Über die Kronenetherkomplexe [K(15-Krone-5)2]3[Sb3I12], [TeCl3(15-Krone-5)][TeCl5] und [TeCl3(15-Krone-5)]2[TeCl6]

On the Crown Ether Complexes [K(15-Crown-5)₂]₃[Sb₃I₁₂], [TeCl₃(15-Crown-5)][TeCl₅], and [TeCl₃(15-Crown-5)]₂[TeCl₆] Orange-coloured crystals of [K(15-crown-5)₂]₃[Sb₃I₁₂] are formed in the reaction of potassium iodide with antimony triiodide and 15-crown-5 in acetonitrile solution. An X-ray structure determination reveals severe disorder of the crown ether molecules, which coordinate to the potassium atoms in a sandwich array; so only the [Sb₃I₁₂]^3? ion and the potassium positions were ascertained. The anion is a centrosymmetric trimer (symmetry C_2h), which can be understood as central SbI₆^3? ion, coordinated by two SbI₃ molecules. (Space group C2/m), Z = 2, 3263 observed, independent reflections, R = 0.06, lattice dimensions at 20°C: a = 2541.1 pm, b = 1441.7 pm, c = 1588.4 pm, β = 113.33°. The tellurium complexes [TeCl₃(15-crown-5)] [TeCl₅] and [TeCl₃(15-crown-5)]₂[TeCl₆] are prepared by reaction of TeCl₄ with 15-crown-5 in acetonitrile solution, forming yellow-green crystals sensitive to moisture. They are characterized by their i.r. spectra.     

Struktur und Eigenschaften des Methylpentafluorphosphatanions, [CH3PF5]—

Structure and Properties of the Methyltetrafluorophosphate Anion, [CH₃PF₅]^— Methyltetrafluorphosphorane reacts with the fluorides NaF, KF, CsF, and (CH₃)₄NF with formation of the corresponding methylpentafluorophosphates. In case of the K and Cs salts K[CH₃PF₅] · CH₃CN and Cs[CH₃PF₅] · CH₃CN, respectively, are formed using acetonitrile as solvent. The salts are characterized by NMR, IR and Raman spectroscopy. The vibrational frequencies are compared with ab initio calculated data (RHF/6‐31+G*). The RHF/6‐31+G* calculation yields for the almost octahedral anion bond distances of d(PF_eq) = 163.7 pm, d(PF_ax) = 162.0 pm, and d(PC) = 184.8 pm.     

Kronenetherkomplexe von Blei(II). Die Kristallstrukturen von [PbCl(18-Krone-6)][SbCl6], [Pb(18-Krone-6)(CH3CN)3][SbCl6]2, and [Pb(15-Krone-5)2][SbCl6]2

Crown Ether Complexes of Lead(II). The Crystal Structures of [PbCl(18-Krone-6)][SbCl₆], [Pb(18-Krone-6)(CH₃CN)₃][SbCl₆]₂ und [Pb(15-Krone-5)₂][SbCl₆]₂ . [PbCl(18-crown-6)][SbCl₆] has been prepared in low yield besides [Pb(CH₃)₂(18-crown-6)][SbCl₆]₂ by the reaction of Pb(CH₃)₂Cl₂ with antimony pentachloride in acetonitrile solution in the presence of 18-crown-6, forming pale-yellow crystals. The other two title compounds are formed as colourless crystals by the reaction of PbCl₂ with antimony pentachloride in acetonitrile solutions in the presence of 18-crown-6 and 15-crown-5, respectively. The complexes were characterized by IR spectroscopy and by crystal structure determinations. [PbCl(18-crown-6)][SbCl₆]: Space group P2₁/c, Z = 8, 5 003 observed unique reflections, R = 0.046. Lattice dimensions at - 80°C: a = 1 386.9; b = 1 642.7; c = 2 172.1 pm, β = 92.95°. The lead atom in the cation [PbCl(18-crown-6)]⁺ is surrounded in an almost hexagonal-planar construction by the six oxygen atoms of the crown ether and an axially oriented Cl atom. [Pb(18-crown-6)(CH₃CN)₃][SbCl₆]₂: Space group P1 , Z = 2, 6 128 observed unique reflections, R = 0.076. Lattice dimensions at - 70°C: a = 1 228.0; b = 1 422.9; c = 1 463.2 pm, α = 69.08°; β = 65.71°; γ = 64.51°. In the cation [Pb(18-crown-6)(CH₃CN)₃]²⁺ the lead atom is coordinated by the six oxygen atoms of the crown ether and by the three nitrogen atoms of the acetonitrile molecules. The structure determination is restricted by disorder. [Pb( 15-crown-5)₂][SbCI₆]₂: Space group P6₃/m, Z = 6, 5 857 observed unique reflections, R = 0.059. Lattice dimensions at -70°C: a = b = 2 198.5; c = 1499.4 pm, α = β = 90°, γ = 120°. In the cation [Pb(l5-crown-5)₂]² the lead atom is sandwich-like coordinated by the ten oxygen atoms of the two crown ether molecules. The structure determination is restricted by disorder.     

Darstellung und Kristallstruktur von K4[SnO3]

Preparation and Crystal Structure of K₄[SnO₃] K₄[SnO₃] crystallizes with the K₄[PbO₃] structure in the orthorhombic spacegroup Pbca (No. 61) with the lattice constants a = 652.2(3) pm, b = 1 112.1(5) pm and c = 1 893.7(7) pm. In the structure isolated ψ-tetrahedral anions [Sn^IIO₃]^4? are arranged in layers perpendicular [001]. The structure of K₄[SnO₃] will be compared with those of stannates and plumbates of composition A₄[M^IIO₃] (A = Na, K, Rb, Cs) and with the known potassium stannates(II).     

Alkalimetall‐Phosphaniminate. Neue Synthesen und die Kristallstrukturen von [RbNPPh3]6 und [CsNPPh3]4

Alkali Metal Phosphoraneiminates. New Syntheses and Crystal Structures of [RbNPPh₃]₆ and [CsNPPh₃]₄ The alkali‐metal phosphoraneiminates MNPPh₃ with M = Na, K, Rb, Cs have been synthesized by reactions of Ph₃PI₂ with the alkali‐metal amides in liquid ammonia and were obtained as pure samples by subsequent extraction with toluene. The ethyl derivative KNPEt₃ has been prepared by an analogous route from Et₃PBr₂ and extraction with hexane. Single crystals of the phosphoraneiminates of rubidium and cesium are obtainable by crystallization from toluene and toluene/hexane, respectively. They were suitable for crystal structure determinations. [RbNPPh₃]₆ · 4¹/₂ toluene ( 1 ): space group P1, Z = 2, lattice dimensions at 193 K: a = 1525.5(2); b = 1902.9(2); c = 2178.3(2) pm; α = 95.435(12)°; β = 91.145(12)°; γ = 90.448(12)°; R₁ = 0.0529. The compound forms a Rb₆N₆ skeleton of a double cube with a common face of two rubidium and two nitrogen atoms, the latter being fivefold coordinated by four rubidium atoms and the phosphorus atom. [CsNPPh₃]₄ · 2 toluene · 3³/₄ hexane ( 2 a ): space group Fd3, Z = 8, lattice dimensions at 123 K: a = b = c = 2679.7(1) pm; R₁ = 0.0405. [CsNPPh₃]₄ · 2 toluene ( 2 b ): space group P2₁/n, Z = 4, lattice dimensions at 193 K: a = 1418.9(1); b = 2258.9(1); c = 2497.6(1) pm; β = 91.055(6)°; R₁ = 0.0278. Both cesium compounds form Cs₄N₄ heterocubane structures which are different by means of the packing and by different bond angles at the cesium and nitrogen atoms.     

Zur Magnetochemie der Fluoroargentate(II): Messungen an Ba[AgF4], Sr[AgF4], Ba2AgF6 sowie K[AgF3] und Cs[AgF3]

Magnetochemistry of Fluoroargentates(II): Investigation of Ba[AgF₄], Sr[AgF₄], Ba₂AgF₆, K[AgF₃], and Cs[AgF₃] Ba[AgF₄] (Θ = -4 K, μ = 1.9₂ μ_B), isostructural with K[BrF₄] with planar [AgF₄] groups, fullfil the Curie-Weiss-law, also Ba₂AgF₆ (Θ = 4 K, Θ = 1.8₅ μ_B) which is related with the structure of Ba₂CuF₆. The variante of perovskite-type K[AgF₃] (orthorhombic) and Cs[AgF₃] (tetragonal perovscite) show collective magnetic interactions (T_N = 80 K, KAgF₃, and 50 K, CsAgF₃) and show a behaviour like AgF₂ (T_N160 K) correspondingly to the magnetic dilution. Above T_N paramagnetism is nearly independend of tempearture.     

Ionische Kronenetherkomplexe von Zinn(II) und Zinn(IV): [Sn(15-Krone-5)] [SnCl6] und [SnCl3(18-Krone-6)]2[Sn2Cl10]; Synthesen,IR-Spektren und 119Sn-Mößbauer-Spektren

Ionic Crown Ether Complexes of Tin(II) and Tin(IV): [Sn(15-Crown-5)][SnCl₆] and [SnCl₃(18-Crown-6)]₂[Sn₂Cl₁₀]; Syntheses, IR Spectra, and ¹¹⁹Sn-Mössbauer Spectra [Sn(15-crown-5)][SnCl₆] ( 1 ,) has been prepared by the reaction of SnCl₂, SnCl₄, and 15-crown-5 in the molar ratio of 1 : 1 : 1 in acetonitrile solution, forming a white insoluble crystal powder. [SnCl₃(18-crown-6)]₂[Sn₂Cl₁₀] ( 2 ,) as well as [SnCl₃(18-crown-6)][BiCl₄] · CH₃CN ( 3 ,) are prepared by the reaction of SnCl₄ with 18-crown-6 (molar ratio 2 : 1), and of SnCl₄, 18-crown-6, and BiCl₃ (molar ratio 1 : 1 : 1), respectively. According to IR-spectroscopy and ¹¹⁹Sn-Mössbauer-spectroscopy 1–3 , have ionic structures; the cation of 1 , being polymeric via a sandwich-like structure.     

Synthesen und Kristallstrukturen der Polytellurido-Komplexe [K(15-Krone-5)2]2[MTe7] mit M = Zn und Hg

Synthesis and Crystal Structures of the Polyellurido Complexes [K(15-Crown-5)₂]₂[MTe₇] with M = Zn and Hg The title compounds were obtained in the presence of 15-crown 5 from solutions of zinc and mercury acetate, respectively, in DMF by addition of a solution of K₂Te₃ in DMF at 0°C (M = Zn) and -50°C (M = Hg). They form black crystal needles with metallic luster. Their crystal structures were determined by X-ray diffraction. The structures of [K(15-crown-5)₂]₂ZnTe₇ and [K(15-crown-5)₂]₂HgTe₇ show two-dimensional disorder as evidence by diffuse scattering. The averaged structures that were determined with the Bragg reflexions correspond to space group Pbcn and have very similar lattice parameters. Nevertheless, the structures differ. [HgTe₇]^2? ions consist of two condensed five membered rings. They are arranged to form strands in the c direction; within of one strand the ions have a definite orientation, but in different strands two different orientations occur randomly. A [ZnTe₇]^2? ion can be thought of consisting of a Zn²⁺ ion, a Te₄^2? ion bonded in a chelate manner and a Te₃^2? ion bonded with one terminal Te atom to the Zn²⁺. The [ZnTe₇]^2? ions are associated to strands in the c direction with two different strand orientations occuring randomly.     

The interaction of group III metal alkyls with crown ethers. The synthesis and structure of [Ga(CH3)3]2[dibenzo18-crown-6] and [Al(CH3)3]2[dicyclohexano-18-crown-6]

[Ga(CH₃)₃]₂[dibenzo-18-crown-6] and [Al(CH₃)₃]₂[dicyclohexyl-18-crown-6] were prepared by the reaction of Ga(CH₃)₃ or Al(CH₃)₃ with the appropriate crown ether in toluene. After filtering and cooling, both products were obtained as colorless, air-sensitive, rectangular crystals. The structures of both compounds were determined from single crystal X-ray diffraction data collected on a CAD-4 diffractomer. [Ga(CH₃)₃]₂[dibenzo-18-crown-6] belongs to the monoclinic space group P2₁/c with unit cell parameters a 11.460(5), b 18.000(7), c 7.495(4) Å, β 105.65(4)°, and ϱ(calc) 1.32 g cm⁻³ for Z  2. Least-squares refinement gave a final R value of 0.061 for 1179 independent observed reflections. The molecule resides on a crystallographic center of inversion. The Ga-O distance of 2.198(8) Å is among the longest yet observed. In order to accommodate the two trialkygallium units, the crown ether is forced to adopt a chair configuration. [Al(CH₃)₃]₂[dicyclohexano-18-crown-6] crystallizes in the space group P2₁/a with cell parameters a 16.423(7), b 9.812(5), c 20.935(8) Å, β 107.41(5)°, and ϱ(calc) 1.07 g cm⁻³ for Z  4. Least-squares refinement gave a final R value of 0.079. The flexibility of the crown ether in this case allows the bonded oxygen atoms to be positioned on the outside of the crown, with all six oxygen atoms in a near-planar arrangement.     

Reactions of 1,4,7-trithiacyclononane, [9]aneS3, with early transition metal halides: synthesis and X-ray structure of {Fe([9]aneS3)2}[Sb2Cl8]

Summary The reactions of titanium(III) and (IV) chlorides with the crown thioether [9]aneS₃ were investigated. [TiCl_3- (MeCN)₃] gives a purple 1:1 adduct with a proposed octahedral structure involving tridentate fac-attachment of the ligand. With [TiCl₄(MeCN)₂] the identity of the yellow 1∶1 adduct obtained is discussed in terms of a six-coordinate species with bidentate ligand chelation. The title compound was isolated from the reactions of [9]aneS₃ with [TiCl₃(MeCN)₃] [SbCl₆] (by accident) and iron filings/SbCl₅ in MeCN solution and characterised crystallographically. The cation has two macrocyclic ligands coordinated facially to a six-coordinate Fe²⁺ ion; the anion comprises dimeric [(SbCl₄)₂] units linked together into a polymeric chain by weak halogen bridging.     

Die Kristallstrukturen von (NH4)2[ReCl6], [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN und [ReCl4(18-Krone-6)]

The Crystal Structures of (NH₄)₂[ReCl₆], [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN and [ReCl₄(18)(Crown-6)] Brown single crystals of (NH₄)₂[ReCl₆] are formed by the reaction of NH₄Cl with ReCl₅ in a suspension of diethylether. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN crystallizes as brown crystal plates from a solution of ReCl₅ in acetonitrile. Lustrous green single crystals of [ReCl₄(18-crown-6)] are obtained by the reaction of 18-crown-6 with ReCl₅ in a dichloromethane suspension. All rhenium compounds are characterized by IR spectroscopy and by crystal structure determinations. (NH₄)₂[ReCl₆]: Space group Fm3 m, Z = 4, 75 observed unique reflections, R = 0.01. Lattice constant at ?70°C: a = 989.0(1) pm. The compound crystallizes in the (NH₄)₂[PtCl₆] type, the Re? Cl distance is 235.5(1) pm. [ReCl₂(CH₃CN)₄]₂[ReCl₆] · 2CH₃CN: Space group P1, Z = 1, 2459 observed unique reflections, R = 0.12. Lattice dimensions at ?60°C: a = 859.0(1), b = 974.2(7), c = 1287.3(7) pm, α = 102.69(5)°, b? = 105.24(7)°, γ = 102.25(8)°. The structure consists of two symmetry-independent [ReCl₂(CH₃CN)₄]⁺ ions with trans chlorine atoms, [ReCl₆]^2? ions, and included acetonitrile molecules. In the cations the Re? Cl bond lengths are 233 pm in average, in the anion they are 235 pm in average. [ReCl₄(18-crown-6)]: Space group P2₁/n, Z = 4, 3 633 observed unique reflections, R = 0.06. Lattice dimensions at ?70°C: a = 1040.2(4), b = 1794.7(5), c = 1090.0(5) pm, b? = 108.91(4)°. The compound forms a molecular structure, in which the rhenium atom is octahedrally coordinated by the four chlorine atoms and by two oxygen atoms of the crown ether molecule.     

Synthesis and structural characterization of [Bse]Ni(PPh3)(NO), a nickel complex with a bent nitrosyl ligand

The nickel nitrosyl compound [Bse^Me]Ni(PPh₃)(NO) has been synthesized by the reaction of Ni(PPh₃)₂(NO)Br with potassium bis(2-seleno-1-methylimidazolyl)hydroborate, [Bse^Me]K. X-ray diffraction studies demonstrate that (i) the B–H group of the [Bse^Me] ligand interacts with the nickel center and (ii) the nitrosyl ligand is bent, with Ni–N–O bond angles of 149.1(3)° and 153.1(3)° for the two crystallographically independent molecules. The bent nature of the nitrosyl ligand in [Bse^Me]Ni(PPh₃)(NO) is in marked contrast to the linearity observed for the tris(2-seleno-1-mesitylimidazolyl)hydroborato counterpart [Tse^Mes]NiNO (180.0°). Density functional theory geometry optimization calculations demonstrate that the Ni?H–B interaction is not responsible for causing the nitrosyl ligand to bend, but rather the difference between [Tse^Mes]NiNO and [Bse^Me]Ni(PPh₃)(NO) is due to the [Tse^Mes] ligand allowing the former molecule to adopt a structure with C₃ symmetry. In contrast, the steric and electronic asymmetry of [Se₂P] donor array of the [Bse^Me] and PPh₃ ligand combination prevents [Bse^Me]Ni(PPh₃)(NO) from having C₃ symmetry and the nitrosyl ligand bends to stabilize the occupied M–N σ^∗ antibonding orbital.     

Chloro- und Polyselenoselenate(II) Darstellung,Struktur und Eigenschaften von [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6] und [Ph4P]2[Se(Se5)2]

Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN, [Ph₄P]₂[Se₂Cl₆], and [Ph₄P]₂[Se(Se₅)₂] By symproportionation of elemental selenium and SeCl₄ in polar protic solvents the novel chloroselenates(+II), [SeCl₄]^2? and [Se₂Cl₆]^2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph₃(C₂H₄OH)P]₂[SeCl₄] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl₄]^2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph₄P]₂[Se₂Cl₆] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se₂Cl₆]^2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se₅)₂]^2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph₄P]₂[Se(Se₅)₂] (space group P2₁/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se₅)₂]^2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se₅]_2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.     

Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy3]4, [KNPCy3]4·2OPCy3, [CsNPCy3]4·4OPCy3 und [Li4(NPPh3)(OSiMe2NPPh3)3(DME)]

The alkalimetal phosphoraneiminates [KNPCy₃]₄, ( 1 ) [KNPCy₃]₄·2OPCy₃ ( 2 ) and [CsNPCy₃]₄·4OPCy₃ ( 3 ) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy₃PI₂ or Cy₃PBr₂ in liquid ammonia, as well as the lithium derivative [Li₄(NPPh₃)(OSiMe₂NPPh₃)₃(DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe₂)n into the LiN bonds of [LiNPPh₃]₆ in DME solution (DME = 1, 2‐dimethoxyethane). 1 : Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2 : Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3 : Space group Cmc2₁, Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4 ·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ₃‐NPCy₃^‐) groups, whereas 4 forms a "heteroleptic" Li₄NO₃ heterocubane.     

Die Kristallstrukturen von [Et3PNAsPh3]2[Ag2Br4] und [Et3PNAsPh3]2[Pd2Br6]

Crystal Structures of [Et₃PNAsPh₃]₂[Ag₂Br₄] and [Et₃PNAsPh₃]₂[Pd₂Br₆] Colourless single crystals of [Et₃PNAsPh₃]₂[Ag₂Br₄]( 1 ) and red single crystals of [Et₃PNAsPh₃]₂[Pd₂Br₆]( 2 ) have been isolated from saturated solutions in acetonitrile of equivalent mixtures of [Et₃PNAsPh₃]Br with AgBr and PdBr₂, respectively. Both complexes were characterized by IR spectroscopy and by crystal structure determinations. 1 : Space group P1¯, Z = 1, lattice dimensions at ‐70°C: a = 985.0(2), b = 1042.2(5), c = 1345.8(5) pm, α = 102.88(2)°, β = 105.73(2)°, γ = 94.94(2)°, R₁ = 0.0577. 2 : Space group P2₁/c, Z = 2, lattice dimension at ‐70°C: a = 1003.0(1), b = 1371.8(2), c = 1974.0(1) pm, β = 93.30(1)°, R₁ = 0.0458. The dimeric anions of 1 and 2 form planar, centrosymmetric complex units.     

New members of the [Mn6/oxime] family and analogues with converging [Mn3] planes

The synthesis, structural, and magnetic characterization of five new members of the hexanuclear oximate [Mn^III₆] family are reported. All five clusters can be described with the general formula [Mn^III₆O₂(R-sao)₆(R′-CO₂)₂(sol)_x(H₂O)_y] (where R-saoH₂ = salicylaldoxime substituted at the oxime carbon with R = H, Me and Et; R′ = 1-naphthalene, 2-naphthalene, and 1-pyrene; sol = MeOH, EtOH, or MeCN; x = 0–4 and y = 0–4). More specifically, the reaction of Mn(ClO₄)₂·6H₂O with salicylaldoxime-like ligands and the appropriate carboxylic acid in alcoholic or MeCN solutions in the presence of base afforded complexes 1–5: [Mn₆O₂(Me-sao)₆(1-naphth-CO₂)₂(H₂O)(MeCN)]·4MeCN (1·4MeCN); [Mn₆O₂(Me-sao)₆(2-naphth-CO₂)₂(H₂O)(MeCN)]·3MeCN·0.1H₂O (2·3MeCN·0.1H₂O); [Mn₆O₂(Et-sao)₆(2-naphth-CO₂)₂(EtOH)₄(H₂O)₂] (3); [Mn₆O₂(Et-sao)₆(2-naphth-CO₂)₂(MeOH)₆] (4) and [Mn₆O₂(sao)₆(1-pyrene-CO₂)₂(H₂O)₂(EtOH)₂]·6EtOH (5·6EtOH). Clusters 3, 4, and 5 display the usual [Mn₆/oximate] structural motif consisting of two [Mn₃O] subunits bridged by two O_oximate atoms from two R-sao^2? ligands to form the hexanuclear complex in which the two triangular [Mn₃] units are parallel to each other. On the contrary, clusters 1 and 2 display a highly distorted stacking arrangement of the two [Mn₃] subunits resulting in two converging planes, forming a novel motif in the [Mn₆] family. Investigation of the magnetic properties for all complexes reveal dominant antiferromagnetic interactions for 1, 2, and 5, while 3 and 4 display dominant ferromagnetic interactions with a ground state of S = 12 for both clusters. Finally, 3 and 4 display single-molecule magnet behavior with U_eff = 63 and 36 K, respectively.     

[K(15-Krone-5)2]2Te8 — ein bicyclisches Polytellurid

[K(15-Crown-5)₂]₂Te₈ – a Bicyclic Polytelluride The octatelluride [K(15-crown-5)₂]₂Te₈ has been synthesized by the oxydation of a potassium tritelluride solution in dimethylformamide by iron(III) chloride in the presence of 15-crown-5, forming black crystals, which were characterized by an X-ray structure determination. Space group Pca2₁, Z = 4, 4 548 observed unique reflections, R = 0.048. Lattice dimensions at –70°C: a = 1 881(1), b = 2 211(2), c = 1 530(1) pm. The structure consists of cations [K(15-crown-5)₂]⁺, in which the potassium ions are sandwichlike coordinated by the oxygen atoms of the two disordered crown ether molecules, and of bicyclic Te₈^2? ions. In these anions a Te²⁺ ion is chelated in a planar fashion by a Te₃^2? and a Te₄^2? unit.     

Kristallstruktur des „supramolekularen”︁ Komplexes [Cs2(18-Krone-6)][HgI4] mit ungewöhnlich koordinierten Cs-Ionen

Crystal Structure of the “Supramolecular” Complex [Cs₂(18-crown-6)][HgI₄] with Unusually Coordinated Cs Ions The reaction of 18-crown-6, 1,4,7,10,13,16-hexaoxacyclooctadecane, with HgI₂/CsI in methanol yields crystals of [Cs₂(C₁₂H₂₄O₆)][HgI₄]. The compound crystallizes monoclinically, space group P2₁/c, Z = 4, a = 1574.8(3), b = 1067.0(3), c = 1693.2(6) pm, and β = 98.29(3)º. The structure consists of a network made up of two different types of [Cs-(18-crown-6)-Cs]²⁺ cations, interconnected by [HgI₄]^2? anions. The cations form an “anti-sandwich” structure with relatively short Cs ? Cs distances of 382 pm in the first type of cations and a longer distance of 480 pm in the second type of cations.     

Synthese und Kristallstruktur des Nitridokomplexes [Na-15-Krone-5]2[MoNF4]2 · 2 CH3CN

Synthesis and Crystal Structure of the Nitrido Complex [Na-15-crown-5]₂[MoNF₄]₂ · 2 CH₃CN The title compound is synthesized by the reaction of [MoCl₄(NSCl)]₂ with excess NaF in boiling acetonitrile in the presence of the crown ether 15-crown-5. [Na-15-crown-5]₂[MoNF₄]₂ · 2 CH₃CN forms yellow crystals, which were characterized by an X-ray structure determination. Space group P1 , Z = 1. Lattice dimensions at ?90°C: a = 855.5, b = 1 069.9, C = 1 143.5 pm, α = 105.71°, β = 95.29°, γ = 102.25° (4 096 independent observed reflexions, R = 0.039). Short Na…?F contacts of 234 pm with the four axial fluoro ligands of the dimeric anion [MoNF₄]₂^2? allow formulation of a triple ion. The centrosymmetric anion is dimerized by bent fluoro bridges with Mo? F distances of 198 and 245 pm. The long Mo? F distances of the MoF₂Mo ring are in transposition to the nitrido ligands, the bond lengths of which (165 pm) correspond to triple bonds.     

Supramolecular Assembling of Complex Tellurium Salts: Synthesis and Crystal Structures of {Cs[PhTeCl4]·CH3OH} and Cs[PhTeBr4]

The direct reaction between PhTeCl₃ and CsCl in methanol affords {Cs[PhTeCl₄]·CH₃OH}. Cs[PhTeBr₄] was prepared by refluxing [2‐Br‐C₅NH₅][PhTeBr₄] and CsCl in ethanol in the presence of an excess of HBr. In {Cs[PhTeCl₄]·CH₃OH} the [PhTeCl₄]^— units form dimers by secondary Te···Cl bonds with methanol molecules bridging adjacent Cs⁺ cations. In both compounds, the alkali metal cation interacts secondarily with the chlorine and bromine Te‐ligands, achieving singular coordination polyhedrons and holding the lattices in supramolecular tridimensional assemblies. The new complexes, {Cs[PhTeCl₄]·CH₃OH} and Cs[PhTeBr₄], crystallize in the space groups P2₁/c and P2₁/n, respectively. Only one such structure has been reported before.