Pentazol‐Derivate und daraus entstehende Azide: [O3S—p‐C6H4—N5]— und [O3S—p‐C6H4—N3]— als Kalium‐Kronenether‐Salze

Pentazole Derivates and Azides Formed from them: Potassium‐Crown‐Ether Salts of [O₃S—p‐C₆H₄—N₅]^— and [O₃S—p‐C₆H₄—N₃]^{— —}O₃S—p‐C₆H₄—N₂⁺ was reacted with sodium azide at —50 °C in methanol, yielding a mixture of 4‐pentazolylbenzenesulfonate and 4‐azidobenzenesulfonate (amount‐of‐substance ratio 27:73 according to NMR). By addition of KOH in methanol at —50 °C a mixture of the potassium salts K[O₃S—p‐C₆H₄—N₅] and K[O₃S—p‐C₆H₄—N₃] was precipitated (ratio 60:40). A solution of this mixture along with 18‐crown‐6 in tetrahydrofurane yielded the crystalline pentazole derivate [THF‐K‐18‐crown‐6][O₃S—p‐C₆H₄—N₅]·THF by addition of petrol ether at —70 °C. From the same solution upon evaporation and redissolution in THF/petrol ether the crystalline azide [THF‐K‐18‐crown‐6][O₃S—p‐C₆H₄—N₃]·THF was obtained. A solution of the latter in chloroform/toluene under air yielded [K‐18‐crown‐6][O₃S—p‐C₆H₄—N₃]·1/3H₂O. According to their X‐ray crystal structure determinations [THF‐K‐18‐crown‐6][O₃S—p‐C₆H₄—N₅]·THF and [THF‐K‐18‐crown‐6][O₃S—p‐C₆H₄—N₃]·THF have the same kind of crystal packing. Differences worth mentioning exist only for the atomic positions of the pentazole ring as compared to the azido group and for one THF molecule which is coordinated to the potassium ion; different orientations of the THF molecule take account for the different space requirements of the N₅ and the N₃ group. In [K‐18‐crown‐6][O₃S—p‐C₆H₄—N₃]·1/3H₂O there exists one unit consisting of one [K‐18‐crown‐6]⁺ and one [O₃S‐C₆H₄—N₃]^— ion and another unit consisting of two [O₃S‐C₆H₄—N₃]^— ions joined via two [K‐18‐crown‐6]⁺ ions and one water molecule. The rate constants for the decomposition [O₃S‐C₆H₄—N₅]^— → [O₃S‐C₆H₄—N₃]^— + N₂ in methanol were determined at 0 °C and —20 °C.     

A three‐component cocrystal: benzoyl(hydroxyimino)acetonitrile–18‐crown‐6–water (2/1/4)

In the title compound, 2C₉H₆N₂O₂·C₁₂H₂₄O₆·4H₂O, the 18‐crown‐6 (1,4,7,10,13,16‐hexaoxacyclooctadecane) molecule resides across a centre of inversion. The adduct exists as a molecular hydrogen‐bonded complex featuring integration of two kinds of synthons, viz. [(18‐crown‐6)(H₂O)₄] [O...O = 2.8645 (18)–2.9014 (18) Å] and an oxime/aqua ensemble, PhC(O)C(CN)NOH...OH₂ [O...O = 2.5930 (18) Å]. The reliability of the oxime/aqua motif, sustained by the highly acidic cyanooxime, is an essential factor in the construction of multicomponent cocrystals and the accommodation of oxime species in macrocyclic hosts. The supramolecular structure is generated by the alternation of hydrophilic [(18‐crown‐6)(H₂O)₄] layers and bilayers of benzoyl(hydroxyimino)acetonitrile molecules, resulting in stacking interactions between the phenyl and cyano groups of 3.666 (2) Å.     

Neue Kronenether‐stabilisierte Oxoniumhalogenochalkogenate: [H3O(Dibromo‐benzo‐18‐Krone‐6)]2[Se3Br10] und [H5O2(Bis‐dibromo‐dibenzo‐24‐Krone‐8]2[Se3Br8]

Novel Oxonium Halogenochalcogenates Stabilized by Crown Ethers: [H₃O(Dibromo‐benzo‐18‐crown‐6)]₂[Se₃Br₁₀] and [H₅O₂(Bis‐dibromo‐dibenzo‐24‐crown‐8]₂[Se₃Br₈] Two novel complex oxonium bromoselenates(II,IV) and –(II) are reported containing [H₃O]⁺ and [H₅O₂]⁺ cations coordinated by crown ether ligands. [H₃O(dibromo‐benzo‐18‐crown‐6)]₂[Se₃Br₁₀] ( 1 ) and [H₅O₂(bis‐dibromo‐dibenzo‐24‐crown‐8]₂[Se₃Br₈] ( 2 ) were prepared as dark red crystals from dichloromethane or acetonitrile solutions of selenium tetrabromide, the corresponding unsubstituted crown ethers, and aqueous hydrogen bromide. The products were characterized by their crystal structures and by vibrational spectra. 1 is triclinic, space group (Nr. 2) with a = 8.609(2) Å, b = 13.391(3) Å, c = 13.928(3) Å, α = 64.60(2)°, β = 76.18(2)°, γ = 87.78(2)°, V = 1404.7(5) ų, Z = 1. 2 is also triclinic, space group with a = 10.499(2) Å, b = 13.033(3) Å, c = 14.756(3) Å, α = 113.77(3)°, β = 98.17(3)°, γ = 93.55(3)°. V = 1813.2(7) ų, Z = 1. In the reaction mixture complex redox reactions take place, resulting in (partial) reduction of selenium and bromination of the crown ether molecules. In 1 the centrosymmetric trinuclear [Se₃Br₁₀]^2? consists of a central Se^IVBr₆ octahedron sharing trans edges with two square planar Se^IIBr₄ groups. The novel [Se₃Br₈]^2? in 2 is composed of three planar trans‐edge sharing Se^IIBr₄ squares in a linear arrangement. The internal structure of the oxonium‐crown ether complexes is largely determined by the steric restrictions imposed by the aromatic rings in the crown ether molecules, as compared to complexes with more flexible unsubstituted crown ether ligands.     

Dinuclear Complexes of Copper(I) with Crown Ether‐containing N‐Thiophosphorylated Bis‐thioureas and 2,2′‐Bipyridine or 1,10‐Phenanthroline: Synthesis,Characterization, and Picrate Extraction Properties

Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)₂P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 ( H₂L^I ), N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐18‐crown‐6 ( H₂L^II ) and N,N′‐bis[C(S)NHP(S)(OiPr)₂]‐1,7‐diaza‐15‐crown‐5 ( H₂L^III ). Reaction of the potassium salts of H₂L^I–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH₂Cl₂ leads to the dinuclear complexes [Cu₂(bpy)₂L^I–III] and [Cu₂(phen)₂L^I–III] . The structures of these compounds were investigated by ¹H, ³¹P{¹H} NMR spectroscopy, and elemental analysis. The crystal structures of H₂L^I and [Cu₂(phen)₂L^I] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe₂)CH₂P(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)₂]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH₄Pic were also studied.     

Bis(adamantan‐1‐aminium) tetrachloridozincate(II) 18‐crown‐6 monohydrate clathrate

The structure of the title compound [systematic name: bis(adamantan‐1‐aminium) tetrachloridozincate(II)–1,4,7,10,13,16‐hexaoxacyclooctadecane–water (1/1/1)], (C₁₀H₁₈N)₂[ZnCl₄]·C₁₂H₂₄O₆·H₂O, consists of supramolecular rotator–stator assemblies and ribbons of hydrogen bonds parallel to [010]. The assemblies are composed of one protonated adamantan‐1‐aminium cation and one crown ether molecule (1,4,7,10,13,16‐hexaoxacyclooctadecane) to give an overall [(C₁₀H₁₈N)(18‐crown‐6)]⁺ cation. The –NH₃⁺ group of the cation nests in the crown and links to the crown‐ether O atoms through N—H...O hydrogen bonds. The 18‐crown‐6 ring adopts a pseudo‐C_3v conformation. The second adamantan‐1‐aminium forms part of ribbons of adamantan‐1‐aminium–water–tetrachloridozincate units which are interconnected by O—H...Cl, N—H...O and N—H...Cl hydrogen bonds via three different continuous rings with R₅⁴(12), R₄³(10) and R₃³(8) motifs.     

4‐Carboxypyridinium perchlorate 18‐crown‐6 dihydrate clathrate and 4‐carboxypyridinium tetrafluoroborate 18‐crown‐6 dihydrate clathrate

Mixtures of 4‐carboxypyridinium perchlorate or 4‐carboxypyridinium tetrafluoroborate and 18‐crown‐6 (1,4,7,10,13,16‐hexaoxacyclooctadecane) in ethanol and water solution yielded the title supramolecular salts, C₆H₆NO₂⁺·ClO₄⁻·C₁₂H₂₄O₆·2H₂O and C₆H₆NO₂⁺·BF₄⁻·C₁₂H₂₄O₆·2H₂O. Based on their similar crystal symmetries, unit cells and supramolecular assemblies, the salts are essentially isostructural. The asymmetric unit in each structure includes one protonated isonicotinic acid cation and one crown ether molecule, which together give a [(C₆H₆NO₂)(18‐crown‐6)]⁺ supramolecular cation. N—H...O hydrogen bonds between the protonated N atoms and a single O atom of each crown ether result in the 4‐carboxypyridinium cations `perching' on the 18‐crown‐6 molecules. Further hydrogen‐bonding interactions involving the supramolecular cation and both water molecules form a one‐dimensional zigzag chain that propagates along the crystallographic c direction. O—H...O or O—H...F hydrogen bonds between one of the water molecules and the anions fix the anion positions as pendant upon this chain, without further increasing the dimensionality of the supramolecular network.     

Neue Halogenochalkogen(IV)‐Säuren: [H3O(Benzo‐18‐Krone‐6)]2[Te2Br10] und [H5O2(Dibenzo‐24‐Krone‐8)]2[Te2Br10]

Novel Halogenochalcogeno(IV) Acids: [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] Systematic studies on halogenochalcogeno(IV) acids containing tellurium and bromine led to the new crystalline phases [H₃O(Benzo‐18‐Crown‐6)]₂[Te₂Br₁₀] ( 1 ) and [H₅O₂(Dibenzo‐24‐Crown‐8)]₂[Te₂Br₁₀] ( 2 ). The [Te₂Br₁₀]^2‐ anions consists of two edge‐sharing distorted TeBr₆ octahedra, the oxonium cations are stabilized by crownether. ( 1 ) crystallizes in the monoclinic space group P2₁/n with a = 14.520(5) Å, b = 22.259(6) Å, c = 16.053(5) Å, β = 97.76(3)° and Z = 4, whereas ( 2 ) crystallizes in the triclinic space group with a = 11.005(4) Å, b = 12.103(5) Å, c = 14.951(6) Å, α = 71.61(3)°, β = 69.17(3)°, γ = 68.40(3)° and Z = 1.     

A novel PtII–dibenzo‐18‐crown‐6 (DB18C6) complex

The novel Pt^II–dibenzo‐18‐crown‐6 (DB18C6) title complex, μ‐[tetrakis­(thio­cyanato‐S)­platinum(II)]‐N:N′‐bis{[2,5,8,­15,18,21‐hexa­oxa­tri­cyclo­[20.4.0.1^9,14]­hexa­cosa‐1(22),9(14),10,12,23,25‐hexaene‐κ⁶O]­potassium(I)}, [K(C₂₀H₂₄O₆)]₂[Pt(SCN)₄], has been isolated and characterized by X‐ray diffraction analysis. The structure analysis shows that the complex displays a quasi‐one‐dimensional infinite chain of two [K(DB18C6)]⁺ complex cations and a [Pt(SCN)₄]^2? anion, bridged by K⁺?π interactions between adjacent [K(DB18C6)]⁺ units.     

A Supermolecule Assembled by Sodium Cation,Crown Ether and α‐Dawson Heteropolyanion

The supermolecular based on sodium molybdate(VI) and sulfate, dibenzo‐18‐crown‐6 was synthesized in acetonitrile and characterized by elemental analysis, IR, ¹H NMR, single crystal X‐ray diffraction, indicating that it contains [S₂Mo₁₈O₆₂]⁴⁺ and [Na(DB18C6)(H₂O)]⁺, where each sodium ion is deviated from the plane defined by the oxygen atoms in the corresponding crown ether. The compound crystallizes in the monoclinic space group C2/c with a=3.29332(10) nm, b=1.90917(6) nm, c=2.63132(7) nm, β=121.6630(10)°, V=14081.8(7) nm³, Z=8, T=293(2) K, and R₁ (wR₂)=0.0177 (0.1525). The compound exhibits a novel organic‐inorganic structure, in which the crown ether‐sodium complexes are coordinated to the terminal oxygen atoms of Mo₁₈O₅₄ and the oxygen atoms of water molecule.     

Formation,Dynamic Behavior,and Chemical Transformation of Pt Complexes with a Rotaxane‐like Structure

The reaction of [Pt(CH₂COMe)(Ph)(cod)] (cod=1,5‐cyclooctadiene) with (ArCH₂NH₂CH₂‐C₆H₄COOH)⁺(PF₆)^? (Ar=4‐tBuC₆H₄ or 9‐anthryl) in the presence of cyclic oligoethers such as dibenzo[24]crown‐8 (DB24C8) and dicyclohexano[24]crown‐8 (DC24C8) produces {(ce)[ArCH₂NH₂CH₂C₆H₄COOPt(Ph)(cod)]}⁺(PF₆)^? (ce=DB24C8 or DC24C8, Ar=4‐tBuC₆H₄ or 9‐anthryl) with interlocked structures. FABMS and NMR spectra of a solution of these compounds indicate that the Pt complexes with a secondary ammonium group and DB24C8 (or DC24C8) make up the axis and cyclic components, respectively. Temperature‐dependent ¹H NMR spectra of a solution of {(DB24C8)[4‐tBuC₆H₄CH₂NH₂CH₂‐C₆H₄COOPt(Ph)(cod)]}⁺(PF₆)^? ({(DB24C8)[ 4 ‐H]}⁺(PF₆)^?) show equilibration with free DB24C8 and the axis component. The addition of DB24C8 to a solution of {(DC24C8)[ 4 ‐H]}⁺(PF₆)^? causes partial exchange of the macrocyclic component of the interlocked molecules, giving a mixture of {(DC24C8)[ 4 ‐H]}⁺(PF₆)^?, {(DB24C8)[ 4 ‐H]}⁺(PF₆)^?, and free macrocyclic compounds. The reaction of 3,5‐Me₂C₆H₃COCl with {(DB24C8)[ 4 ‐H]}⁺(PF₆)^? affords the organic rotaxane {(DB24C8)(4‐tBuC₆H₄CH₂NH₂CH₂‐C₆H₄COOCOC₆H₃Me₂‐3,5)}⁺(PF₆)^? through C? O bond formation between the aroyl group and the carboxylate ligand of the axis component. The addition of 2,2′‐bipyridine (bpy) to a solution of {(DB24C8)[ 4 ‐H]}⁺(PF₆)^? induces the degradation of the interlocked structure to form a complex with trigonal bipyramidal coordination, [Pt(Ph)(bpy)(cod)]⁺(PF₆)^?, whereas the reaction of bpy with [Pt(OCOC₆H₄Me‐4)(Ph)(cod)] produces the square‐planar complex [Pt(OCOC₆H₄Me‐4)(Ph)(bpy)].     

Transport properties of solid state crown ether channel systems

Single crystals of [(H₂O)⊂(DB18C6)(μ₂-H₂O)_2/2][(H₃O)⊂(DB18C6)(μ₂-H₂O)_2/2]I₃ 1 were shown to possess ideally stacked crown ether molecules which form channels running in one direction through the solid state structure. By immersion of single crystals of 1 into NaOH, ion exchange takes place to yield the compound [(Na)⊂(DB18C6)(μ₂-H₂O)_2/2][(Na)⊂(DB18C6)(μ₂-OH)_2/2]I₃ 2, with slightly but significantly different cell parameters. Both compounds were tested for transport properties through these channels by using two different devices, one for water transport, the other for NaOH transport, through single crystals of 1 and 2, respectively. The results indicate that transport can take place via a hopping mechanism.     

Solvent‐Vapor‐Induced Reversible Single‐Crystal‐to‐Single‐Crystal Transformation of a Triphosphaazatriangulene‐Based Metal–Organic Framework

A triphosphaazatriangulene (H₃L) was synthesized through an intramolecular triple phospha‐Friedel–Crafts reaction. The H₃L triangulene contains three phosphinate groups and an extended π‐conjugated framework, which enables the stimuli‐responsive reversible transformation of [Cu(HL)(DMSO)?(MeOH)]_n, a 3D‐MOF that exhibits reversible sorption characteristics, into (H₃L?0.5 [Cu₂(OH)₄?6 H₂O] ?4 H₂O), a 1D‐columnar assembled proton‐conducting material. The hydrophilic nature of the latter resulted in a proton conductivity of 5.5×10^?3 S cm^?1 at 95 % relative humidity and 60 °C.     

Natriumkomplexe mit Salicylideniminen: Synthesen,Strukturen, CO2‐Aufnahme und Carboxylierung von 2‐Fluorpropiophenon bzw. Estronmethylether

Chiral salicylidenphenethylamines (R)‐HA or (S)‐HA , 2‐salicylidenfurfuryl‐imines HB , and 2‐salicylidenaminoethanol HC react with sodium hydride or sodium hexamethyldisilylamide to form the sodium complexes [Na(R)‐A] ₄ · 0,5 Et ₂ , [Na(S)‐A] ₄ · 0,5 Et ₂ O (1) , [NaB] ₄ · 0,5 Ph‐Me (2) and [(dme)NaC] ₄ (3) . In the presence of 18‐crown‐6 the complex [Na(18‐crown‐6)(thf) ₂ ] ₂ [Na ₂ (C)] ₄ · THF (4) can also be isolated. The crystal structure analyses of both 1 and 2 show that heterocubane structures with a Na₄O₄ frame work are formed. Additionally, the imine nitrogen atom is bonded at the Na atom which has the coordination number 4 in 1 . Additional coordination of the furfuryl oxygen atom results in the coordination number five for the sodium atom in 2 . In 3 which is also a tetramer, two Na₂O₂ units are connected via two imino‐ethanol bridges Na(1)‐N(=CH‐phenolat)‐CH₂CH₂‐OH‐Na(2A). The crystal structure analysis displays that 4 is an ionic compound consisting of two [(thf)₂Na(18‐crown‐6)]⁺ cations and the dinuclear dianion [Na ₂ (C) ₄ ] ^2? . Both 1 and 2 are carboxylation reagents which transfer CO₂ to 2‐fluoropropiophenone. 1 is more active than 2 , but 3 and 4 are inactive.     

(18‐Crown‐6)‐μ‐oxo‐hexa­kis(tetra­hydro­borato)diuranium(IV): an unprecedented asymmetric dinuclear complex

In the title compound, (1,4,7,10,13,16‐hexa­oxacyclo­octa­decane‐1κ⁶O)‐μ‐oxo‐1:2κ²O:O‐hexa­kis(tetra­hydro­borato)‐1κ³H;2κ²H;2κ²H;2κ³H;2κ³H;2κ³H‐diuranium(IV), [U₂(BH₄)₆O(C₁₂H₂₄O₆)], one of the U atoms (U1), located at the centre of the crown ether moiety, is bound to the six ether O atoms, and also to a tridentate tetra­hydro­borate group and a μ‐oxo atom in axial positions. The other U atom (U2) is bound to the same oxo group and to five tetra­hydro­borate moieties, three of them tridentate and the other two bidentate. The two metal centres are bridged by the μ‐oxo atom in an asymmetric fashion, thus giving the species (18‐crown‐6)(κ³‐BH₄)U=(μ‐O)—U(κ³‐BH₄)₃(κ²‐BH₄)₂, in which the U1=O and U2—O bond lengths to the μ‐O atom [1.979 (5) and 2.187 (5) Å, respectively] are indicative of the presence of positive and negative partial charges on U1 and U2, respectively.     

Reaction of the Pincer‐type Ligand {2, 6‐[P(O)(OEt)2]2‐4‐tert‐Bu‐C6H2}— with [Ph3C]+[PF6]—. Unprecedented Rearrangement and Carbon‐Carbon Bond Formation

The reaction of the organolithium derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu‐C₆H₂}Li ( 1 ‐Li) with [Ph₃C]⁺[PF₆]^— gave the substituted biphenyl derivative 4‐[(C₆H₅)₂CH]‐4′‐[tert‐Bu]‐2′, 6′‐[P(O)(OEt)₂]₂‐1, 1′‐biphenyl ( 5 ) which was characterized by ¹H, ¹³C and ³¹P NMR spectroscopy and single crystal X‐ray analysis. Ab initio MO‐calculations reveal the intramolecular O···C distances in 5 of 2.952(4) and 2.988(5)Å being shorter than the sum of the van der Waals radii of oxygen and carbon to be the result of crystal packing effects. Also reported are the synthesis and structure of the bromine‐substituted derivative {2, 6‐[P(O)(OEt)₂]₂‐4‐tert‐Bu]C₆H₂}Br ( 9 ) and the structure of the protonated ligand 5‐tert‐Bu‐1, 3‐[P(O)(OEt)₂]₂C₆H₃ ( 1 ‐H). The structures of 1 ‐H, 5 , and 9 are compared with those of related metal‐substituted derivatives.     

A molecule based on polyoxometalate acid and crown ether: synthesis and characterization of [(H3O)(C20H24O6)]2[HPMo12O40]·C20H24O6·3MeCN·H2O (C20H24O6=dibenzo-18-crown-6)

The new molecule based on 12-molybdophosphate acid and dibenzo-18-crown-6, [(H₃O)(C₂₀H₂₄O₆)]₂[HPMo₁₂O₄₀]·C₂₀H₂₄O₆·3MeCN·H₂O 1, was synthesized in acetonitrile and characterized by elemental analyses, IR, ¹H NMR, electrospray mass spectra and single crystal X-ray diffraction, indicating that it contains [(H₃O)(dibenzo-18-crown-6)]⁺ cations, where oxonium ions are out of the planes defined by crown ether oxygen atoms, and disordered PMo₁₂O₄₀³⁻ anions with α-Keggin structure where the crystal has high lattice energy so that it is difficult to dissolve it. The crystallographic disorder averages Mo-Mo distances and Mo-O_b/c-Mo angles between the M₃ triplets and within the M₃ triplet. The interactions between crown ether molecules and oxonium ions are hydrogen-bonding with the O(crown ether)-OH₃⁺ distances of 2.510(10)-2.783(7) Å. The interactions between [(H₃O)(dibenzo-18-crown-6)]⁺ cations and PMo₁₂O₄₀³⁻ anions are dominantly electrostatic. The electrical conductivity is <10⁻⁷ S.cm⁻¹.     

Complexes of Crown Ether‐Containing N‐Phosphorylated Thioamides and Thioureas with CoII,ZnII and PdII Cations

The reaction of the potassium salts of N‐phosphorylated thioureas [4′‐benzo‐15‐crown‐5]NHC(S)NHP(Y)(OiPr)₂ (Y = S, HL^I ; Y = O, HL^II ) with Zn^II and Co^II cations in aqueous EtOH leads to complexes of formulae Zn(L^I,II‐S,Y)₂ (Y = S, 1 ; Y = O, 2 ) and Co(L^I‐S,S′)₂ ( 3 ), while interaction of the potassium salt of N‐phosphorylated thioamide [4′‐benzo‐15‐crown‐5]C(S)NHP(O)(OiPr)₂ ( HL^III ) with Zn^II in the same conditions leads to the complex Zn(HL^III)(L^III‐S,O)₂ ( 4 ). The reaction of the potassium salt of crown ether‐containing N‐phosphorylated bis‐thiourea N,N′‐[C(S)NHP(O)(OiPr)₂]₂‐1,10‐diaza‐18‐crown‐6 ( H₂L ) with Co^II, Zn^II and Pd^II cations in anhydrous CH₃OH leads to complexes M₂(L‐O,S)₂ (M = Co, 5 ; Zn, 6 ; M = Pd, 7 ). Thioamide HL^III was investigated by single‐crystal X‐ray diffraction.     

Hydrated hexacyanometallate(III) salts of triaqua(18‐crown‐6)lanthanoid(III) and tetraaqua(18‐crown‐6)lanthanoid(III) cations containing nine‐ and ten‐coordinate lanthanoids

Tetraaqua(18‐crown‐6)cerium(III) hexacyanoferrate(III) dihydrate, [Ce(C₁₂H₂₄O₆)(H₂O)₄][Fe(CN)₆]·2H₂O, and tetraaqua(18‐crown‐6)neodymium(III) hexacyanoferrate(III) dihydrate, [Nd(C₁₂H₂₄O₆)(H₂O)₄][Fe(CN)₆]·2H₂O, are isomorphous and isostructural in the C2/c space group, where the cations, which contain ten‐coordinate lanthanoid centres, lie across twofold rotation axes and the anions lie across inversion centres. In these compounds, an extensive series of O—H...O and O—H...N hydrogen bonds links the components into a continuous three‐dimensional framework. Triaqua(18‐crown‐6)lanthanoid(III) hexacyanoferrate(III) dihydrate, [Ln(C₁₂H₂₄O₆)(H₂O)₃][Fe(CN)₆]·2H₂O, where Ln = Sm, Eu, Gd or Tb, are all isomorphous and isostructural in the P space group, as are triaqua(18‐crown‐6)gadolinium(III) hexacyanochromate(III) dihydrate, [Gd(C₁₂H₂₄O₆)(H₂O)₃][Cr(CN)₆]·2H₂O, and triaqua(18‐crown‐6)gadolinium(III) hexacyanocobaltate(III) dihydrate, [Gd(C₁₂H₂₄O₆)(H₂O)₃][Co(CN)₆]·2H₂O. In these compounds, there are two independent anions, both lying across inversion centres, and the lanthanoid centres exhibit nine‐coordination; in the crystal structures, an extensive series of hydrogen bonds links the components into a three‐dimensional framework.     

[Na(DB18-C-6)(H2O)2][Na(DB18-C-6)(SCN)2]：Two-Di-mensional Network Complex Assembled by π-π Stacking Interactios,Hydrogen Bonds and Electrostatic Interactions

A novel two‐dimensional network dibenzo‐18‐crown‐6 (DB18‐C6) complex: [Na (DB18‐C‐6) (H₂O)₂] [Na (DB18‐C‐6) (SCN)₂] has been isolated and characterized by elemental, IR and X‐ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2₁/c with cell dimensions a = 1.06178(7), b = 1.40243(8), c = 3.03496(19) nm, β = 90.4220(10)°, V = 4.5292(5) nm³, Z=4, D_calcd =1.351 g/ cm³, F(000) = 1936, R₁ = 0.0369, wR₂ = 0.0821. The most interesting feature in this structure is that complex cation and complex anion form a two‐dimensional network via τ‐τ stacking interactions, hydrogen bonds and electrostatic interactions.     

Two nickel(II) bis[(pyridin‐2‐yl)methyl]amine complexes with homophthalic and benzene‐1,2,4,5‐tetracarboxylic acids

Two new Ni^II complexes involving the ancillary ligand bis[(pyridin‐2‐yl)methyl]amine (bpma) and two different carboxylate ligands, i.e. homophthalate [hph; systematic name: 2‐(2‐carboxylatophenyl)acetate] and benzene‐1,2,4,5‐tetracarboxylate (btc), namely catena‐poly[[aqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)]‐μ‐2‐(2‐carboxylatophenyl)aceteto‐κ²O:O′], [Ni(C₉H₆O₄)(C₁₂H₁₃N₃)(H₂O)]_n, and (μ‐benzene‐1,2,4,5‐tetracarboxylato‐κ⁴O¹,O²:O⁴,O⁵)bis(aqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)) bis(triaqua{bis[(pyridin‐2‐yl)methyl]amine‐κ³N,N′,N′′}nickel(II)) benzene‐1,2,4,5‐tetracarboxylate hexahydrate, [Ni₂(C₁₀H₂O₈)(C₁₂H₁₃N₃)₂(H₂O)₂]·[Ni(C₁₂H₁₃N₃)(H₂O)₃]₂(C₁₀H₂O₈)·6H₂O, (II), are presented. Compound (I) is a one‐dimensional polymer with hph acting as a bridging ligand and with the chains linked by weak C—H...O interactions. The structure of compound (II) is much more complex, with two independent Ni^II centres having different environments, one of them as part of centrosymmetric [Ni(bpma)(H₂O)]₂(btc) dinuclear complexes and the other in mononuclear [Ni(bpma)(H₂O)₃]²⁺ cations which (in a 2:1 ratio) provide charge balance for btc⁴⁻ anions. A profuse hydrogen‐bonding scheme, where both coordinated and crystal water molecules play a crucial role, provides the supramolecular linkage of the different groups.