Coordination of Alkaline Earth Metal Ions in the Inverted Cucurbit[7]uril Supramolecular Assemblies Formed in the Presence of [ZnCl4]2− and [CdCl4]2−

A convenient method to isolate inverted cucurbit[7]uril (iQ[7]) from a mixture of water‐soluble Q[n]s was established by eluting the soluble mixture of Q[n]s on a Dowex (H⁺ form) column so that iQ[7] could be selected as a ligand for coordination and supramolecular assembly with alkaline earth cations (AE²⁺) in aqueous HCl solutions in the presence of [ZnCl₄]^2? and [CdCl₄]^2? anions as structure‐directing agents. Single‐crystal X‐ray diffraction analysis revealed that both iQ[7]–AE²⁺–[ZnCl₄]^2?–HCl and iQ[7]–AE²⁺–[CdCl₄]^2?–HCl interaction systems yielded supramolecular assemblies, in which the [ZnCl₄]^2? and [CdCl₄]^2? anions presented a honeycomb effect, and this resulted in the formation of linear iQ[7]/AE²⁺ coordination polymers through outer‐surface interactions of Q[n]s.     

Synthesis,Isolation and Crystal Structures of the Metalated Ylides [Cy3P-C-SO2Tol]M (M = Li,Na, K)

The preparation and isolation of the metalated ylides [Cy₃PCSO₂Tol]M ( ^Cy1-M ) (with M = Li, Na, K) are reported. In contrast to its triphenylphosphonium analogue the synthesis of ^Cy1-M revealed to be less straight forward. Synthetic routes to the phosphonium salt precursor ^Cy1 - H₂ via different methods revealed to be unsuccessful or low-yielding. However, nucleophilic attack of the ylide Cy₃P = CH₂ at toluenesulfonyl fluoride under basic conditions proved to be a high-yielding method directly leading to the ylide ^Cy1-H . Metalation to the yldiides was finally achieved with strong bases such as nBuLi, NaNH₂, or BnK. In the solid state, the lithium compound forms a tetrameric structure consisting of a (C–S–O–Li)₄ macrocycle, which incorporates an additional molecule of lithium iodide. The potassium compound forms a C₄-symmetric structure with a (K₄O₄)₂ octahedral prism as central structural motif. Upon deprotonation the P–C–S linkage undergoes a remarkable contraction typical for metalated ylides.     

ChemInform Abstract: [Ta3O3]A (A: Li,Na, K) and [Ta3O3]B[Ta3O3] (B: Ca,Sr, Ba): Sandwich‐Type Complexes Containing Ta3O3‐ δ and π Double Aromatic Ligands.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Die Clusterazide M2[Nb6Cl12(N3)6]·(H2O)4—x (M = Ca,Sr, Ba)

The Cluster Azides M₂[Nb₆Cl₁₂(N₃)₆]·(H₂O)_4—x (M = Ca, Sr, Ba) The isotypic cluster compounds M₂[Nb₆Cl₁₂(N₃)₆] · (H₂O)_4—x (M = Ca (1) , M = Sr (2) and M = Ba (3) ) have been synthesized by the reaction of an aequeous solution of Nb₆Cl₁₄ with M(N₃)₂. 1 , 2 and 3 crystallize in the space group Fd3¯ (No. 227) with the lattice constants a = 1990.03(23), 2015.60(12) and 2043, 64(11) pm, respectively. All compounds contain isolated 16e— clusters whose terminal positions are all occupied by orientationally disordered azide ligands.     

Metalated 1, 3‐Azaphospholes: η1‐(1H‐1, 3‐Benzazaphosphole‐P)M(CO)5 and μ2‐[(1, 3‐Benzazaphospholide‐P)(cyclopentadienide)nickel] Complexes

1H‐1, 3‐Benzazaphospholes react with M(CO)₅(THF) (M = Cr, Mo, W) to give thermally and relatively air stable η¹‐(1H‐1, 3‐Benzazaphosphole‐P)M(CO)₅ complexes. The ¹H‐ and ¹³C‐NMR‐data are in accordance with the preservation of the phosphaaromatic π‐system of the ligand. The strong upfield ³¹P coordination shift, particularly of the Mo and W complexes, forms a contrast to the downfield‐shifts of phosphine‐M(CO)₅ complexes and classifies benzazaphospholes as weak donor but efficient acceptor ligands. Nickelocene reacts as organometallic species with metalation of the NH‐function. The resulting ambident 1, 3‐benzazaphospholide anions prefer a μ₂‐coordination of the η⁵‐CpNi‐fragment at phosphorus to coordination at nitrogen or a η³‐heteroallyl‐η⁵‐CpNi‐semisandwich structure. This is shown by characteristic NMR data and the crystal structure analysis of a η⁵‐CpNi‐benzazaphospholide. The latter is a P‐bridging dimer with a planar Ni₂P₂ ring and trans‐configuration of the two planar heterocyclic phosphido ligands arranged perpendicular to the four‐membered ring.     

μ‐Rhodizonato‐1κO,1:2κO′,2κO′′‐tetra(triphenylphosphine)disilver(I): A Molecular Complex with the [C6O6]2– Ligand Template

The first silver rhodizonate and overall fourth transition metal rhodizonate complex is presented. The title compound shows a so far unobserved coordination mode of the rhodizonate ligand, which is atypically distorted from planarity. The structure discussion is accompanied by a thorough literature review of the hitherto structurally characterized rhodizonate salts and complexes.     

Polysulfonylamine. CLIV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 7 [2] Ein dreidimensionales Koordinationspolymer aus Schichten und Pfeilern: Kristallstruktur von Ba[(CH3SO2)2N]2·2H2O

Polysulfonylamines. CLIV. Crystal Structures of Metal Di(methanesulfonyl)amides. 7. A Three‐Dimensional Coordination Polymer Built up from Layers and Pillars: Crystal Structure of Ba[(CH₃SO₂)₂N]₂·2H₂O The barium compound BaA₂·2H₂O, derived from HA = di(methanesulfonyl)amine, has been characterized by single crystal X‐ray diffraction at —95 °C (monoclinic, space group P2₁/n, Z = 4). Despite numerous metal‐ligand bonds, the independent anions A^— and A′^— retain the pseudo‐C₂ symmetric conformation that commonly occurs in organic onium salts BH⁺A^—. The large cation attains ninefold coordination via interactions with one (O, N)‐chelating A^—, three κ¹O‐bonding A^—, two κ¹O‐bonding A′^— and two monodentate water molecules; if a distinctly longer barium‐water distance is included, the coordination number may alternatively be viewed as 9 + 1 and one water molecule regarded as an asymmetrically μ₂‐bridging ligand. In contrast to the previously reported layer structures of SrA₂ and PbA₂, the present crystal displays a three‐dimensional coordination assembly consisting of layers formed by the cations, the water molecules and the pentadentate A^— ligands, and of interlayer pillars provided by the bidentate A′^— ligands; however, the Ba²⁺/A^— substructure turns out to be topologically and crystallographically congruent with the corresponding M²⁺/A^— substructures in SrA₂ and PbA₂. The crystal cohesion of the barium complex is reinforced by four O(W)—H···O=S hydrogen bonds and several non‐classical C—H···O=S hydrogen bonds.     

Aufbau von Erdalkalimetall‐Arsen‐Käfigstrukturen durch die Metallierung von Triisopropylsilylarsan mit Calcium‐, Strontiumund Barium‐bis[bis(trimethylsilyl)amid] in Tetrahydrofuran

Formation of Alkaline Earth Metal‐Arsenic Cages via the Metalation of Triisopropylsilylarsane with Calcium, Strontium, and Barium Bis[bis(trimethylsilyl)amide] in Tetrahydrofuran The metalation of triisopropylsilylarsane with the alkaline earth metal bis[bis(trimethylsilyl)amides] in tetrahydrofuran yields the THF complexes of calcium ( 1 ), strontium ( 2 ), and barium‐bis(triisopropylsilylarsanide) ( 3 ). Dissolving of these compounds in toluene leads to the elimination of triisopropylsilylarsane and the formation of the THF complexes of tetraalkaline earth metal hexakis(triisopropylsilylarsanide)‐triisopropylsilylarsanediide of calcium ( 4 ), strontium ( 5 ), and barium ( 6 ), respectively. The central polyhedron of compound 4 can be described as two trigonal bipyramids with the metal atoms in apical positions, connected via the arsanediide substituent as a common corner. The central moieties of the compounds 5 and 6 consist of four trigonal bipyramids which are connected by common edges as well as common faces.     

[PbAsSiiPr3]6 — the First Structurally Characterized Compound with Chemical Bonds between Lead and Arsenic

The compound [PbAsSiiPr₃]₆ ( 1 ) could be obtained by the reaction of PbCl₂ with iPr₃SiAs(SiMe₃)₂ in THF at 0 °C. Central structural motif is a hexagonal prism built by six lead and six arsenic atoms. The average Pb—As bond length is 281 pm. The cluster crystallizes in the monoclinic space group C2/c, the lattice constants are: a = 4460.8(9) b = 2296.6(5), c = 2734.4(6) pm, β = 117.57(3)°. The thermogravimetric analysis in vacuum shows the tendecy of 1 to decompose under formation of elementary lead and volatile arsenic compounds.     

M(SCN)2 (M = Eu,Sr, Ba): Kristallstruktur,thermisches Verhalten,Schwingungsspektroskopie

M(SCN)₂ (M = Eu, Sr, Ba): Crystal Structure, Thermal Behaviour, Vibrational Spectroscopy Single crystals of M(SCN)₂ (M = Eu, Sr, Ba) have been obtained via metathesis of NaSCN and MCl₂ (M = Eu, Sr, Ba) at 340 °C. The isotypic crystal structures of the thiocyanates M(SCN)₂ (C2/c, Z = 4, Eu: a = 979.3(2), b = 660.8(1), c = 815.7(2) pm, β = 91.58(3)°, R_all = 0.0245, Sr: a = 985.5(2), b = 662.9(2), c = 819.6(2) pm, β = 91.29(3)°, R_all = 0.0435, Ba: a = 1018.8(2), b = 687.2(1), c = 852.2(1) pm, β = 92.43(2)°, R_all = 0.0392) contain alternating layers of M²⁺ and SCN^–. According to M(SCN)_4/4(NCS)_4/4 M²⁺ is eight‐coordinated by four sulfur and four nitrogen atoms forming a square antiprism. Thermal investigations show that the compounds melt without decomposition. Vibrational spectroscopic investigations are presented and discussed.     

A Novel Beryllium Thiolate Resulting from N−Si Bond Cleavage: Liberation of Ammonia in the Reaction of Be[N(SiMe3)2]2 with HSPh

A side reaction leads to the product. In the synthesis of [{Be(SPh)₂(py)(NH₃)}₂{[18]crown-6}] ( 1 , py=pyridine) from [Be{N(SiMe₃)₂}₂] and HSPh, the coordinated ammonia molecules (see the structure of 1 in the picture) are formed in a competing reaction between liberated hexamethyldisilazane and the thiol.     

A Structurally Characterized Cobalt(I) σ‐Alkane Complex

A cobalt σ‐alkane complex, [Co(Cy₂P(CH₂)₄PCy₂)(norbornane)][BAr^F₄], was synthesized by a single‐crystal to single‐crystal solid/gas hydrogenation from a norbornadiene precursor, and its structure was determined by X‐ray crystallography. Magnetic data show this complex to be a triplet. Periodic DFT and electronic structure analyses revealed weak C?H→Co σ‐interactions, augmented by dispersive stabilization between the alkane ligand and the anion microenvironment. The calculations are most consistent with a η¹:η¹‐alkane binding mode.     

Ba7Fe6F32 · 2H2O: Original isolated trimers [Fe3F16]7− in a new defective jarlite-type compound

Ba₇Fe₆F₃₂ · 2H₂O was prepared from HF aqueous solution in a teflon bomb (Berghof) at 180°C. A partial exchange F^?/OH^? can be realized in more diluted HF medium and leads to Ba₇Fe₆F_32–x(OH)_x · 2H₂O. The compounds crystallize in the monoclinic system, space group C2/m (Z = 2) with a = 17.023(1) Å, b = 11.482(1) Å, c = 7.624(1) Å, β = 101.13(1)° for x = 0 and a = 17.036(2) Å, b = 11.489(1) Å, c = 7.620(2) Å, β = 101.48(1)° for x ≈? 5.3. The structures were determined from 2 256 and 1 343 independent reflections for x = 0 and x ≈? 5.3 respectively, collected with a Siemens AED2 four-circle diffractometer with the MoKα radiation (R = 0.0235 and R_w = 0.0240 for x = 0 and R = 0.0324 and R_w = 0.0335 for x ≈? 5.3). The structure, closely related to that of the Jarlite-type, is built up from isolated octahedra trimers [Fe₃F₁₆]^7?, connected together by Ba²⁺-cations. The location of anions and water molecules is discussed from bond valence calculations. Magnetic and Mössbauer studies are reported and discussed.     

[PdCl(TeMe2)3](BArF) – The First Structurally Characterized Palladium(II) Complex with TeMe2 Ligands

[PdCl(TeMe₂)₃]BAr^F ( 4 ) forms as the major tellurium containing product from the reaction of [(4‐Mebti)PdCl] with TeMe₂ and Na(BAr^F) and is isolated by crystallization from the reaction mixture. At ?20 °C, the compound forms orange columns from toluene/pentane, space group , with Z = 2. In the solid, the cationic [PdCl(TeMe₂)₃]⁺ complex ions show a non‐planar PdClTe₃ coordination unit and are associated to dimers via weak Pd···Te interactions.     

Synthesis,Structure, and Physical Properties of a Barium Complex with 5‐Sulfoisophthalic Acid Sodium Salt

The complex [Ba₃(sip)₂(H₂O)₉] · H₂O ( 1 ) (NaH₂sip = 5‐sulfoisophthalic acid sodium) was synthesized and characterized by single‐crystal X‐ray diffraction. Structural determination reveals that the asymmetric unit in 1 contains two crystallographically independent Ba^II atoms. The Ba1 atom is eight‐coordinate with distorted monocapped pentagonal bipyramidal arrangement, whereas the Ba2 atom is ten‐coordinated with bicapped tetragonal prismatic arrangement. The two carboxylate groups of sip^3– adopt different coordination modes, μ₂‐η¹:η¹‐bridging, and μ₂‐η²:η¹‐bridging. The sulfonate group coordinates to three different Ba^II atoms in a tridentate μ₃ mode to generate a ladder‐like one‐dimensional chain. The chains are connected by μ₂‐η¹:η¹‐bridging carboxylate groups to form a wave‐like two‐dimensional network, which are further linked by sip^3– anions to generate a three‐dimensional structure. The thermal stability and luminescence properties of complex 1 were also investigated.     

Alkaline Earth Diazapentadienyl Compounds: Structure of [Ba2{(C6H11)NC(Me)CHC(Me)N(C6H11)}3{(SiMe3)2N}]

Three different bonding modes in one molecule! The diazapentadienyl ligands in the title compound 1 adopt η¹,η¹-N,N-chelating plus η⁵-terminal, η¹η¹-N,N chelating plus η⁵-bridging, and novel η¹-N plus η³-1-aza-allyl bonding modes. R=cyclohexyl.     

ACu9X4 ‐ Neue Verbindungen mit der CeNi8, 5Si4, 5‐Struktur (A: Sr,Ba; X: Si,Ge)

ACu₉X₄ ‐ New Compounds with CeNi_{8, 5}Si_{4, 5} Structure (A: Sr, Ba; X: Si, Ge) The new compounds SrCu₉Si₄ (a = 8.146(1), c = 11.629(2)Å), BaCu₉Si₄ (a = 8.198(2), c = 11.735(2)Å), SrCu₉Ge₄ (a = 8.273(2), c = 11.909(5)Å), and BaCu₉Ge₄ (a = 8.338(4), c = 12.011(7)Å) are formed by reaction of the elements at 1000° ‐ 1100 °C. They are isotypic (I4/mcm, Z = 4) and crystallize in an ordered variant of the cubic NaZn₁₃ type structure, also built up by the binary phase BaCu₁₃. In the ternary compounds the positions of Cu2 are orderly occupied by copper and silicon and germanium, respectively. This results in a lowering of symmetry and a distortion of the polyhedra. The metallic conductivity of the compounds was confirmed by measurements on BaCu₉Si₄.