Neue Polyiodide des Caesiums mit Doppel‐ und Tripeldecker‐Kationen, [Cs(Benzo‐18‐Krone‐6)2]Ix und [Cs2(Benzo‐18‐Krone‐6)3](Ix)2 (x = 3, 5)

New Polyiodides of Cesium containing Double and Triple Decker Cations, [Cs(benzo‐18‐crown‐6)₂]I_x and [Cs₂(benzo‐18‐crown‐6)₃](I_x)₂ (x = 3, 5) [Cs(b18c6)₂]I_x (x = 3 (1) , 5 (3) ) and [Cs₂(b18c6)₃](I_x)₂ (x = 3 (2) , 5 (4) ) (b18c6 = benzo‐18‐crown‐6) have been synthesized by the reaction of benzo‐18‐crown‐6 (C₁₆H₂₄O₆), cesium iodide (CsI) and iodine (I₂) in acetonitrile ( 1 ), ethanol/dichloromethane ( 2 , 4 ) and 2‐methoxyethanol ( 3 ). Their crystal structures were determined on the basis of single crystal X‐ray data {( 1 ): monoclinic, C2/c, Z = 4, a = 2048.8(5), b = 1329.5(5), c = 1588.7(5) pm, β = 110.23(1)°; ( 2 ): monoclinic, C2/c, Z = 4, a = 2296.0(1), b = 2092.7(1), c = 1373.6(1) pm, β = 100.21(1)°; ( 3 ): monoclinic, P2₁/n, Z = 4, a = 1586.3(1), b = 1745.5(1), c = 1608.6(1) pm, β = 92.37(1)°; ( 4 ): triclinic, , Z = 2, a = 1241.7(1), b = 1539.8(2), c = 1938.4(2) pm, α = 91.15(1), β = 100.53(1), γ = 95.26(1)°}. As expected, double decker cations centered by Cs atoms, [Cs(b18c6)₂]⁺, are found in the structures of ( 1 ) and ( 3 ). In contrast, the triple decker cation found in ( 2 ) and ( 4 ) is less common. The triiodide anions of ( 1 ) and ( 2 ) can be regarded as normal and the chain‐type pentaiodide anions of ( 3 ) and ( 4 ) fall into the known systematic sequence of these anions. The differences in the connectivity of the crystallographically independent I₅^? anions in ( 4 ) are surprising with respect to the fact that, so far, independent pentaiodide anions do not show variations in their scheme of connectivity within one crystal structure.     

M(benzo‐18‐crown‐6)I4 (M = Cd,Hg): Tetraiodide,Iodide–Iodine Adduct,or an Inclusion Compound of Iodine in MI2@(benzo‐18‐crown‐6)?

M(benzo‐18‐crown‐6)I₄ (M = Cd, Hg) are obtained as red columnar crystals from the reactions of benzo‐18‐crown‐6 (b18c6), cadmium and mercury iodide, respectively, and iodine in molar ratios of 1:1:2 in acetonitrile. They both crystallize with the orthorhombic crystal system, P2₁2₁2₁, a = 833.7(1), b = 1610.9(1), c = 1846.8(1) pm, V = 2480.3(1) 10⁶·pm³, Z = 4, for M = Cd and a = 823.4(1), b = 1616.5(1), c = 1866.1(1) pm, V = 2483.8(2) 10⁶·pm³ for M = Hg. The crystal structures consist of [M(b18c6)]I₂ molecules which are connected to a slightly lengthened iodine molecule via a secondary contact, according to the formulation I₂@[MI₂@(b18c6)].     

Pb(18‐crown‐6)Cl2 and Hg(18‐crown‐6)I2: Molecular Dihalides Trapped in a Crown Ether

Pb(18‐crown‐6)Cl₂ and Hg(18‐crown‐6)I₂ are obtained as transparent colourless crystals of needle and hexagonal shape, respectively, by isothermal evaporation of their dichloromethane solutions. Pb(18‐crown‐6)Cl₂ crystallizes with the trigonal crystal system [ , no. 148, a = b = 1176.3(2), c = 1191.8(3) pm, V = 1428.2(5) 10⁶·pm³, Z = 3] whereas Hg(18‐crown‐6)I₂ crystallizes with the orthorhombic crystal system (Pnma, no. 62, a = 1613.9(2) pm, b = 2822.2(5) pm, c = 841.3(1) pm, V = 3832(1)10⁶·pm³, Z = 8). Both compounds are characterized by linear MX₂ (HgI₂ or PbCl₂) molecular units which are encrypted by the crown ether. In both cases, the divalent metal ion resides in the middle of the crown ether resulting in a hexagonal bipyramidal coordination environment for the metal cations. The molecular symmetry comes close to D_3d. Hg(18‐crown‐6)I₂ and Pb(18‐crown‐6)Cl₂ differ in the way the single MX₂@18‐crown‐6 units are packed. Whereas the Hg(18‐crown‐6)I₂ molecules are arranged in a (distorted) cubic closest packing, the Pb(18‐crown‐6)Cl₂ molecules adopt a hexagonal closest packing.     

An Unusual Mixed‐Anionic Iodine‐Rich Polyiodide: [Rb(crypt‐2,2,2)]4(I5)2(I8)

Black crystals of [Rb(crypt‐2,2,2)]₄(I₅)₂(I₈) were obtained from a dichloromethane/ethanol solution of RbI, I₂ and Kryptofix‐2,2,2®. The crystal structure (monoclinic, P2₁/c (no. 14), a = 1250.1(1), b = 2555.2(2), c = 2313.4(3) pm, β = 121.45(1)°, V = 6309.9(11)·10⁶ pm³, Z = 2) consists of [Rb(crypt‐2,2,2)]⁺ cations leaving three‐dimensional channels for the V‐shaped (I₅)^? and Z‐shaped (I₈)^2? anions which are isolated from each other.     

Die Molekül‐ und Kristallstruktur des Rubidium(Dibenzo‐18‐Krone‐6)‐pentaiodids [Rb(C20H24O6)]I5

Molecular and Crystal Structure of Rubidium(dibenzo‐18‐crown‐6)pentaiodide [Rb(C₂₀H₂₄O₆)]I₅ [Rb(Dibenzo‐18‐crown‐6)]₂(I₅)₂ is obtained as dark brown columns by reacting dibenzo‐18‐crown‐6, rubidium iodide, and iodine in a molar ratio of 1 : 1 : 6 in ethanole / dichlormethane (1:1). [Rb(C₂₀H₂₄O₆)]₂(I₅)₂ crystallizes with four formula units per unit cell in the orthorhombic space group Pnma with a = 1725.15(2) pm, b = 1863.76(3) pm and c = 1885.19(3) pm. The crystal structure consists of pentaiodide units I₅^—, which are linked to one another by head‐to‐tail‐contacts. The I₂ units, which stick out of the chain, are twisted against each other, in a way that neither a cis or a trans configuration is formed. By secondary bonding, the iodine atoms form nets of 18‐member planar rings with an almost rectangular form. This net‐like structural element has not been described up to now.     

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.     

Komplexe einwertiger Dibenzo‐18‐Krone‐6‐Kationen mit Triiodid als Anionen

Complexes of Monovalent Dibenzo‐18‐crown‐6 Cations with Triiodide as Anions The new polyiodides [NH₄(db18c6)]₂(I₃)₂ ( 1 ), [NH₄(db18c6)](db18c6)I₃ ( 2 ), [Na_1/2(db18c6)H₂O]₂I₃ ( 3 ), [Rb(db18c6)]I₃ ( 4 ), [Rb(db18c6)]₂(I₃)₂ ( 5 ), [Cs(db18c6)]I₃ ( 6 ), and [Cs₂(db18c6)₃][Cs(db18c6)_3/2](I₃)₃ ( 7 ) were obtained from reactions of dibenzo‐18‐crown‐6 (db18c6) and iodine with NH₄I, NaI, RbI, and CsI. Their crystal structures were determined by single‐crystal X‐ray diffraction. ( 1 ) M = NH₄, ( 5 ) M = Rb: monoclinic, P2₁/n, a = 1409,67(8), b = 2211,63(14), c = 1627,16(10) pm, β = 101,030(5)°, Z = 4 (crystal data for M = NH₄); ( 2 ): monoclinic, Pn, a = 1345,26(14), b = 773,82(4), c = 2095,10(20) pm, β = 94,439(8)°, Z = 2; ( 3 ): orthorhombic, Pnaa, a = 931,59(13), b = 2213,3(5), c = 2223,9(4) pm, Z = 4; ( 4 ): monoclinic, P2₁/n, a = 999,50(6), b = 1711,33(10), c = 1517,45(9) pm, β = 99,021(5)°, Z = 4; ( 6 ): triclinic, , a = 705,16(9), b = 1137,93(14), c = 1678,90(20) pm, α = 73,719(10), β = 79,782(10), γ = 83,669(10)°, Z = 2; ( 7 ): triclinic, , a = 1519,25(6), b = 1702,49(7), c = 2136,41(9) pm, α = 102,641(3), β = 101,989(3), γ = 91,911(3)°, Z = 2. 1 : 1 cations centered by M, [M(db18c6)]⁺, are found in the structures of ( 1 – 6 ). In contrast, the triple decker cation found in ( 7 ) is less common. The crystal structures are completed by mostly asymmetrically linear I₃^? anions.     

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.     

Complexation of Alkali Triflates by Crown Ethers: Synthesis and Crystal Structure of [Na(12‐crown‐4)2][SO3CF3], [Na(15‐crown‐5)][SO3CF3], [Rb(18‐crown‐6)][SO3CF3], and [Cs(18‐crown‐6)][SO3CF3]

Complexes of trifluoromethanesulfonates (triflates) with alkali metals Na, Rb, Cs have been prepared in the presence of various macrocyclic polyether crowns [(12‐crown‐4), (15‐crown‐5) and (18‐crown‐6)]. Depending on the combination of alkali ion with crown, the complexes include separated ion pairs [Na(12‐crown‐4)₂] [SO₃CF₃] ( 1 ) and contact ion pairs [Na(15‐crown‐5)] [SO₃CF₃] ( 2 ), [Rb(18‐crown‐6)] [SO₃CF₃] ( 3 ), and [Cs(18‐crown‐6)] [SO₃CF₃] ( 4 ), in which the triflate acts as a bidentate ligand. It is shown that the choice of crown ether is of paramount importance in determining the solid‐state structural outcome. The complex resulting from the pairing of crown ether ( 1 ) develops, when the crown ether is too small in relation to the alkali ion radius. When the cavity size of the crown ether is matched with the alkali ion radius, simple monomeric structures are identified in 2 , 3 and 4 . The title compounds crystallize in the monoclinic crystal system: 1 : space group P2/c with a = 9.942(3), b = 11.014(2), c = 10.801(3) Å, β = 97.30(2)°, V = 1173.1(4) ų, Z = 2, R1 = 0.0812, wR2 = 0.1133: 2 : space group P2₁/m with a = 7.949(2), b = 12.063(3), c = 9.094(2) Å, β = 105.98(2)°, V = 838.3(4) ų, Z = 2, R1 = 0.0869, wR2 = 0.1035: 3 : space group P2₁/c with a = 12.847(5), b = 8.448(2), c = 22.272(6) Å, β = 122.90(3)°, V = 2029.5(1) ų, Z = 4, R1 = 0.0684, wR2 = 0.1044: 4 : space group P2₁/n with a = 12.871(3), b = 8.359(1), c = 19.019(4) Å, β = 92.61(2)°, V = 2044.2(6) ų, Z = 4, R1 = 0.0621, wR2 = 0.0979.     

[Rb4Sn9] — A Low Dimensional Arrangement of Zintl Ions in [Rb(18‐crown‐6)]2Rb2[Sn9](en)1.5

The compound [Rb(18‐crown‐6)]₂Rb₂[Sn₉](en)_1.5 ( 1 ) was synthesized from an alloy of formal composition K₂Rb₂Sn₉ by dissolving in ethylenediamine (en) followed by the addition of 18‐crown‐6 and toluene. 1 crystallizes in the monoclinic space group P2₁/n with a = 10.557(2), b = 25.837(5), c = 20.855(4)Å, β = 102.39°, and Z = 4. The structure consists of [Sn₉]^4— cluster anions, which are connected via Rb atoms to infinite [Rb₄Sn₉] layers. The layers of binary composition are separated by the crown ether molecules. The crown ether molecules are bound by one side via the Rb atoms to the [Sn₉]^4— anions. The other side, which is turned away from the Rb atoms, shows only weak van der Waals interactions to the crown ether molecules of the next layer. Comparison with other compounds of similar composition shows, that the variation of the alkali metals and the complexing organic molecules leads to the low dimensional arrangement of the clusters.     

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.     

Alkali Cation Ligating Chains and Sheets of the Macrocycle 1, 7‐Dithia‐18‐Crown‐6 with Bridging Iodo‐ and Thiocyanatocuprate(I) Units

Treatment of an acetonitrile solution of CuI with 1, 7‐dithia‐18‐crown‐6 (1, 7‐DT18C6) at 100°C affords the coordination polymer ¹[(CuI)₂(1, 7‐DT18C6)₂] ( 1 ) in which 1, 7‐DT18C6 ligands bridge (CuI)₂ rings into double chains. 1D polymers of the type ¹[M{(Cu₃I₄)(1, 7‐DT18C6)}] (M = K, 2 ; M = Cs, 3 ) can be isolated under similar conditions in the presence of respectively KI and CsI. Both contain bridging heptacyclic [Cu₆I₈]^2— units but crystallise in different space groups, namely P1 and C2/m. The cesium cation of 3 is markedly displaced from the best plane through the thiacrown ether donor atoms. Reaction of 1, 7‐DT18C6 with CuSCN in the presence of NaSCN yields ²[{Na(CH₃CN)₂} {(CuSCN)₂(1, 7‐DT18C6)}][Cu(SCN)₂] ( 4 ), in which ¹[(CuSCN)₂] double chains are linked through macrocycles into sheets. Infinite ¹[{Cu(SCN)₂}^—] chains compensate the charge of the Na⁺ cations. Complex 1 can imbibe 0.90 mol CsNO₃ per mol of 1, 7‐DT18C6 pairs.     

Kristallzüchtung und Strukturbestimmung eines metallorganischen Donator/Akzeptor‐Komplexes von I2C=CI2

Crystallization and Structure Determination of an I₂C=CI₂ organometallic Donor/Acceptor Complex The rectangular D_2h molecule I₂C=CI₂ contains 95.5% iodine with the rather bulky I substituents hiding the CC‐π‐system and heavily penetrating each other [1]. Starting both from the structure determination of a sublimed novel P2₁/n polymorph and extensive DFT calculations, numerous hitherto unknown donor/acceptor complexes of I₂C=CI₂ have been crystallized and structurally characterized [2]. Here we report the first adduct of tetraiodoethylene to a metalorganic complex, {[Pb²⁺(18‐crown‐6)(I^–)₂]…I₂C=CI₂}, crystallized from lead(18‐crown‐6)diiodide and I₂C=CI₂ in chloroform. The structure consists of polymer chains with angles ∢IPbI of 159° and distances I^–…I₂C=CI₂ between 348 to 359 pm. Both the 18‐crown‐6 ligand and the chloroform solvent molecule included in the crystal are considerably disordered. Space group Pnma (IT Nr. 62), Z = 4, lattice dimensions at 150 K, a = 1724.2(2), b = 1416.4(2), c = 1330.8(2), V = 3250.0(8) · 10⁶ pm³, R = 0.0428.     

Rb{Pr6C2}I12, an Iodide with a 13‐Electron Isolated Octahedral {Pr6C2} Cluster

Rb{Pr₆(C)₂}I₁₂ was obtained from a mixture of RbI, PrI₃, Pr and C as black single crystals at elevated temperatures. The black crystals are triclinic, (no. 2), a = 960.1(2), b = 957.0(2), c = 1003.4(2) pm, α = 71.74(2), β = 70.69(2), γ = 72.38(2)°, V = 805.6(3) 10⁶ pm³, Z = 1; R₁ = 0.0868 for all 2749 measured independent reflections. Rb{Pr₆(C)₂}I₁₂ contains {Pr₆(C₂)} clusters isolated from each other, surrounded by twelve edge‐bridging and six terminal ligands. The [{Pr₆(C)₂}Iⁱ₁₂I^a₆]^? units are connected via i‐a/a‐i bridges according to {Pr₆C₂}Iⁱ_6/1I^i‐a_6/2I^a‐i_6/2 with rubidium ions occupying twelve‐coordinate interstices.     

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.     

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.     

Bulky Cations and Four different Polyiodide Anions in [Lu(Db18c6)(H2O)3(thf)6]4(I3)2(I5)6(I8)(I12)

Black single crystals of [Lu(Db18c6)(H₂O)₃(thf)₆]₄(I₃)₂(I₅)₆(I₈)(I₁₂) were obtained from lutetium, I₂ and Db18c6 (dibenzo‐18‐crown‐6) in THF solution. In the bulky cation, Lu³⁺ is surrounded by nine oxygen atoms, six of Db18c6 and three of water molecules to which two THF molecules are attached each. Meanwhile, four polyiodide anions, (I₃)^–, (I₅)^–, (I₈)^2– and (I₁₂)^2–, in a 2:6:1:1 ratio form a three‐dimensional network and leave space for the bulky cations.     

Trapping a Silicon(I) Radical with Carbenes: A Cationic cAAC–Silicon(I) Radical and an NHC–Parent‐Silyliumylidene Cation

The trapping of a silicon(I) radical with N‐heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAAC_Me] (cAAC_Me=:C(CMe₂)₂(CH₂)NAr, Ar=2,6‐i Pr₂C₆H₃) with H₂SiI₂ in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAAC_Me)₂Si:^.]⁺I⁻ ( 1 ), which features a cationic cAAC–silicon(I) radical, and [cAAC_Me−H]⁺I⁻. In addition, the reaction of the NHC–iodosilicon(I) dimer [I_Ar(I)Si:]₂ (I_Ar=:C{N(Ar)CH}₂) with 4 equiv of I_Me (:C{N(Me)CMe}₂), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(I_Me)₂SiH]⁺I⁻ ( 2 ) comprising the first NHC–parent‐silyliumylidene cation. Its further reaction with fluorobenzene afforded the C_Ar−H bond activation product [1‐F‐2‐I_Me‐C₆H₄]⁺I⁻ ( 3 ). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1 . Compounds 1 – 3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X‐ray crystallography.     

Lamellar Copper(I) Thiocyanate‐Based Coordination Polymers containing the Alkali Cation ligating Thiacrown Ether 1,10‐Dithia‐18‐crown‐6

The lamellar coordination polymer [(CuSCN)₂(μ‐1,10DT18C6)] (1,10DT18C6 = 1,10‐dithia‐18‐crown‐6), in which staircase‐like CuSCN double chains are bridged by thiacrown ether ligands, may be prepared in two triclinic modifications 1 a and 1 b by reaction of CuSCN with 1,10DT18C6 in respectively benzonitrile or water. Performing the reaction in acetonitrile in the presence of an equimolar quantity of KSCN leads, in contrast, to formation of the K⁺ ligating 2‐dimensional thiocyanatocuprate(I) net [{Cu₂(SCN)₃}^–] of 2 , half of whose Cu(I) atoms are connected by 1,10DT18C6 macrocycles. The potassium cations in [{K(CH₃CN)}{Cu₂(SCN)₃(μ‐1,10DT18C6)}] ( 2 ) are coordinated by all six potential donor atoms of a single thiacrown ether in addition to a thiocyanate S and an acetonitrile N atom. Under similar conditions, reaction of CuI, NaSCN and 1,10DT18C6 affords [{Na(CH₃CN)₂}{Cu₄I₄(SCN)(μ‐1,10DT18C6)}] ( 3 ), which contains distorted Cu₄I₄ cubes as characteristic molecular building units. These are bridged by thiocyanate and thiacrown ether ligands into corrugated Na⁺ ligating sheets. In the presence of divalent Ba²⁺ cations, charge compensation requirements lead to formation of discrete [Cu(SCN)₃(1,10DT18C6‐κS)]^2– anions in [Ba{Cu(SCN)₃(1,10DT18C6‐κS)}] ( 4 ).     

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.