[(1R,2R)‐1,2‐Di­amino­cyclo­hexane‐κ2N,N′](α‐di­imine‐κ2N,N′)­platinum(II) bis­(hexa­fluoro­phosphate), where α‐di­imine is 2,2′‐bi­pyridine and 1,10‐phen­anthroline

The title Pt^II complexes, viz. (2,2′‐bi­pyridine‐κ²N,N′)[(1R,2R)‐1,2‐di­amino­cyclo­hexane‐κ²N,N′]­platinum(II) bis­(hexa­fluoro­phosphate), [Pt(C₆H₁₄N₂)(C₁₀H₈N₂)](PF₆)₂, and [(1R,2R)‐1,2‐di­amino­cyclo­hexane‐κ²N,N′](1,10‐phenanthroline‐κ²N,N′)platinum(II) bis­(hexa­fluoro­phosphate), [Pt(C₆H₁₄N₂)(C₁₂H₈N₂)](PF₆)₂, containing an aromatic α‐di­imine and a non‐planar di­amino­cyclo­hexane, both form a ladder‐type structure, which is constructed via loose π–π stacking on the α‐di­imine ligands and hydrogen bonding between the cyclic amines and the counter‐anions. In the former compound, there are two independent complex cations, both of which have a twofold axis through the Pt atom.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and polymeric adducts with 1,2‐bis(4‐pyridyl)­ethene and 1,6‐di­amino­hexane

In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,2‐bis(4‐pyridyl)­ethene (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₀N₂, there is an intramolecular O—H?O hydrogen bond in the ferro­cene­diol component and a single O—H?N hydrogen bond linking the diol to the di­amine, which is disordered over two sets of sites, so forming a finite monomeric adduct. In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,6‐di­amino­hexane (2/1), 2[Fe(C₁₈H₁₅O)₂]·C₆H₁₆N₂, the amine lies across a centre of inversion in space group P. There is an intramolecular O—H?O hydrogen bond in the ferrocenediol, and the molecular components are linked by O—H?N and N—H?O hydrogen bonds, one of each type, into a C(13)[R(12)] chain of rings.     

Azido­[1,1′‐bis­(di­phenyl­phosphino)­ferrocene](penta­methyl­cyclo­penta­dienyl)­rhodium(III) hexa­fluoro­phosphate

In the title compound, azido‐2κN‐bis­[μ‐(1η⁵:2κP)‐di­phenyl­phosphino­cyclo­penta­dienyl][2(η⁵)‐penta­methyl­cyclo­penta­di­enyl]­iron(III)­rhodium(III) hexa­fluoro­phosphate, [{Rh(C₁₀H₁₅)(N₃)}{Fe(μ‐C₁₇H₁₄P)₂}]PF₆ or [FeRh(C₁₀H₁₅)(μ‐C₁₇H₁₄P)₂(N₃)]PF₆, the coordination sphere of Rh^III can be described as pseudo‐tetrahedral, composed of two P atoms from a 1,1′‐bis­(di­phenyl­phosphino)­ferrocene (dppf) ligand, an azido N atom and the centroid of the ring of a C₅Me₅ (Cp*) ligand. The two cyclo­penta­dienyl rings in the dppf moiety adopt an eclipsed conformation. The Rh⋯Fe distance is 4.340 (2) Å.     

1d‐3,4‐Di‐O‐(di­phenyl­methylphos­pho­nio)‐1,2,5,6‐tetra‐O‐methyl‐chiro‐inositol diiodide

The title compound, 3,4,5,6‐tetra­methoxy­cyclo­hexane‐1,2‐diyl­dioxy­bis­(methyl­di­phenyl­phospho­nium) diiodide, C₃₆­H₄₄­O₆­P₂²⁺·­2I^?, was prepared from a New Zealand natural product, d ‐chiro‐inositol, in order to develop new catalytic metal complexes. The inositol ring retains its usual chair conformation with only minor perturbations caused by the bound di­phenyl­methyl­phosphines. Crystal‐packing forces are provided by C—H?I cation–anion interactions.     

A new chain‐like cadmium(II) coordination polymer containing chains of water mol­ecules

The title cadmium(II) polymer, catena‐poly[[[bis­(4‐amino­pyridine‐κN)­aqua­cadmium(II)]‐μ‐1,4‐phenyl­enediacetato‐κ⁴O,O′:O′′,O′′′] dihydrate], {[Cd(C₁₀H₈O₄)(C₅H₆N₂)₂(H₂O)]·2H₂O}_n, comprises one‐dimensional wave‐like chains, in which the Cd atom is coordinated by 1,4‐phenyl­enediacetate and 4‐amino­pyridine molecules. The 1,4‐phenylenediacetate ligands lie about inversion centres. Extensive hydrogen‐bonding inter­actions between the chains lead to a three‐dimensional structure. Free water mol­ecules form chains in the structure.     

[Bis­(di­phenyl­phosphino)­alkane](pentane‐2,4‐di­thionato) complexes of nickel(II)

The structures of a series of four‐coordinate nickel(II) complexes of the form [Ni(sacsac)L] PF₆ (sacsac = pentane‐2,4‐di­thione anion; L = (Ph₂P)₂(CH₂)_n, n = 1,2,3) have beendetermined. These are [bis­(di­phenyl­phosphino)­methane](pentane‐2,4‐di­thionato‐S,S′)­nickel(II) hexa­fluoro­phosphate, [Ni(C₂₅H₂₂P₂)(C₅H₇S₂)]PF₆, [1,2‐bis­(di­phenylphosphino)­ethane](pentane‐2,4‐di­thionato–S,S′)­nickel(II) hexa­fluoro­phosphate, [Ni(C₂₆H₂₄P₂)(C₅H₇S₂)]PF₆, and [1,3‐bis­(di­phenyl­phosphino)­propane](pentane‐2,4‐di­thionato‐S,S′)­nickel(II) hexa­fluoro­phosphate, [Ni(C₂₇H₂₆P₂)(C₅H₇S₂)]PF₆. All have a distorted square‐planar arrangement about Ni with angles around Ni varying with the length of the hydro­carbon chain.     

NiII and ZnII complexes of the hexadentate macrocyclic ligand cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine

The title pendent‐arm macrocyclic hexa­amine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni^II and Zn^II complexes (both as perchlorate salts), namely (cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­nickel(II) di­per­chlorate, [Ni(C₁₂H₃₀N₆)]­­(ClO₄)₂, and (cis‐6,13‐di­methyl‐1,4,8,11‐tetraaza‐cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­zinc(II) di­per­chlorate, [Zn(C₁₂H₃₀N₆)]­(ClO₄)₂. Distortion of the N—M—N valence angles from their ideal octahedral values becomes more pronounced with increasing metal‐ion size and the present results are compared with other structures of this ligand.     

A mixed‐valence diacetate‐bridged MnII–MnIII complex incorporating a bridging phenolate ligand

The synthesis and characterization of a new unsymmetrical dinucleating N,O‐donor ligand, 2‐[N,N‐bis­(2‐pyridyl­methyl)­amino­methyl]‐6‐[N‐(3,5‐di‐tert‐butyl‐2‐oxidobenzyl)‐N‐(2‐pyridyl­amino)­aminomethyl]‐4‐methyl­phenol (H₂Ldtb), as well as the X‐ray crystal structure of its corresponding mixed‐valence diacetate‐bridged manganese complex, di‐μ‐acetato‐μ‐{2‐[N,N‐bis­(2‐pyridylmethyl)amino­methyl]‐6‐[N‐(3,5‐di‐tert‐butyl‐2‐oxidobenzyl)‐N‐(2‐pyridyl­amino)­aminomethyl]‐4‐methylphenolato}dimanganese(II,III) tetra­phenyl­borate, [Mn^IIMn^III(C₄₂H₄₉N₅O₂)(C₂H₃O₂)₂](C₂₄H₂₀B), are reported. The complex may be regarded as an inter­esting structural model for the mixed‐valence Mn^II–Mn^III state of manganese catalase.     

Two dimeric CuII benzoate derivatives solvated with aceto­nitrile

The title compounds, tetrakis(μ‐benzoato‐O:O′)­bis(2,6‐di­amino­pyridine)‐1κN,2κN‐dicopper(II)–aceto­nitrile (1/2), [Cu₂(C₇H₅O₂)₄(C₅H₇N₃)₂]·2C₂H₃N, (I), and bis­(aceto­nitrile)‐1κN,2κN‐tetrakis(μ‐benzoato‐O:O′)­dicopper(II)–aceto­nitrile (1/1.5), [Cu₂(C₇H₅O₂)₄(C₂H₃N)₂]·1.5C₂H₃N, (II), crystallize as aceto­nitrile solvates exhibiting different stability. They have similar molecular structures with discrete dimeric units located at crystallographic inversion centres. The copper ions are bridged by four benzoate groups and neutral N‐donor ligands, viz. 2,6‐di­amino­pyridine in (I) and aceto­nitrile in (II), are coordinated at apical positions. The diverse stability is probably due to hydrogen‐bond interactions of the solvated aceto­nitrile mol­ecules with neighbouring dimers in compound (I).     

cis‐[1,4‐Bis(di­phenyl­phosphino)­butane](μ‐tetra­thio­tungstato)­palladium(II) N,N′‐di­methyl­form­amide hemisolvate hemihydrate

In the title compound, [1,4‐bis(di­phenyl­phosphino)­butane‐2κ²P,P′]­di‐μ‐thio‐1:2κ⁴S‐di­thio‐1κ²S‐palladium(II)­tung­sten(VI) N,N′‐di­methyl­form­amide hemisolvate hemihydrate, [PdWS₄­(C₂₈H₂₈P₂)]·0.5C₃H₇NO·0.5H₂O, the Pd atom is coordinated by two S atoms from the distorted‐tetrahedral [WS₄]²⁻ anion and two P atoms from the dppb mol­ecule [dppb is 1,4‐bis(di­phenyl­phos­phino)­butane] in an approximately square‐planar configuration. A puckered seven‐membered ring is formed by the Pd atom and the dppb ligand.     

A trichloro‐bridged binuclear ruthenium complex with 1,1,1‐tris(diphenylphosphinomethyl)ethane

The tri­chloro‐bridged dinuclear Ru^II complex tri‐μ‐chloro‐bis{[1,1,1‐tris­(di­phenyl­phosphino­methyl)­ethane‐κ³P,P′,P′′]ruthenium(II)} hexa­fluoro­phosphate ethanol solvate, [Ru₂Cl₃(tripod)₂]PF₆·C₂H₆O, containing the tripod [1,1,1‐tris­(di­phenyl­phosphino­methyl)­ethane, C₄₁H₃₉P₃] ligand, was unexpectedly obtained from the reaction of [Ru^IIICl₃(tripod)] with 1,4‐bis­(di­phenyl­phosphino)­butane (dppb), followed by pre­cipitation with NH₄PF₆. The magnetic moment of the compound at room temperature indicates that the dinuclear [Ru₂(μ‐Cl)₃(tripod)₂]⁺ cation is diamagnetic. A single‐crystal X‐ray structure determination revealed that the two Ru atoms are bridged by the three Cl atoms. The coordination sphere of each Ru atom is completed by the three P atoms of a tripod ligand. The two P₃Ru units are exactly eclipsed, while the bridging Cl atoms are staggered with respect to the six P atoms. The Ru⋯Ru distance is 3.3997 (7) Å and the mean Cl—Ru—Cl bond angle is 77.7°.     

The diprotonated 2,2‐(propane‐1,3‐di­yl)bis­(1,1,3,3‐tetra­methyl­guanidinium) cation: packing and conformational changes

Subject to packing with different anions, the title cation undergoes various conformational changes with significantly different N—C—C—C torsion angles, as well as different angles between the NCN₂ guanidine planes. The 2,2‐(propane‐1,3‐di­yl)bis­(1,1,3,3‐tetra­methyl­guanidinium) salts reported here, viz. the dibromide, C₁₃H₃₂N₆²⁺·2Br⁻, the tetra­phenyl­borate chloride, C₁₃H₃₂N₆²⁺·C₂₄H₂₀B⁻·Cl⁻, the tetra­chloro­mercurate, (C₁₃H₃₂N₆)[HgCl₄], and the bis­(trifluoro­methanesulfonate), C₁₃H₃₂N₆²⁺·2CF₃SO₃⁻, are dominated by strong inter­molecular N—H⋯X hydrogen bonds, which form different packing patterns.     

Platinum complexes of oxopurines: cis‐bis(theophyllinato‐N7)bis(triphenylphosphine)platinum(II) and cis‐chloro(theobrominato‐N1)bis(triphenylphosphine)platinum(II) ethanol hemisolvate

The syntheses and structures of two mixed‐ligand complexes of platinum(II) with deprotonated oxopurine bases and tri­phenyl­phosphine are reported, namely the theophyllinate complex cis‐bis(1,2,3,6‐tetra­hydro‐1,3‐di­methyl­purine‐2,6‐dionato‐κN⁷)­bis(tri­phenyl­phosphine‐κP)­platinum(II), [Pt(C₇H₇N₄O₂)₂(C₁₈H₁₅P)₂], (I), and the theobrominate complex cis‐chloro(1,2,3,6‐tetrahydro‐3,7‐dimethylpurine‐2,6‐dionato‐κN¹)­bis(tri­phenyl­phosphine‐κP)­platinum(II) ethanol hemisolvate, [PtCl(C₇H₇N₄O₂)(C₁₈H₁₅P)₂]·0.5C₂H₅OH, (II). In (I), the coordination geometry of Pt is square planar, formed by the two coordinating N atoms of the theophyl­linate anions in a cis arrangement and two P atoms from the tri­phenyl­phosphine groups. In (II), there are two crystallographically independent mol­ecules. They both exhibit a square‐planar coordination geometry around Pt involving one Cl atom, the coordinating N atom of the theobrominate anion and two P atoms from the tri­phenyl­phosphine groups. The two tri­phenyl­phosphine groups are arranged in a cis configuration in both structures. The heterocyclic rings are rotated with respect to the coordination plane of the metal by 82.99 (8) and 88.09 (8)° in complex (I), and by 85.91 (16) and 88.14 (18)° in complex (II). Both structures are stabilized by intramolecular stacking interactions involving the purine rings and the phenyl rings of adjacent tri­phenyl­phosphine moieties.     

Tri­azido­cobalt(III) complexes with tridentate amine ligands

The title compounds, [N‐(2‐amino­ethyl)‐1,3‐propane­di­amine‐κ³N]­tri­azido­cobalt(III), [Co(N₃)₃(C₅H₁₅N₃)], [N‐(2‐amino­ethyl)‐N‐methyl‐1,3‐propane­di­amine‐κ³N]­tri­azido­cobalt(III), [Co(N₃)₃(C₆H₁₇N₃)], [N‐(2‐amino­propyl)‐1,3‐pro­pane­di­am­ine‐κ³N]­tri­azido­cobalt(III), [Co(N₃)₃(C₆H₁₇N₃)], and [N‐(2‐amino­propyl)‐N‐methyl‐1,3‐pro­pane­di­am­ine‐κ³N]triazidocobalt(III), [Co(N₃)₃­(C₇­H₁₉­N₃)], each consist of a Co^III atom, three azide ligands in a meridional configuration and a tridentate amine ligand, namely aepn [N‐(2‐amino­ethyl)‐1,3‐propane­di­amine] or dpt [N‐(3‐amino­propyl)‐1,3‐pro­pane­di­amine], or their N‐methyl­­ated analogs.     

Bis­(acetato‐κ2O,O′)(2,9‐di­methyl‐1,10‐phenanthroline‐κ2N,N′)mercury(II) in two differently hydrated crystal forms

Two differently hydrated crystal forms of the title compound, viz. bis­(acetato‐κ²O,O′)(2,9‐di­methyl‐1,10‐phenanthroline‐κ²N,N′)­mercury(II), [Hg(C₂H₃O₂)₂(C₁₄H₁₂N₂)] or [HgAc₂(dmph)] [dmph is 2,3‐di­methyl‐1,10‐phenantroline (neocuproine) and Ac is acetate], (I), and tris­[bis­(acetato‐κ²O,O′)(2,9‐di­methyl‐1,10‐phenanthroline‐κ²N,N′)­mercury(II)] hexadecahydrate, [Hg(C₂H₃O₂)₂(C₁₄H₁₂N₂)]₃·16H₂O or [HgAc₂(dmph)]₃·16H₂O, (II), are presented. Both structures are composed of very simple monomeric units, which act as the building blocks of complex packing schemes stabilized by a diversity of π–π and hydrogen‐bonding interactions.     

(R)‐(+)‐2,2′‐Bis­(di­phenyl­phosphinoyl)‐1,1′‐bi­naphthyl

The title compound, BINAP oxide, C₄₄H₃₂O₂P₂, (I), was synthesized by direct oxidation of (R)‐(+)‐2,2′‐bis­(di­phenyl­phosphino)‐1,1′‐bi­naphthyl (BINAP) with tert‐butyl hydro­peroxide in toluene solution. The angle between the naphthyl planes of the bi­naphthyl group is 94.17 (3)°.     

Pentane and tetra­hydro­furan solvates of trans‐di­chloro­bis­[1,2‐ethane­diyl­bis­(di­phenyl­phos­phine)‐P,P′]­molybdenum(II)

trans‐[MoCl₂(dppe)₂] [dppe is 1,2‐ethane­diyl­bis­(di­phenyl­phos­phine), C₂₆H₂₄P₂] was obtained as a side product from the reaction of trans‐[Mo(dppe)₂(N₂)₂] with Cp*GeCl to give the germyl­yne complex trans‐[Cl(dppe)₂Mo[triple‐bond]Ge(η¹‐Cp*)]. The crystal structures of the hemi­pentane (0.5C₅H₁₂) and di­tetra­hydro­furan (2C₄H₈O) solvates of trans‐[MoCl₂(dppe)₂], (IIIa) and (IIIb), respectively, have been determined.     

The first metalloporphyrin dimer linked by a bridging phenylenedicarbene ligand

In the first bis­[ruthenium(II)–porphyrin]–dicarbene complex, μ‐[1,4‐phenyl­ene­bis(phenyl­methyl­idene‐κC)]bis­[(ethanol‐κO)(5,10,15,20‐tetra‐p‐tolyl­porphyrinato‐κ⁴N)ruthenium(II)] 1,2‐di­chloro­ethane trisolvate, [Ru₂(C₂₀H₁₄)(C₄₈H₃₆N₄)₂(C₂H₆O)₂]·3C₂H₄Cl₂, an inversion center is located at the center of the μ‐phenyl­ene group, leading to a parallel arrangement for the pair of porphyrin ring systems. The bond lengths and angles compare favourably with literature values for ruthenium–porphyrin–monocarbene complexes; the Ru=C(carbene) bond length and the C(phenyl)—C(carbene)—C(phenyl­ene) angle are 1.865 (3) Å and 112.3 (3)°, respectively. The Ru^II ion is displaced out of the C₂₀N₄ porphyrin least‐squares plane (by 0.2373 Å) toward the bridging ligand of the C_i‐symmetry dimer. The porphyrin ring systems of the dimer thus exhibit mildly domed conformations.     

2,4‐Di­nitro­phenyl­hydrazones of 2,4‐di­hydroxy­benz­aldehyde, 2,4‐di­hydroxy­aceto­phenone and 2,4‐di­hydroxy­benzo­phenone

In 2,4‐di­hydroxy­benz­aldehyde 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­form­amide solvate {or 4‐[(2,4‐di­nitro­phenyl)­hydrazono­methyl]­benzene‐1,3‐diol N,N‐di­methyl­form­amide solvate}, C₁₃H₁₀N₄O₆·C₃H₇NO, (X), 2,4‐di­hydroxy­aceto­phenone 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­form­am­ide solvate (or 4‐{1‐[(2,4‐di­nitro­phenyl)hydrazono]ethyl}benzene‐1,3‐diol N,N‐di­methyl­form­amide solvate), C₁₄H₁₂N₄O₆·C₃H₇NO, (XI), and 2,4‐di­hydroxy­benzo­phenone 2,4‐di­nitro­phenyl­hydrazone N,N‐di­methyl­acet­amide solvate (or 4‐­{[(2,4‐di­nitro­phenyl)hydrazono]phenyl­methyl}benzene‐1,3‐diol N,N‐di­methyl­acet­amide solvate), C₁₉H₁₄N₄O₆·C₄H₉NO, (XII), the molecules all lack a center of symmetry, crystallize in centrosymmetric space groups and have been observed to exhibit non‐linear optical activity. In each case, the hydrazone skeleton is fairly planar, facilitated by the presence of two intramolecular hydrogen bonds and some partial N—N double‐bond character. Each molecule is hydrogen bonded to one solvent mol­ecule.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and dimeric 1:1 adducts with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐­diamino­ethane

In ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–4,4′‐ethyl­enedi­pyridine (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₂N₂, there is an intra­molecular O—H?O hydrogen bond in the ferrocenediol component and a single O—H?N hydrogen bond linking the two components into a finite monomeric adduct. Ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–ethyl­enedi­amine (1/1), [Fe(C₁₈H₁₅O)₂]·C₂H₈N₂, crystallizes with Z′ = 2 in space group P, and there are two independent four‐component aggregates in the structure, both of which are centrosymmetric. In the first type of aggregate, the molecular components are linked by O—H?N and N—H?O hydrogen bonds, in which both di­amine N atoms participate; in the second type of aggregate, the di­amine component is disordered over two sets of sites, but only one N atom is involved in the hydrogen bonding.