 (12) Å].     

β‐Pyridinium di­chloro­iodide

The β modification of pyridinium di­chloro­iodide, C₅H₆N⁺·Cl₂I^?, was obtained as yellow crystals by the reaction of (C₅NH₅)AuCl₃, C₅H₆N⁺·Cl^? and I₂ in a vacuum‐sealed ampoule. The di­chloro­iodide ion is nearly symmetric and linear with I—Cl bond lengths of 2.544 (3) and 2.550 (3) Å and a Cl—I—Cl angle of 179.68 (12)°.     

A pyrazine bis‐adduct of a binuclear rhodium(II) carboxylate containing 3,4,5‐triethoxybenzoate as the ­equatorial ligand

The title compound, tetrakis(μ‐3,4,5‐triethoxy­benzoato‐κ²O:O′)­bis­[(pyrazine‐κN)­rhodium(II)](Rh—Rh), [Rh₂(C₁₃H₁₇O₅)₄(C₄H₄N₂)₂], crystallizes on an inversion centre in the triclinic space group . The equatorial carboxyl­ate ligands bridge the two Rh^II atoms, giving a binuclear lantern‐like structure. The pyrazine mol­ecules occupy the two axial coordination sites. The phenyl rings are tilted by ca 10° with respect to the attached carboxyl­ate groups. The pyrazine planes have a torsion angle of ca 19° around the Rh—N bond with respect to the plane of the nearer carboxyl­ate group and are not coplanar with the Rh—Rh bond.     

Three monoalkoxy‐substituted nido‐platinaboranes: [(PPh3)2PtB10H11‐8‐(OCH3)], [(PPh3)2PtB10H11‐8‐{OCH(CH3)2}] and [(PPh3)2PtB10H10‐9‐{OCH(CH3)2}]

Each of the title compounds, 8‐methoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane hemisolvate, [Pt(CH₁₄B₁₀O)(C₁₈H₁₅P)₂]·0.5CH₂Cl₂, (I), 8‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (II), and 9‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (III), has an 11‐vertex nido polyhedral skeleton, with the 7‐platinum centre ligating to two exo‐polyhedral PPh₃ groups and an alkoxy‐substituted polyhedral borane ligand. Compounds (II) and (III) are isomers. The Pt—B distances are in the range 2.214 (7)–2.303 (7) Å for (I), 2.178 (16)–2.326 (16) Å for (II) and 2.205 (6)–2.327 (6) Å for (III).     

Paddlewheel dirhodium complexes bridged by para‐substituted benzoates

The dirhodium complex bis­(benzonitrile)tetra­kis[μ‐4‐(diethyl­amino)benzoato‐κ²O:O′]dirhodium(II)(Rh—Rh) benzonitrile disolvate, [Rh₂(C₁₁H₁₄NO₂)₄(C₇H₅N)₂]·2C₇H₅N, lies about an inversion centre. The dirhodium complex (methanol)tetra­kis(μ‐4‐nitro­benzoato‐κ²O:O′)(pyridine)dirhodium(II)(Rh—Rh) dichloro­methane solvate, [Rh₂(C₇H₄NO₄)₄(C₅H₅N)(CH₄O)]·CH₂Cl₂, lies in a general position in the unit cell, but the complexes dimerize around an inversion centre via O—H⋯O hydrogen bonding of the axial MeOH to a carboxyl­ate O atom. In the latter crystal structure, π–π stacking inter­actions between the bridging 4‐nitro­benzoate ligands and the axial pyridine ligand are observed between adjacent mol­ecules.     

Bis{μ‐2‐[(2,3‐dichloro­phenyl)­amino]­benzoato‐κO}di‐μ2‐ethoxo‐octa­methyl­di‐μ3‐oxo‐tetra­tin(IV)

The title compound, [Sn₄(CH₃)₈(C₁₃H₈Cl₂NO₂)₂(C₂H₅O)₂O₂], is a centrosymmetric dimer, with three linearly fused four‐membered Sn—O—Sn—O rings. The coordination poly­hedron of the Sn atom bonded to the carboxyl­ate can be described as trigonal–bipyramidal distorted toward square‐pyramidal. That of the second Sn atom is similar, but the distortion towards square‐pyramidal geometry is greater. The Sn—O and Sn—C distances are 2.020 (2)–2.226 (2) and 2.096 (4)–2.114 (4) Å, respectively. The benzene rings of the 2‐[(2,3‐dichloro­phenyl)­amino]benzoate ligand subtend an angle of 50.49 (17)°; the conformation of the ligand is stabilized by intra­molecular N—H⋯Cl and N—H⋯O hydrogen bonds. The structure is assembled viaπ–π stacking inter­actions to form chains parallel to [10].     

An organometallic RhIII complex with a distorted octahedral structure: (acetonitrile‐κN)dimethyl(1,4,7‐trimethyl‐1,4,7‐triazacyclononane‐κ3N,N′,N′′)rhodium(III) tetraphenylborate

In the title compound, [Rh(CH₃)₂(C₂H₃N)(C₉H₂₁N₃)](C₂₄H₂₀B), the geometry around the Rh^III centre is distorted octahedral, with elongated Rh—N bonds trans to the metal‐bonded methyl groups. The metal‐containing cations are located in channels formed by an anionic supramolecular mesh, in which aromatic π–π interactions between anionic [B(Ph)₄]^? units play a major role.     

A novel bridged asymmetric binuclear manganese(II) complex with DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benz­imidazol‐2‐yl­methyl)‐1,4,7‐tri­aza­heptane]

The crystal structure of the title compound, tetra­chloro­[μ‐1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐yl­methyl)‐1,4,7‐tri­azaheptane]­dimanganese(II) methanol pentasolvate tetrahydrate, [Mn₂Cl₄(C₄₄H₄₃N₁₃)]·5CH₄O·4H₂O, contains an ­asymmetric dinuclear Mn^II–DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐yl­methyl)‐1,4,7‐tri­aza­heptane] complex with an intra‐ligand bridging group (–NCH₂CH₂N–), as well as several solvate mol­ecules (methanol and water). Both Mn^II cations have similar distorted octahedral coordination geometries. One Mn^II cation is coordinated by a Cl⁻ anion and five N atoms from the ligand, and the other is coordinated by three Cl⁻ anions and three N atoms of the same ligand. The Mn⋯Mn distance is 7.94 Å. A Cl⋯H—O⋯H—O⋯H—N hydrogen‐bond chain is also observed, connecting the two parts of the complex.     

A paramagnetic precursor for polymeric supramolecular assemblies based on multiply bonded dimetal units: μ‐acetato‐aceto­nitrile­tris(μ‐N,N′‐di­phenyl­formamidinato)­di­ruthenium tetra­fluoro­borate di­chloro­methane hemisolvate

The title compound, [Ru₂(C₁₃H₁₁N₂)₃(C₂H₃O₂)(C₂H₃N)]BF₄·0.5CH₂Cl₂ or [Ru₂(μ‐DPhF)₃(μ‐O₂CMe)(MeCN)]BF₄·0.5CH₂Cl₂, where DPhF is N,N′‐diphenyl­formamidinate, crystallized as dark‐blue block‐shaped crystals. In the unit cell, the diruthenium cation lies on a general position, and the BF₄⁻ anions reside on two independent special positions with crystallographic twofold symmetry. Disorder was observed for one of the phenyl groups in the formamidinate ligand, the axial aceto­nitrile mol­ecule and the interstitial di­chloro­methane mol­ecule. The compound, which exhibits a long Ru—Ru bond of 2.4131 (5) Å, is the first {Ru₂}⁵⁺ formamidin­ate species that is both equatorially and axially functionalized so that it can be used as a precursor for polymeric paramagnetic supramolecular assemblies.     

μ‐Oxo‐bis[(η5‐1,2‐dicarbaundecabor­ato)bis(N,N‐dimethylacetamidinato)tantalum] dichloromethane hemisolvate

The structure of the title compound, [Ta₂O(C₂B₉H₁₁)₂(C₄H₉­N₂)₄]·0.5CH₂Cl₂, contains two (C₂B₉H₁₁)Ta[NC(Me)NMe₂]₂ units bridged by a nearly linear [Ta—O—Ta 163.4 (4)°] μ‐oxo ligand. The dichloromethane molecule lies on a twofold axis.     

Di‐μ‐chloro‐bis­{bis­[2,5‐bis­(4‐methoxy­phenyl)‐1,3,4‐oxadiazole‐κ2C2′,N]iridium(III)] dichloro­methane disolvate

In the title compound, [Ir₂(C₁₆H₁₃N₂O₃)₄Cl₂]·2CH₂Cl₂, the two Ir atoms, 3.7075 (6) Å apart, are bridged by two Cl atoms which straddle a twofold axis of rotation through the two Ir atoms. Each Ir centre resides in a distorted octa­hedral environment completed by two chelating 2,5‐bis­(4‐methoxy­phenyl)‐1,3,4‐oxadiazole ligands, with trans‐N—N and cis‐C—C dispositions. In the stacking structure, there are two types of hydrogen bonds, involving the meth­oxy substitutent, an N atom of the oxadiazole ring and the dichloro­methane solvent mol­ecules.     

Dibromo[5,10,15,20‐tetrakis(4‐methoxyphenyl)porphyrinato‐κ4N]platinum(IV) chloroform acetonitrile solvate

In the title compound, [PtBr₂(C₄₈H₃₆N₄O₄)]·0.896CHCl₃·0.569CH₃CN, the centrosymmetric metal complex is octahedral, with the porphyrin ring essentially planar and the Br atoms occupying axial positions. The two independent methoxy­phenyl substituents are tilted at angles of 89.0 and 67.0° with respect to the porphyrin plane. The Pt—N distances are 2.035 (4) and 2.036 (4) Å and the Pt—Br distance is 2.4666 (6) Å. Chloro­form and aceto­nitrile solvent mol­ecules, exhibiting substantial disorder, occupy positions between the porphyrin mol­ecules. This is the first crystal and molecular structure of a Pt^IV–porphyrin complex to be reported.     

Di‐μ‐hydroxo‐bis({bis­[2‐(2‐pyridyl)ethyl]amine‐κ3N}copper(II)) dichloride hexahydrate

The title compound, [Cu₂(OH)₂(C₁₄H₁₇N₃)₂]Cl₂·6H₂O, is a crystallographically centrosymmetric dimer of square‐pyramidal Cu^II centres, with a basal–basal [Cu₂(μ‐OH)₂]²⁺ bridging motif and apical pyridyl donors. The Cl⁻ anion is hydrogen bonded to one O—H and one N—H group, and to three different water mol­ecules. Because of disorder, the network of intramolecular hydrogen bonding in the hydrated lattice is only partly resolved.