Synthese und Kristallstrukturen neuer phosphorverbrückter bimetallischer Cluster der Elemente Quecksilber und Eisen

Synthesis and Crystal Structures of New Phosphorus‐bridged Bimetallic Clusters of the Elements Mercury and Iron The reaction of [Fe(CO)₄(HgX)₂] (X = Cl, Br) with P(SiMe₃)₂^tBu in the presence of tertiary phosphines and phosphinium salts leads to the ionic compounds [PPh₄]₂[Hg₁₂{Fe(CO)₄}₈(P^tBu)₄X₂] (X = Cl, Br) ( 1 , 2 ). If [Fe(CO)₄(HgX)₂] reacts with P(SiMe₃)₂^tBu the polymeric polynuclear complex [Hg₁₅{Fe(CO)₄}₃(P^tBu)₈Br₈]n ( 3 ) as well as the twenty mercury‐ and eight iron‐atoms containing [Hg₂₀{Fe(CO)₄}₈(P^tBu)₁₀X₄]‐clusters (X = Br, Cl) ( 4 , 5 ) are formed. The reaction of [Fe(CO)₄(HgX)₂] with LiPPh₂ yields to the phosphanido‐bridged [Hg₄{Fe(CO)₄}₂(PPh₂)₂Cl₂] ( 6 ), where as the use of LiP(SiMe₃)Ph leads to the diphosphinidene‐bridged cluster [Li(thf)₄]₂[Hg₁₀{Fe(CO)₄}₆(P₂Ph₂)₂Br₆] ( 7 ). The structures of the compounds 1–7 were characterized by X‐ray single crystal structure analysis.     

Formation of Unusual Complexes from the Reaction of [C(NMe2)3][(CO)4Fe{C(O)NMe2}] with InMe3; Crystal Structures of [C(NMe2)3]3[Fe2(CO)6(μ‐CO){μ‐InFe(CO)4(μ‐O2CNMe2)InFe(CO)4}] and [C(NMe2)3]2[{(CO)4Fe}2In(O2CNMe2)]·THF

The carbamoyl complex [C(NMe₂)₃][(CO)₄Fe{C(O)NMe₂}] ( 1 ) reacts with InMe₃ under loss of the methyl groups to produce a variety of compounds from which only the anionic cluster complexes [C(NMe₂)₃]₃[Fe₂(CO)₆(μ‐CO){μ‐InFe(CO)₄(μ‐O₂CNMe₂)InFe(CO)₄}] ([C N ₃]₃[ 2 ]) and [C(NMe₂)₃]₂[{(CO)₄Fe}₂In(O₂CNMe₂)]·THF ([C N ₃]₂[ 3 ]·THF) could be crystallized and characterized by X‐ray analyses. The anion [ 2 ]^3? has a Fe₂(CO)₉‐like structure and both anions contain the carbaminato ligand either in a bridging or in a chelating function.     

A Deeper Insight in Solutions Containing the Hypothetical Labile Complex Species “Fe(CO)4THF”

In the literature it was proposed that the treatment of [Fe₂(CO)₉] in THF resulted, during dissolution, in deep red solutions which should presumably contain labile complexes “Fe(CO)₄THF”. This was supported by the fact that such solutions afforded, in the presence of N‐donor ligands like pyridine (py) or pyrazine (pz), metal carbonyl complexes of the formula [Fe(CO)₄(py)] and [Fe(CO)₄(pz)], respectively. Herein we describe how the true nature of these solutions can be better explained by a valence‐disproportionation reaction of the diiron nonacarbonyl, induced by the donor solvent THF, resulting in the compound [Fe(THF)₆][Fe₃(CO)₁₁]. The formation of the undecacarbonyl‐triferrate(2–) in such solutions was unambiguously confirmed by IR spectroscopy and by the isolation and crystallization of the corresponding salt (PPN)₂[Fe₃(CO)₁₁]; its molecular structure was determined, however, already described in the literature.     

Synthesen und Strukturen neuer amido- und imidoverbrückter Cobaltcluster: [Li(THF)2]3[Co3(μ2-NHMes)3Cl6] (1), [Li(DME)3]2[Co18(μ4-NPh)3(μ3-NPh)12Cl3] (2), [Li(DME)3]2[Co6(μ4-NPh)(μ2-NPh)6(PPh2Et)2] (3) und [Li(THF)4][Co8(μ3-NPh)6(μ2-NPh)3(PPh3)2] (4)

Syntheses and Crystal Structures of new Amido- und Imidobridged Cobalt Clusters: [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] (1), [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] (2), [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] (3), and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] (4) The reactions of cobalt(II)-chloride with the lithium-amides LiNHMes and Li₂NPh leads to an amido-bridged multinuclear complex [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] ( 1 ) as well as to the imido-bridged cobalt cluster [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] ( 2 ). In the presence of tertiary phosphines two imido-bridged cobalt clusters [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] ( 3 ) and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] ( 4 ) result. The structures of 1 – 4 were characterized by X-ray single crystal structure analysis.     

Bis{tris[(1H‐benzimidazol‐3‐ium‐2‐yl)methyl]amine} tetraaquaocta‐μ2‐chlorido‐octachloridopentacadmate(II) monohydrate

The title compound, (C₂₄H₂₄N₇)₂[Cd₅Cl₁₆(H₂O)₄]·H₂O, contains a [Cd₅Cl₁₆(H₂O)₄]⁶⁻ anion, two triply protonated tris[(1H‐benzimidazol‐3‐ium‐2‐yl)methyl]amine cations and one solvent water molecule. The structure of the anion is a novel chloride‐bridged pentanuclear cluster. The five unique Cd^II centres have quite different coordination environments. Two of the central hexacoordinated Cd^II cations have a CdOCl₅ chromophore, in which each Cd^II cation is ligated by four bridging chloride ligands, one terminal chloride ligand and one water molecule, adopting a distorted octahedral environment. The third central Cd^II cation is octahedrally coordinated by four bridging chloride ligands and two water molecules. Finally, the two terminal Cd^II cations are pentacoordinated by two bridging and three terminal chloride ligands and adopt a trigonal–bipyramidal geometry. A three‐dimensional supramolecular network is formed through intra‐ and intermolecular O—H...O, O—H...Cl, N—H...Cl and N—H...O hydrogen bonds and π–π interactions between the cations and anions.<!?tpb=20.6pt>     

TMEDA in Iron‐Catalyzed Kumada Coupling: Amine Adduct versus Homoleptic “ate” Complex Formation

The reactions of iron chlorides with mesityl Grignard reagents and tetramethylethylenediamine (TMEDA) under catalytically relevant conditions tend to yield the homoleptic “ate” complex [Fe(mes)₃]^? (mes=mesityl) rather than adducts of the diamine, and it is this ate complex that accounts for the catalytic activity. Both [Fe(mes)₃]^? and the related complex [Fe(Bn)₃]^? (Bn=benzyl) react faster with representative electrophiles than the equivalent neutral [FeR₂(TMEDA)] complexes. Fe^I species are observed under catalytically relevant conditions with both benzyl and smaller aryl Grignard reagents. The X‐ray structures of [Fe(Bn)₃]^? and [Fe(Bn)₄]^? were determined; [Fe(Bn)₄]^? is the first homoleptic σ‐hydrocarbyl Fe^III complex that has been structurally characterized.     

Reaktionen von Nitrosylkomplexen. XIII. Synthese neuer zwei- und dreikerniger heterobimetallischer Komplexe mit NO-Brückenliganden

Reactions of Nitrosyl Complexes. XIII. Synthesis of Novel Di- and Trinuclear Heterobimetallic Complexes with Bridging NO Ligands By reaction of [{Cp′Fe(μ-NO)}₂] with [Cp′Mn(CO)₂ · (THF)] (Cp′ = μ⁵-C₅H₄Me) in THF [Cp₃′Fe₂Mn(μ-CO)₂(μ-NO) · (μ₃-NO)] 1 is formed in high yield. The reaction of [{Cp′Fe(μ-NO)}₂]Na with [Cp′Mn(CO)₂NO]BF₄ in DME/acetone yields besides known [{Cp′Mn(CO)(NO)}₂] 2 the novel complex [Cp₂′FeMn(μ-NO)₂NO] 3 . By interaction between [Cp′Mn(CO)₂(THF)] and 3 , [Cp₃′FeMn₂(μ-CO)(μ-NO)₂ · (μ₃-NO)] 4 is formed. The complex 4 represents the hitherto unknown missing link in the series of the isoelectronic clusters [Cp₃′Mn₃(μ-NO)₃(μ₃-NO)], 1 , and [Cp₃′Fe₃(μ-CO)₃(μ₃-NO)]. Attempts to synthesize the unknown complex [(Cp′FeNO)₂ · Cr(CO)₅] by addition of carbene analogous Cr(CO)₅ fragments to the Fe=Fe bond in [{Cp′Fe(μ-NO)}₂] only led to very low yields of [Cp₂′FeCr(CO)₅] 5 . The new complexes were characterized by mass, NMR and IR spectra.     

Umsetzung von C(NMe2)4 mit Ni(CO)4 – Synthesen und Strukturen von [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12] und [C(NMe2)3]3[Ni6(CO)12][O2CNMe2]

Reaction of C(NMe₂)₄ with Ni(CO)₄ – Syntheses and Structures of [C(NMe₂)₃][(CO)₃NiC(O)NMe₂], [C(NMe₂)₃]₂[Ni₅(CO)₁₂], and [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] The reaction of C(NMe₂)₄ with Ni(CO)₄ in THF produces the carbamoyl complex [C(NMe₂)₃][(CO)₃NiC(O)NMe₂] ( 1 ); side products are the purple cluster compound [C(NMe₂)₃]₂[Ni₅(CO)₁₂] · THF ( 2 · THF) and the red cocristallization product [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms C_Carbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.     

Bis[2‐(3‐pyridinio)benzimidazolium] di‐μ‐chloro‐bis­[trichloro­cadmium(II)]

The title compound, (C₁₂H₁₁N₃)₂[Cd₂Cl₈], consists of two discrete 2‐(3‐pyridinio)benzimidazolium cations and one [Cd₂Cl₈]⁴⁻ anion. The dimeric [Cd₂Cl₈]⁴⁻ anion lies about an inversion centre and consists of two distorted [CdCl₅] trigonal bipyramids which share a common edge. The two Cd atoms are each coordinated by two μ‐Cl atoms and three terminal Cl atoms, with a Cd·Cd separation of 3.9853 (6) Å. The packing displays two‐dimensional hydrogen‐bonded sheets, which are further linked by C—H·Cl contacts and π–π stacking inter­actions to yield a three‐dimensional network.     

Zinc cadmium ammine aqua monophosphate and its thermal transformations

Synthesis of amorphous zinc cadmium ammine aqua monophosphates Zn_3?x Cd _x (PO₄). 2n(NH₃) · m(H₂O) (x = 0.6–2.4, n = 1.3–3.1, m = 2.3–3.4) with variable molar ratio of the cations described. The sequence of thermal transformations of compound [Zn_1.5Cd_1.5(NH₃)_1.4(H₂O)_3.2(PO₄)₂] with equimolar ratio of cations is studied, and schemes of its transformation into the crystalline zinc cadmium monophosphate Zn_1.5Cd_1.5(PO₄)₂ are suggested.     

The bimolecular structure of aquahexa‐μ‐chlorido‐μ4‐oxido‐tris(tetrahydrofuran‐κO)tetracopper(II)–hexa‐μ‐chlorido‐μ4‐oxido‐tetrakis(tetrahydrofuran‐κO)tetracopper(II)–tetrahydrofuran (2/1/4)

The title bimolecular structure, [Cu₄Cl₆O(C₄H₈O)₃(H₂O)]₂[Cu₄Cl₆O(C₄H₈O)₄]·4C₄H₈O, at 100 K has monoclinic (P2₁/c) symmetry. The structure contains nine symmetry‐independent molecules expressed in simplest molecular form as 6[Cu₄Cl₆O(C₄H₈O)₃(H₂O)·2(C₄H₈O)]:3Cu₄Cl₆O(C₄H₈O)₄. The compound exhibits a supercell (smaller than the unit cell based on weak reflections) structure due to pseudotranslational symmetry. The structure displays O—H...O hydrogen bonding between bound water ligands and tetrahydrofuran (THF) solvent molecules. The structure exhibits disorder for 12 of the THF molecules, of which seven are ligated to Cu and five are hydrogen bonded to H₂O ligands.     

Bis(N‐acetyltriethylphosphaniminium)‐tetraacetato‐dichloro‐dicuprat(II), [MeC(O)N(H)PEt3]2[Cu2(O2C–Me)4Cl2]

Bis(N‐acetyltriethylphosphaneiminium)‐tetraacetato‐dichloro‐dicuprate(II), [MeC(O)N(H)PEt₃]₂[Cu₂(O₂C–Me)₄Cl₂] The title compound has been prepared by the reaction of Me₃SiNPEt₃ with [Cu₂(O₂C–Me)₄] and MeC(O)Cl in dichloromethane solution to give colourless crystals which include four molecules CH₂Cl₂ per formula unit. The complex is characterized by IR spectroscopy and by a crystal structure determination. [MeC(O)N(H)PEt₃]₂[Cu₂(O₂C–Me)₄Cl₂] · 4 CH₂Cl₂: Space group P2₁/n, Z = 2, lattice dimensions at –70 °C: a = 794.1(1), b = 2356.9(6), c = 1327.3(2) pm; β = 91.00(1)°; R₁ = 0.0597. The structure consists of N‐acetyltriethylphosphaneiminium cations and dianions [Cu₂(O₂C–Me)₄Cl₂]^2– which form an iontriple with N–H…Cl hydrogen bridges.     

Synthesis of three-component high nuclearity cluster complexes with ruthenium carbido carbonyl clusters as a building block

Treatment of AgNO₃ with the Rh-Ru and Cu-Ru hetero bimetallic clusters, [PPN][RhRu₅C(CO)₁₄(cod)] and [PPh₄]₂[CuRu₆C(CO)₁₆Cl], afforded novel three-component complexes having one silver-, and two silver-bridges between respective cluster units, [PPN]{Ag[RhRu₅C(CO)₁₄(cod)]₂} and [PPh₄]₂{Ag₂[CuRu₆C(CO)₁₆Cl]₂}, respectively. Reaction of the ruthenium-copper cluster [PPh₄]₂{Cu₄[Ru₆C(CO)₁₆]₂Cl₂} (6) with Pd₂(dba)₃ · CHCl₃ gave another three-component cluster [PPh₄]₂{Cu₄Pd₂[Ru₆C(CO)₁₆]₂Cl₂} by incorporation of two palladium atoms. However, a similar reaction of 6 with Pt(dba)₂ gave only a two-component cluster complex, [PPh₄]₂{Pt₂[Ru₆C(CO)₁₅]₂}, while the reaction of silver analog [PPN]₂{Ag₄[Ru₆C(CO)₁₆]₂Cl₂} with Pd₂(dba)₃ · CHCl₃ resulted in the formation of known ruthenium-palladium cluster [PPN]₂{Pd₄[Ru₆C(CO)₁₆]₂}. Treatment of 6 with [RhCl(CO)₂]₂ gave two two-component clusters, [PPh₄][RhRu₅C(CO)₁₆] and [PPh₄]₂{Cu₇[Ru₆C(CO)₁₅]₂Cl₃}. All the new mixed-metal high nuclearity clusters have been characterized by single crystal X-ray analyses.     

Probing the Metal Composition of Ternary 12–12′‐16 Nanoclusters via Electrospray Ionization Mass Spectrometry

The reaction of [(3,5‐Me₂–C₅H₃N)₂Zn(SeSiMe₃)₂] with a solution of Cd(OAc)₂, Se(Ph)SiMe₃ and PPr₃ at low temperature was used to prepare single crystals of ternary group 12–12′‐16 nanoclusters with the composition [Zn_1.8Cd_8.2Se₄(SePh)₁₂(PPr₃)₄]. A ligand exchange reaction using Na[SePh] was performed to displace the neutral PPr₃ ligands. The resulting clusters were probed using electrospray ionization mass spectrometry to determine the number of zinc and cadmium atoms in the cluster and compared to the all cadmium cluster [Cd₁₀Se₄(SePh)₁₂(PPr₃)₄]. The dianionic clusters [Zn_xCd_10–xSe₄(SePh)₁₄]^2– where x = 0, 1, 2 were assigned in the mass spectra, revealing that the clusters exhibit elemental distributions that are quite narrow in these experiments.     

Design and synthesis of methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl]sulfanyl}acetate (phpy2NS) as a ligand for complexes of Group 12 elements: structural assessment and hydrogen‐bonded supramolecular assembly analysis

The reaction of 2‐cyanopyridine with N‐phenylthiosemicarbazide afforded 2‐[amino(pyridin‐2‐yl)methylidene]‐N‐phenylhydrazine‐1‐carbothioamide (Ham4ph) and crystals of 4‐phenyl‐5‐(pyridin‐2‐yl)‐2,4‐dihydro‐3H‐1,2,4‐triazole‐3‐thione (pyph3NS, 1 , C₁₃H₁₀N₄S). Crystals of methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl]sulfanyl}acetate (phpy2NS, 2 , C₁₆H₁₄N₄O₂S), derived from 1 , were obtained by the reaction of Ham4ph with chloroacetic acid, followed by the acid‐catalyzed esterification of the carboxylic acid with methyl alcohol. Crystals of bis(methanol‐κO)bis(methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl‐κ²N¹,N⁵]sulfanyl}acetato)zinc(II)/cadmium(II) hexabromidocadmate(II), [Zn_0.76Cd_0.24(C₁₆H₁₄N₄O₂S)₂(CH₃OH)₂][Cd₂Br₆] or [Zn_0.76Cd_0.24(phpy2NS)₂(MeOH)₂][Cd₂Br₆], 3 , and dichlorido(methyl 2‐{[4‐phenyl‐5‐(pyridin‐2‐yl)‐4H‐1,2,4‐triazol‐3‐yl‐κ²N¹,N⁵]sulfanyl}acetato)mercury(II), [HgCl₂(C₁₆H₁₄N₄O₂S)] or [Hg(phpy2NS)Cl₂], 4 , were synthesized using ligand 2 and CdBr₂ or HgCl₂, respectively. The molecular and supramolecular structures of the compounds were studied by X‐ray diffractometry. The asymmetric unit of 3 is formed from CdBr₃ and M(phpy2NS)(MeOH) units, where the metal centre M has a 76% occupancy of Zn^II and 24% of Cd^II. The M²⁺ centre of the cation, located on a crystallographic inversion centre, is hexacoordinated and appears as a slightly distorted octahedral [MN₄O₂]²⁺ cation. The Cd centre of the anion is coordinated by two terminal bromide ligands and two bridging bromide ligands that generate [Cd₂Br₆]^2? cadmium–bromide clusters. These clusters display crystallographic inversion symmetry forming two edge‐shared tetrahedra and serve as agents that direct the structure in the formation of supramolecular assemblies. In mononuclear complex 4 , the coordination geometry around the Hg²⁺ ion is distorted tetrahedral and comprises two chloride ligands and two N‐atom donors from the phpy2NS ligand, viz. one pyridine N atom and the other from triazole. In the crystal packing, all four compounds exhibit weak intermolecular interactions, which facilitate the formation of three‐dimensional architectures. Along with the noncovalent interactions, the structural diversity in the complexes can be attributed to the metal centre and to the coordination geometry, as well as to its ionic or neutral character.     

Reaktionen von Zink- und Cadmiumhalogeniden mit Tris(trimethylsilyl)phosphan und Tris(trimethylsilyl)arsan

Reactions of Zinc and Cadmium Halides with Tris(trimethylsilyl)phosphane and Tris(trimethylsilyl)arsane ZnCl₂ reacts with E(SiMe₃)₃ (E = P, As) in toluene in the presence of PⁿPr₃ to give the binuclear complexes [Zn₂Cl₂{E(SiMe₃)₂}₂(PⁿPr₃)₂] · C₇H₈ (E = P 1 , As 2 ). Therefore by the use of PⁱPr₃ clusters consisting of ten metal atoms are obtained, [Zn₁₀Cl₁₂(ESiMe₃)₄(PⁱPr₃)₄] (E = P 3 , As 4 ). As a result of the reaction of CdBr₂ with P(SiMe₃)₃ the compound [CdBr₂{P(SiMe₃)₃}]₂ ( 5 ) can be isolated at –40 °C. In the presence of PⁿPr₃ CdBr₂ reacts with P(SiMe₃)₃ forming the binuclear complex [Cd₂Br₂{P(SiMe₃)₂}₂(PⁿPr₃)₂] · thf ( 6 ). The same reaction with PⁱPr₃ yields to the cluster [Cd₁₀Br₁₂(PSiMe₃)₄{P(SiMe₃)₃}₄] · 2 C₇H₈ ( 7 ). ZnI₂ and CdI₂ react with As(SiMe₃)₃ to yield the complexes [MI₂{As(SiMe₃)₃}]₂ (M = Zn 8 , Cd 9 ). In the case of CdI₂ additionally the cluster [Cd₁₀I₁₂(AsSiMe₃)₄ · {As(SiMe₃)₃}₄] · 4,5 C₇H₈ ( 10 ) is formed which is analogous to the compounds 3 , 4 and 7 . In the presence of [PⁿBu₄]I 8  reacts in THF to give the ionic compound [PⁿBu₄]₂[Zn₆I₆(AsSiMe₃)₄(thf)₂] · C₆H₆ ( 11 ).     

Extended Architectures Constructed from Sandwich Tetra‐Metal‐Substituted Polyoxotungstates and Transition‐Metal Complexes

Three unprecedented 2D architectures made up of sandwich‐type tetra‐metal‐substituted polyoxotungstates and transition‐metal complexes, [Cu(dien)(H₂O)]₂{[Cu(dien)(H₂O)]₂‐[Cu(dien)(H₂O)₂]₂[Cu₄(SiW₉O₃₄)₂]}? 5H₂O ( 1 ; dien=diethylenetriamine), [Zn(enMe)₂(H₂O)]₂{[Zn(enMe)₂]₂[Zn₄‐ (HenMe)₂(PW₉O₃₄)₂]}?8H₂O ( 2 ; enMe =1,2‐diaminopropane), and [Zn(enMe)₂‐(H₂O)]₄[Zn(enMe)₂]₂{(enMe)₂{[Zn‐ (enMe)₂]₂[Zn₄(HSiW₉O₃₄)₂]}{[Zn‐ (enMe)₂(H₂O)]₂[Zn₄(HSiW₉O₃₄)₂]}}? 13H₂O ( 3 ) were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single‐crystal X‐ray diffraction. Compound 1 consists of anions [Cu₄(SiW₉O₃₄)₂]^12? linked by copper complexes into a 2D structure, whereas 2 is constructed from novel inorganic–organic hybrid anions [Zn₄(HenMe)₂(PW₉O₃₄)₂]^8? linked by zinc complexes into a 2D structure. The most interesting is the unique 2D network 3 , which consists of anions [Zn₄(PW₉O₃₄)₂]^10? with two types of bridging groups: zinc complexes and enMe ligands.     

Oligonukleare Benzylthiolat‐Zinkkomplexe

Oligonuclear Benzylthiolate Zinc Complexes From solutions of zinc nitrate and sodium benzylthiolate crystallize, depending on the reaction conditions, tetraalkylammonium salts of the zinc complexes [Zn₂(SBz)₆]^2—, [Zn₄(SBz)₁₀]^2—, and [Zn₈(S)(SBz)₁₆]^2—. In each complex the zinc ions are tetrahedrally coordinated by sulfur atoms. [Zn₄(SBz)₁₀]^2— has an adamantane framework. The bridging thiolate sulfur atoms in [Zn₈(S)(SBz)₁₆]^2—, unlike those in icosahedral reference compounds, form a cuboctahedral framework.     

catena‐Poly[[bis­[μ‐2,4‐dichloro‐6‐(2‐pyridyl­methyl­imino­meth­yl)phenolato]dicadmium(II)]‐di‐μ‐thiocyanato]

The title complex, [Cd₂(C₁₃H₉Cl₂N₂O)₂(NCS)₂]_n, is a novel thio­cyanate‐bridged polynuclear cadmium(II) compound. The Cd^II atom is six‐coordinated in a distorted octa­hedral configuration, with one O and two N atoms of one Schiff base mol­ecule and one terminal S atom of a bridging thio­cyanate ligand defining the equatorial plane, and one terminal N atom of another bridging thio­cyanate ligand and one O atom of another Schiff base mol­ecule occupying axial positions. Adjacent inversion‐related [2,4‐dichloro‐6‐(2‐pyridylmethyl­imino­meth­yl)phenolato]cadmium(II) moieties utilize bridging phenolate and thio­cyanate groups to form polymeric chains running along the b axis.     

Supramolecular Hydrogen‐Bonded Frameworks from a New Bisphosphonic Acid and Transition Metal Ions

The reaction of 2‐morpholinoethylimino‐bis(methylenephosphonic acid) (H₄L) with cobalt(II), nickel(II) acetate, and cadmium(II) chloride in ethanol/water mixed solvents afforded three new crystal‐engineered supramolecular metal phosphonates, Co(H₃L)₂ · 2H₂O ( 1 ), Ni(H₃L)₂ · 2H₂O ( 2 ), and [Cd₂Cl₄(H₂O)₆]_0.5[H₄L] ( 3 ) by using a layering technique. The cobalt(II) ions in complex 1 are hexacoordinated by four phosphonate oxygen atoms and two imino nitrogen atoms. The mononuclear units of complex 1 are connected through hydrogen bonds to form a three dimensional supramolecular network. The structure of compound 2 is analogous to that of 1 except that the cobalt(II) ion in compound 1 is replaced by nickel(II) in compound 2 . In the molecular structure of compound 3 , cadmium is coordinated to three chloride ions and three aqua oxygen atoms to form a novel neutral dinuclear complex. Several hydrogen bonds connect the dinuclear complex and the neutral form of the ligand to build a supramolecular three dimensional structure.