Kristallstrukturen „supramolekularer”︁ (Benzo‐18‐krone‐6)kaliumtetrathiocyanatometallate: Ein dimerer Komplex {[K(Benzo‐18‐krone‐6)]2[Hg(SCN)4]}2 und zwei isomere Komplexe [K(Benzo‐18‐krone‐6)][Cd(SCN)3] mit kettenförmigen Trithiocyanatocadmat‐Anionen

Crystal Structures of „Supramolecular”︁ Benzo‐18‐crown‐6 Potassium Tetrathiocyanato Metallates: A Dimeric Complex {[K(Benzo‐18‐crown‐6)]₂[Hg(SCN)₄]}₂ and Two Isomeric Complexes [K(Benzo‐18‐crown‐6)][Cd(SCN)₃] Containing Trithiocyanato Cadmate Anions with Chain Structures By reaction of potassium thiocyanatomercurate(II) complexes with benzo‐18‐crown‐6 (2,3‐benzo‐1,4,7,10,13,16‐hexaoxacyclooctadec‐2‐ene) crystals of {[K(benzo‐18‐crown‐6)]₂[Hg(SCN₄)]}₂ ( 1 ) were obtained. 1 crystallizes monoclinic, space group P2₁/n (non‐standard setting of P2₁/c), a = 1737.35(2), b = 1377.16(2), c = 1984.12(3) pm, β = 100.637(1)°, Z = 2. With potassium tetrathiocyanatocadmate(II) two modifications of a complex [K(benzo‐18‐crown‐6)][Cd(SCN)₃] ( 2 , 3 ), of different symmetry were formed. 2 crystallizes monoclinic, P2₁/c, a = 1158,31(3), b = 1096,55(2), c = 2028,46(2) pm, β = 99,5261(2)°, Z = 4, 3  orthorhombic, P2₁cn, a = 1105,95(3), b = 1413,07(4), c = 1617,10(5) pm, Z = 4. 1 has a dimeric structure, built up from a dication K₂(benzo‐18‐crown‐6)₂]²⁺ and two [K(benzo‐18‐crown‐6)]⁺ cations, which are bridged by two [Hg(SCN)₄]^2– anions. In 2 and 3 triply bridged infinite [{Cd(SCN)₃^–}_n] zigzag chains, stretching along screw axes, are to be found as anions. In 2 these chains exist in two conformations related by inversion symmetry, whereas in 3 only one form can be found. [K(benzo‐18‐crown‐6)]⁺ cations are linked to the anion chains via K · · · S interactions of different lengths.     

Two—dimensional Network Crown Ether Complex.Synthesis and Crystal Structure of 18—Crown—6 Complex：[K（18—C—6）]2[Cd—（nmt）2]

The novel complex [K(18-C-6)]2[Cd(mnt)2][18-C-6-18-crown-6,nmt=1,2-dicyanoethene-1,2-dithiolate,C2S2-(CN)2^2-] was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complex displays two-dimensional network structure of [K(18-C-6)] complex segments and [Cd(nmt)2] complex segment bridged by S-K-S,S-K-N and N-K-N interactions between adjacent[K(18-C-6)] and [Cd(mnt)2]units.     

Fine‐tuning of electromembrane extraction selectivity using 18‐crown‐6 ethers as supported liquid membrane modifiers

Selectivity of electromembrane extractions (EMEs) was fine‐tuned by modifications of supported liquid membrane (SLM) composition using additions of various 18‐crown‐6 ethers into 1‐ethyl‐2‐nitrobenzene. Gradually increased transfer of K⁺, the cation that perfectly fits the cavity of 18‐crown‐6 ethers, was observed for EMEs across SLMs modified with increasing concentrations of 18‐crown‐6 ethers. A SLM containing 1% w/v of dibenzo‐18‐crown‐6 in 1‐ethyl‐2‐nitrobenzene exhibited excellent selectivity for EMEs of K⁺. The established host–guest interactions between crown ether cavities in the SLM and potassium ions in donor solution ensured their almost exhaustive transfer into acceptor solution (extraction recovery ～92%) within 30 min of EME at 50 V. Other inorganic cations were not transferred across the SLM (Ca²⁺ and Mg²⁺) or were transferred negligibly (NH₄⁺, Na⁺; extraction recovery < 2%) and had only subtle effect on EMEs of K⁺. The high selectivity of the tailor‐made SLM holds a great promise for future applications in EMEs since the range of similar selective modifiers is very broad and may be applied in various fields of analytical chemistry.     

Isolated pentaiodide anions in [K(18‐crown‐6)]I5

(1,4,7,10,13,16‐Hexaoxa­cyclo­octa­decane‐κ⁶O)­potassium penta­iodide, [K(C₁₂H₂₄O₆)]I₅, obtained by slow evaporation of an ethanol solution of KI, 18‐crown‐6 and I₂, contains [K(18‐crown‐6)]⁺ cations (C_i symmetry) and I₅⁻ anions (C₂ symmetry), which are arranged in alternating layers parallel to (001). In contrast to the well known tendency of I₅⁻ ions to form chains and nets, the I₅⁻ units in the title compound are isolated.     

碱金属碘化物与冠醚或穴醚的配合物中I3-和I-的氧化还原行为及其在染料敏化纳米薄膜太阳电池中的应用研究

本文利用超微铂电极和循环伏安法研究了在碱金属碘化物与冠醚或穴醚配合物的3-甲氧基丙腈(MePN)溶液中I₃^-和I^-的氧化还原行为。发现I₃^-和I^-在其中的表观扩散系数与阳离子有关，且I₃^-的表观扩散系数符合以下规律：1,2-二甲基-3-丙基咪唑阳离子(DMPI⁺)> [Na(¯¯15-C-5]⁺ > [K(¯¯18-C-6]⁺ > [Na(¯¯2.2.1-cryptand]⁺，I^-的表观扩散系数则为：[Na(¯¯2.2.1-cryptand]⁺> [Na(¯¯15-C-5]⁺ ≈[K(¯¯18-C-6]⁺> DMPI⁺。比较了由上述配合物和1,2-二甲基-3-丙基咪唑碘(DMPII)组成的染料敏化纳米薄膜太阳电池(DSC)的光伏性能，结果表明由上述配合物组成的DSC，其短路电流略高于DMPII，填充因子略低于DMPII，这与I^-和I₃^-在其中的表观扩散系数的大小是相一致的。此外，电解质溶液中的溶剂对DSC的光电转换效率也有较大影响，以MePN为溶剂，含DMPII的DSC的光电转换效率要高于[K(¯¯18-C-6]I，而以乙腈为溶剂，两者的光电转换效率并没有明显的差别。     

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.     

Unusual centrosymmetric structure of [M(18‐crown‐6)]+ (M = Rb,Cs and NH4) complexes stabilized in an environment of hexachloridoantimonate(V) anions

In (1,4,7,10,13,16‐hexaoxacyclooctadecane)rubidium hexachloridoantimonate(V), [Rb(C₁₂H₂₄O₆)][SbCl₆], (1), and its isomorphous caesium {(1,4,7,10,13,16‐hexaoxacyclooctadecane)caesium hexachloridoantimonate(V), [Cs(C₁₂H₂₄O₆)][SbCl₆]}, (2), and ammonium {ammonium hexachloridoantimonate(V)–1,4,7,10,13,16‐hexaoxacyclooctadecane (1/1), (NH₄)[SbCl₆]·C₁₂H₂₄O₆}, (3), analogues, the hexachloridoantimonate(V) anions and 18‐crown‐6 molecules reside across axes passing through the Sb atoms and the centroids of the 18‐crown‐6 groups, both of which coincide with centres of inversion. The Rb⁺ [in (1)], Cs⁺ [in (2)] and NH₄⁺ [in (3)] cations are situated inside the cavity of the 18‐crown‐6 ring; they are situated on axes and are equally disordered about centres of inversion, deviating from the centroid of the 18‐crown‐6 molecule by 0.4808 (13), 0.9344 (7) and 0.515 (8) Å, respectively. Interaction of the ammonium cation and the 18‐crown‐6 group is supported by three equivalent hydrogen bonds [N...O = 2.928 (3) Å and N—H...O = 162°]. The centrosymmetric structure of [Cs(18‐crown‐6)]⁺, with the large Cs⁺ cation approaching the centre of the ligand cavity, is unprecedented and accompanied by unusually short Cs—O bonds [2.939 (2) and 3.091 (2) Å]. For all three compounds, the [M(18‐crown‐6)]⁺ cations and [SbCl₆]⁻ anions afford linear stacks along the c axis, with the cationic complexes embedded between pairs of inversion‐related anions.     

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.     

Cation Effect on Formation of Preyssler‐type 30‐Tungsto‐5‐phosphate: Enhanced Yield of Na‐encapsulated Derivative and Direct Synthesis of Ca‐ and Bi‐Encapsulated Derivatives

The effect of cations in a reaction mixture for the preparation of the Preyssler‐Jeannin‐Pope type 30‐tungsto‐5‐phosphate [P₅W₃₀O₁₁₀Na]^14– is investigated. Reaction of phosphate and tungstate with a P/W ratio of ca. 3.9 in an acidic aqueous solution without cations selectively leads to the Dawson‐type 18‐tungsto‐2‐phosphate, [P₂W₁₈O₆₂]^6–. Amongst all the alkali cations, only Na⁺ allows formation of the Preyssler‐type polyanion [P₅W₃₀O₁₁₀Na]^14–, with an encapsulated Na⁺ ion, and the product yield can be improved by increasing Na⁺ amount. The presence of Li⁺ ions instead results in the Dawson‐type polyanion [P₂W₁₈O₆₂]^6–, whereas K⁺, Rb⁺, and Cs⁺ selectively result in the Keggin‐type polyanion [PW₁₂O₄₀]^3–. An improved synthetic procedure for the Na⁺‐encapsulated Preyssler‐ion leading to a higher isolated yield is presented. Furthermore, addition of Ca²⁺ and Bi³⁺ compounds allows formation of the Ca²⁺‐ and Bi³⁺‐encapsulated Preyssler‐type polyanions, [P₅W₃₀O₁₁₀Ca]^13– and [P₅W₃₀O₁₁₀Bi]^12–, respectively. Furthermore, single‐crystal XRD structure of the Bi³⁺‐encapsulated Preyssler‐type polyanions, [P₅W₃₀O₁₁₀Bi]^12–, is presented for the first time.     

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.     

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.     

Strukturen der Alkalimetallsalze aromatischer,heterocyclischer Amide: Synthese und Struktur von Kronenether‐Addukten der Alkalimetall‐indolide

Structures of Alkali Metal Salts of Aromatic, Heterocyclic Amides: Synthesis and Structure of Crown Ether Adducts of the Alkali Metal Indolides The synthesis of five alkali metal indolide crown ether complexes is reported. Lithium‐indolide(12‐crown‐4) ( 1 ) was synthezised from butyllithium, indole, and 12‐crown‐4; sodium‐indolide(15‐crown‐5) ( 2 ) from sodium metal, indole, and 15‐crown‐5; potassium‐indolide(18‐crown‐6) ( 3 ) from potassium hydride, indole, and 18‐crown‐6. Rubidium‐ and cesium‐indolide(18‐crown‐6) ( 4 , 5 ) were made from Rb‐ and Cs‐hexamethyldisilazide, indole, and 18‐crown‐6. The structures of 2 , 4 , and 5 could be determined by X‐ray diffraction. The complexes 2 and 4 are mononuclear, the indolide anion shows an η¹(N)‐coordination to the metal cation. Complex 5 is dinuclear with a central [Cs—N—]₂‐ring.     

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.     

Potassium di­cyano­argentate(I) 1,4,7,10,13,16‐hexaoxa­cyclo­octadecane

The crystal structure of the title compound, K[Ag(CN)₂]·C₁₂H₂₄O₆, conventionally denoted K(18‐crown‐6)Ag(CN)₂, where 18‐crown‐6 is 1,4,7,10,13,16‐hexa­oxa­cyclo­octa­decane, is characterized by closely packed linear chains formed by the coordination of the nitrile N atoms of the [Ag(CN)₂]⁻ anions to the K⁺ cations. The K atoms lie on centers of inversion and are additionally bound to the six O atoms of the crown ether.     

Propane‐1,3‐diaminium tetrachloridozincate(II) 18‐crown‐6 clathrate

The reaction of propane‐1,3‐diamine hydrochloride, 18‐crown‐6 and zinc(II) chloride in methanol solution yields the title complex salt [systematic name: propane‐1,3‐diaminium tetrachloridozincate(II)–1,4,7,10,13,16‐hexaoxacyclooctadecane (1/1)], (C₃H₁₂N₂)[ZnCl₄]·C₁₂H₂₄O₆, with an unusual supramolecular structure. The diprotonated propane‐1,3‐diaminium cation forms an unexpected 1:1 supramolecular rotator–stator complex with the crown ether, viz. [C₃H₁₂N₂(18‐crown‐6)]²⁺, in which one of the –NH₃⁺ substituents nests in the crown and interacts through N—H...O hydrogen bonding. The other –NH₃⁺ group interacts with the [ZnCl₄]²⁻ anion via N—H...Cl hydrogen bonding, forming cation–crown–anion ribbons parallel to [010].     

Synthesis of a “Masked” Terminal Nickel(II) Sulfide by Reductive Deprotection and its Reaction with Nitrous Oxide

The addition of 1 equiv of KSCPh₃ to [L^RNiCl] (L^R={(2,6‐iPr₂C₆H₃)NC(R)}₂CH; R=Me, tBu) in C₆H₆ results in the formation of [L^RNi(SCPh₃)] ( 1 : R=Me; 2 : R=tBu) in good yields. Subsequent reduction of 1 and 2 with 2 equiv of KC₈ in cold (?25 °C) Et₂O in the presence of 2 equiv of 18‐crown‐6 results in the formation of “masked” terminal Ni^II sulfides, [K(18‐crown‐6)][L^RNi(S)] ( 3 : R=Me; 4 : R=tBu), also in good yields. An X‐ray crystallographic analysis of these complexes suggests that they feature partial multiple‐bond character in their Ni? S linkages. Addition of N₂O to a toluene solution of 4 provides [K(18‐crown‐6)][L^tBuNi(SN?NO)], which features the first example of a thiohyponitrite (κ²‐[SN?NO]^2?) ligand.     

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.     

Quecksilber(II)‐chlorid‐ und ‐iodid‐Komplexe von Dithia‐ und Tetrathiakronenethern

Mercury(II) Chloride and Iodide Complexes of Dithia‐ and Tetrathiacrown Ethers The complexes [(HgCl₂)₂((ch)₂30S₄O₆)] ( 1 ), [HgCl₂(mn21S₂O₅)] ( 2 ), [HgCl₂(ch18S₂O₄)] ( 3 ) and [HgI(meb12S₂O₂)]₂[Hg₂I₆] ( 4 ) have been synthesized, characterized and their crystal structures were determined. In [(HgCl₂)₂((ch)₂30S₄O₆)] two HgCl₂ units are discretely bonded within the ligand cavity of the 30‐membered dichinoxaline‐tetrathia‐30‐crown‐10 ((ch)₂30S₄O₆) forming a binuclear complex. HgCl₂ forms 1 : 1 “in‐cavity” complexes with the 21‐membered maleonitrile‐dithia‐21‐crown‐7 (mn21S₂O₅) ligand and the 18‐membered chinoxaline‐dithia‐18‐crown‐6 (ch18S₂O₄) ligand, respectively. The 12‐membered 4‐methyl‐benzo‐dithia‐12‐crown‐4 (meb12S₂O₂) ligand gave with two equivalents HgI₂ the compound [HgI(meb12S₂O₂)]₂[Hg₂I₆]. In the cation [HgI(meb12S₂O₂)]⁺ meb12S₂O₂ forms with the cation HgI⁺ a half‐sandwich complex.     

One‐dimensionally linked Chain Crown Ether Complexes. Syntheses and Crystal Structures of Complexes [K(18‐Crown‐6)]2[M(SeCN)4](H2O) (M = Pd,Pt)

18‐crown‐6(18‐C‐6) complexes with K₂[M(SeCN)₄] (M = Pd, Pt): [K(18‐C‐6)]₂[Pd(SeCN)₄] (H₂O) ( 1 ) and [K(18‐C‐6)]₂[Pt(SeCN)₄](H₂O) ( 2 ) have been isolated and characterized by elemental analysis, IR spectroscopy and single crystal X‐ray analysis. The complexes crystallize in the monoclinic space group P2₁/n with cell dimensions: 1 : a = 1.1159(3) Å, b = 1.2397(3) Å, c = 1.6003(4) Å, β = 92.798(4)°, V = 2.2111(8) ų, Z = 2, F(000) = 1140, R₁ = 0.0418, wR₂ = 0.0932 and 2 : a = 1.1167(3) Å, b = 1.2394(3) Å, c = 1.5968(4) Å, β = 92.945(4)°, V = 2.2071(9) ų, Z = 2, F(000) = 1204, R₁ = 0.0341, wR₂ = 0.0745. Both complexes form one‐dimensionally linked chains of [K(18‐C‐6)]⁺ cations and [M(SeCN)₄]^2— (M = Pd, Pt) anions bridged by K‐O‐K interactions between adjacent [K(18‐C‐6)]⁺ units.     

Copper(I) π‐Complexes with 2‐Butyne‐1,4‐diol. Synthesis and Crystal Structure of Na[CuCl2(HOCH2C≡CCH2OH)]·2H2O

Crystals of anionic Na[CuCl₂(HOCH₂C≡CCH₂OH)]·2H₂O π‐complex have been synthesized by interaction of 2‐butyne‐1,4‐diol with CuCl in a concentrated aqueous NaCl solution and characterized by X‐ray diffraction at 100 K. The crystals are triclinic: space group , a = 7.142(3), b = 7.703(3), c = 10.425(4) Å, α = 105.60(3), β = 99.49(3), γ = 110.43(3)°, V = 495.9(4) ų, Z = 2, R = 0.0203 for 3496 reflections. The structure is built of discrete [CuCl₂(HOCH₂C≡CCH₂OH)]^? anionic stacks and polymeric cations among the stacks. The Cu^I atom adopts trigonal planar coordination of two Cl^? anions and the C≡C bond of 2‐butyne‐1,4‐diol, Cu–(C≡C) distance is equal to 1.903(3) Å. Na⁺ cations environment is octahedral and consists of O and Cl atoms. The crystal packing is governed by strong hydrogen bonds of O–H···Cl and O–H···O types.