First characterization of the ammine-ammonium complex [(NH4(NH3)4)2(mu-NH3)2]2+ in the crystal structure of [NH4(NH3)4][B(C6H5)4].NH3 and the [NH4(NH3)4]+ complex in [NH4(NH3)4][Ca(NH3)7]As3S6.2NH3 and [NH4(NH3)4][Ba(NH3)8]As3S6.NH3

The compound [NH4(NH3)4][B(C6H5)4].NH3 (1) was prepared by the reaction of NaB(C(6)H(5))(4) with a proton-charged ion-exchange resin in liquid ammonia. [NH(4)(NH(3))(4)][Ca(NH(3))(7)]As(3)S(6).2NH(3) (2) and [NH4(NH3)4][Ba(NH3)8]As3S6.NH3 (3) were synthesized by reduction of As(4)S(4) with Ca and Ba in liquid ammonia. All ammoniates were characterized by low-temperature single-crystal X-ray structure analysis. They were found to contain the ammine-ammonium complex with the maximal possible number of coordinating ammonia molecules, the [NH4(NH3)4]+ ion. 1 contains a special dimer, the [(NH4(NH3)4)2(mu-NH3)2]2+ ion, which is formed by two[NH4(NH3)4]+ ions linked by two ammonia molecules. The H(3)N-H...N hydrogen bonds in all three compounds range from 1.82 to 2.20 A (DHA = Donor-H...Acceptor angles: 156-178 degrees). In 2 and 3, additional H(2)N-H...S bonds to the thioanions are observed, ranging between 2.49 and 3.00 A (DHA angles: 120-175 degrees). Two parallel phenyl rings of the [B(C(6)H(5))(4)](-) anion in 1 form a pi...pi hydrogen bond (C...C distance, 3.38 A; DHA angles, 82 degrees), leading to a dimeric [B(C6H5)4]2(2-) ion.     

Rubidiumhexaamidolanthanat und -neodymat,Rb3[La(NH2)6] und Rb3[Nd(NH2)6]; Strukturverwandtschaft zu K3[Cr(OH6)] und K4CdCl6

Rubidium Hexaamidolanthanate and -neodymate, Rb₃[La(NH₂)₆] and Rb₃[Nd(NH₂)₆]; Compounds. Structurally Related to K₃[Cr(OH)₆] and K₄CdCl₆ Colourless Rb₃[La(NH₂)₆] (a = 12.298(4) Å, c = 13.759(2) Å, N = 6, R3 c) and pale blue Rb₃[Nd(NH₂)₆] (a = 12.199(6) Å, c = 13.626(4) Å, N = 6, R32) have been prepared by the reaction of the corresponding metals (Rb: La resp. Nd = 3:1) with NH₃(P(NH₃) = 4–4.5 kbar) at 300°C. Single crystal x-ray methods gave their structures. It is shown by space group relations that these compounds are structurally related to one another and to further ternary amides as well as to K₃[Cr(OH)₆] and K₄CdCl₆.     

Synthese und Kristallstruktur von Rb8[P4N6(NH)4](NH2)2 mit dem adamantanartigen Anion [P4N6(NH)4]6−

Synthesis and Crystal Structure of Rb₈[P₄N₆(NH)₄](NH₂)₂ with the Adamantane-like Anion [P₄N₆(NH)₄]^6? RbNH₂ reacts with P₃N₅ (molar ratio 6:1) at 400°C within 5 d to colourless Rb₈[P₄N₆(NH)₄](NH₂)₂. Suitable crystals for a X-ray structure determination were obtained: The compound contains adamantane-like molecular anions [P₄N₆(NH)₄]^6?. Their centres of gravity are arranged in a distorted hexagonal primitive array. All trigonal prisms of this array contain one amide ion. Rubidium ions connect the anions irregularly.     

Stabilization of the P(CF3)(2)(-) and P(C6F5)(2)(-) ions by coordination to pentacarbonyl tungsten: structures of [18-crown-6-K]P(CF3)2, [18-crown-6-K][W[P(CF3)2](CO)5], and [18-crown-6-K][[W(CO)5]2[mu-P(C6F5)2]].THF

The stabilization of the P(CF(3))(2)(-) ion by intermediary coordination to the very weak Lewis acid acetone gives access to single crystals of [18-crown-6-K]P(CF(3))(2). The X-ray single crystal analysis exhibits nearly isolated P(CF(3))(2)(-) ions with an unusually short P-C distance of 184(1) pm, which can be explained by negative hyperconjugation and is also found by quantum chemical hybrid DFT calculation. Coordination of the P(CF(3))(2)(-) ion to pentacarbonyl tungsten has only a minor effect on electronic and geometric properties of the P(CF(3))(2) moiety, while a strong increase in thermal stability of the dissolved species is achieved. The hitherto unknown P(C(6)F(5))(2)(-) ion is stabilized by coordination to pentacarbonyl tungsten and isolated as a stable 18-crown-6 potassium salt, [18-crown-6-K][W[P(C(6)F(5))(2)](CO)(5)], which is fully characterized. The tungstate, [W[P(C(6)F(5))(2)](CO)(5)](-), decomposes slowly in solution, while coordination of the phosphorus atom to a second pentacarbonyl tungsten moiety results in an enhanced thermal stability in solution. The single-crystal X-ray analysis of [18-crown-6-K][[W(CO)(5)](2)[mu-P(C(6)F(5))(2)]].THF exhibits a very tight arrangement of the two C(6)F(5) and two W(CO)(5) groups around the central phosphorus atom. NMR spectroscopic investigations of the [[W(CO)(5)](2)[mu-P(C(6)F(5))(2)]](-) ion exhibit a hindered rotation of both the C(6)F(5) and W(CO)(5) groups in solution.     

Diaquabromo(18-crown-6)rubidium and triaqua(18-crown-6)barium dibromide monohydrate: Synthesis and crystal structures

Two complexes are synthesized: diaquabromo(18-crown-6)rubidium [RbBr(18-crown-6)(H₂O)₂] (I) and triaqua(18-crown-6)barium dibromide monohydrate [Ba(18-crown-6)(H₂O)₃]²⁺ 2Br^? · H₂O (II). The orthorhombic structure of compound I (space group Pnma, a = 10.124 Å, b = 15.205 Å, c = 12.544 Å, Z = 4) and the monoclinic structure of compound II (space group C 2/c, a = 17.910 Å, b = 10.315 Å, c = 14.879 Å, β = 123.23°, Z = 4) are determined by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.063 (I) and 0.042 (II) for all 2293 (I) and 3363 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). The complex molecule [RbBr(18-crown-6)(H₂O)₂] in compound I and the randomly disordered cation [Ba(18-crown-6)(H₂O)₃]²⁺ in compound II are of the host-guest type: their Rb⁺ or Ba²⁺ cation (its coordination number is nine) is located in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In structure I, the coordination polyhedron of Rb⁺ is a distorted hexagonal pyramid with a triple apex at the Br^? ligand and two O atoms of the water molecules. In structure II, the Ba²⁺ polyhedron is a distorted hexagonal bipyramid with one apex at the O atom of the water molecule and the other split apex at two O atoms of water molecules.     

Non-classical hydrogen bonding in [K(1-aza-18-crown-6)]BH4 and its 18-crown-6 counterpart

The extended structures of [K(1-aza-18-crown-6)]BH(4) and its 18-crown-6 analogue exhibits significantly different primary and secondary stabilizing interactions. However, their respective ion pairs display similar cation-to-anion interactions, in spite of the differences in the nature of the crown ether ligand.     

Solvent extraction of Li+, H3O+ and NH4 + into nitrobenzene by using sodium dicarbollylcobaltate and calix[4]arene-bis(t-octylbenzo-18-crown-6)

From extraction experiments and $ \gamma $ -activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺ (aq) + NaL⁺ (nb) ? ML⁺ (nb) + Na⁺ (aq) taking place in the two–phase water–nitrobenzene system (M⁺= Li⁺, H₃O⁺, NH₄ ⁺; L = calix[4]arene-bis(t-octylbenzo-18-crown-6); aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Furthermore, the stability constants of the ML⁺ complexes in nitrobenzene saturated with water were calculated; they were found to increase in the following cation order: H₃O⁺ < Li⁺ < NH₄ ⁺.     

Reaction of lead halides with 18-crown-6 and dicyclohexano-18-crown-6: Solvent extraction,synthesis and crystal structure of [Pb(18-crown-6)I2]

Abstract

Solvent extraction of lead halides with 18-crown-6 (18C6), dicyclohexano-18-crown-6 (DC18C6, cis-syn-cis and cis-anti-cis isomers) in chloroform was studied, and the extraction constants corrected for side reactions and ionic strength effects were obtained. The compounds of the same composition as those being extracted were also isolated in crystal form. The molecular structure of the [Pb(18C6)I₂] complex has been determined. Crystals are monoclinic, P2₁/n, a = 11.237(2), b = 10.992(2), c = 8.139(2)Å, β = 97.32(3)°, V = 997.1(7)ų, D_calc = 2.416(2)gcm^?3, Z = 2 for the composition C₁₂H₂₄O₆PbI₂. The final R-factor is 0.043 for 558 unique reflections. The lead atom is coordinated to six oxygen atoms of the crown ether and two iodine atoms forming a hexagonal bipyramidal coordination polyhedron. The 18C6 molecule and the two halogen atoms form a hydrophobic coating for the lead atom which may be assumed to be the main reason of high extraction constants of the iodine complexes. For 10-coordinate lead ion (bidentate counter ions) the cis-syn-cis isomer of DC18C6 appears to be the best extraction reagent, while for 8-coordinate lead ion (monodentate halide anion) no difference between isomers was observed.     

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.     

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.     

Synthese und Kristallstruktur von Na10[P4(NH)6N4](NH2)6(NH3)0,5 mit dem adamantanartig aufgebauten Anion [P4(NH)6N4]4−

Synthesis and Crystal Structure of Na₁₀[P₄(NH)₆N₄](NH₂)₆(NH₃)_0.5 with an Adamantane-like Anion [P₄(NH)₆N₄]^4? Crystals of Na₁₀[P₄(NH)₆N₄](NH₂)₆(NH₃)_0.5 were obtained by the reaction of P₃N₅ with NaNH₂ (molar ratio 1:20) within 5 d at 600°C in autoclaves. The following data characterize X-ray investigations: Fm3 m, Z = 8, a = 15.423(2) Å, Z(F) = 261 with F ≥ 3 σ(F) Z(Variables) = 27, R/R_w = 0.086/0.089 The compound contains the hitherto unknown anion [P₄(NH)₆N₄]^4?, which resembles adamantane. The total structure can be described as follows: The centers of gravity of units of [Na₈(NH₂)₆(NH₃)]²⁺ – 8Na⁺ on the corners of a cube, 6NH₂^? on the ones of an inscribed octahedron with NH₃ in the center – follow the motif of a cubic-closest packed arrangement. Units of [Na₁₂(NH₂)₆]⁶⁺ – 12Na⁺ on the corners of a cuboctahedron and 6NH₂^? on the ones of an inscribed octahedron – occupy all octahedral and those of [P₄(NH)₆N₄]^4? all tetrahedral sites.     

UF6 and UF4 in Liquid Ammonia: [UF7(NH3)]3− and [UF4(NH3)4]

From the reaction of uranium hexafluoride UF₆ with dry liquid ammonia, the [UF₇(NH₃)]^3? anion and the [UF₄(NH₃)₄] molecule were isolated and identified for the first time. They are found in signal‐green crystals of trisammonium monoammine heptafluorouranate(IV) ammonia (1:1; [NH₄]₃[UF₇(NH₃)] ? NH₃) and emerald‐green crystals of tetraammine tetrafluorouranium(IV) ammonia (1:1; [UF₄(NH₃)₄] ? NH₃). [NH₄]₃[UF₇(NH₃)] ? NH₃ features discrete [UF₇(NH₃)]^3? anions with a coordination geometry similar to a bicapped trigonal prism, hitherto unknown for U^IV compounds. The emerald‐green [UF₄(NH₃)₄] ? NH₃ contains discrete tetraammine tetrafluorouranium(IV) [UF₄(NH₃)₄] molecules. [UF₄(NH₃)₄] ? NH₃ is not stable at room temperature and forms pastel‐green [UF₄(NH₃)₄] as a powder that is surprisingly stable up to 147 °C. The compounds are the first structurally characterized ammonia complexes of uranium fluorides.     

Neue Oxoterbate(IV) mit Lithium Rb2Li14[Tb3O14] und Li6Tb2O7

New Oxoterbates(IV) with Lithium: On Rb₂Li₁₄[Tb₃O₁₄] and Li₆Tb₂O₇ For the first time we prepared Rb₂Li₁₄[Tb₃O₁₄] as yellow single crystals from Li₈TbO₆ and Rb₂O (Tb:Rb = 1:2) [Ag-cylinder, 500°C, 30 d, then Au-tube, 700°C, 27 d]. The structure refinement [652 I₀ (h kl), four circle diffractometer Philips PW 1100, ω-scan, MoKα, R = 4.69%, R_w = 3.24%, absorption considered, Immm with a = 1 283.07(10), b = 790.87(7), c = 736.87(7)pm, Z = 2, d_x = 4.30 g · cm^?3] confirms that it is isotypic with K₂Li₁₄[Pb₃O₁₄]. Furthermore we got for the first time Li₆Tb₂O₇ as a bright yellow compound from Li₂O₂ and “Tb₄O₇*” [(Li:Tb = 3.4:1), Au-ube, 750°C, 13 d (powder), 850°C 22 d (single crystals)] and by thermal decomposition of Rb₂Li₁₄[Tb₃O₁₄] (Au-tube, 850°C, 25 d). Powder and single crystal data [1 327 I₀ (h kl), four circle diffractometer PW 1100, ω-scan, AgKα, R = 9.38%, R_w = 5.23%, absorption not considered, P2₁/a, a = 1 056.30(10), b = 613.50(4), c = 546.56(5) pm, β = 109.668(7)°, Z = 2, d_x = 4.67 g · cm^?3 d_pyc = 4.53 g · cm^?3] reveal a new type of structure that may be deduced by the NaCl-type of structure. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Double complexes [Co(NH3)5(H2O)]2[Zr3F18]·6H2O and [Co(NH3)6]2[Zr3F18]·6H2O

The structures of orthorhombic bis[pentaammineaquacobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Ibam), [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O, (I), and bis[hexaamminecobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Pnna), [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), consist of complex [Co(NH₃)_x(H₂O)_y]³⁺ cations with either m [in (I)] or and 2 [in (II)] symmetry, [Zr₃F₁₈]⁶⁻ anionic chains located on sites with 222 [in (I)] or 2 [in (II)] symmetry, and water molecules.     

三水合硝酸钪18-冠-6配合物的合成及其晶体结构

报道了[Sc(NO3)3(OH2)3].(18-冠-6)的合成及其晶体结构.Sc(III)离子同三个双齿配体硝酸根与三个水分子氧配位,构成九配位的配合物.配位多面体是稍有扭曲的单帽四方反棱柱.配位水分子的六个氢原子分别与上下两层冠醚环上的氧原子生成氢键,形成多层夹心分子缔合物.     

Structural diversity of lithium sulfenamides: 7Li NMR studies in solution and crystal structures of [Li2(eta2-(CH3)3C-NS-C6H4CH(3)-4)2(THF)2] and [Li2(eta1-4-CH3C6H4-NS-C6H4CH(3)-4)2(THF)4

Two lithium sulfenamides were prepared by reaction of (CH(3))(3)C-N(H)-S-C(6)H(4)CH(3)-4 (1) and 4-CH(3)C(6)H(4)-N(H)-S-C(6)H(4)CH(3)-4 (2) with an alkyllithium. The unsolvated sulfenamide Li[(CH(3))(3)C-NS-C(6)H(4)CH(3)-4] (3) was soluble enough for variable-temperature (VT) (7)Li NMR to provide evidence of a dynamic exchange of oligomers in solution. The crystal structures of the solvated sulfenamides of [Li(2)(eta(2)-(CH(3))(3)C-NS-C(6)H(4)CH(3)-4)(2)(THF)(2)] (4) and of [Li(2)(eta(1)-4-CH(3)C(6)H(4)-NS-C(6)H(4)CH(3)-4)(2)(THF)(4)] (6) consisted of dimers in which the anions display different hapticities. The VT (7)Li NMR spectra of 4 suggest that the two different structures exist in equilibrium in toluene-THF mixtures. These compounds are easily oxidized to the neutral thioaminyl radicals as identified by EPR spectroscopy.