Bismuth Polyanions in Solution: Synthesis and Structural Characterization of (2, 2, 2‐crypt‐A)2Bi4 (A = K,Rb) and the Formation of the Laves Phases ABi2 (A = K,Rb, Cs) from Solution

The possibility to synthesize and isolate different types of bismuth polyanions by dissolving various intermetallic precursors (binary samples from A‐Bi or ternary samples from A‐A'‐Bi systems, A and A' = K, Rb, Cs) in ethylenediamine or dimethylform amide in the presence of sequestering agents (2, 2, 2‐crypt or 18‐crown‐6) was investigated. The crystals of (2, 2, 2‐crypt‐K)₂Bi₄ ( 1 ) and (2, 2, 2‐crypt‐Rb)₂Bi₄ ( 2 ) compound were obtained from such solutions, the latter for the first time, and their structures were determined. The two compounds are isostructural (P1, Z=1, a = 11.052(2) Å, b = 11.370(2) Å, c = 11.698(2) Å, α = 61.85(3) °, β = 82.58(3) °, γ = 81.87(3) °, R₁ = 0.058, wR² = 0.149 for 1 and a = 11.181(2) Å, b = 11.603(2) Å, c = 11.740(2) Å, α = 61.96(3) °, β = 81.45(3) °, γ = 82.26(3) °, R₁ = 0.041, wR² = 0.109) and contain Bi₄^2— square planar cluster anions and cryptated alkali metal cations. In the case of the presence of 18‐crown‐6 the Laves phases ABi₂ (A = K, Rb, Cs) could be isolated from the solutions. A mechanism for the formation of ABi₂ is proposed.     

Zintl‐Verbindungen mit Gold und Germanium: M3AuGe4 mit M = K,Rb und Cs

Zintl‐Compounds with Gold and Germanium: M₃AuGe₄ with M = K, Rb, Cs Black, brittle single crystals of M₃AuGe₄ with M = K, Rb, Cs were synthesized by reactions of alkali metal azides (MN₃) with gold sponge and germanium powder at T = 1120 K. The structures of the compounds (space group Pmmn, Z = 2, K₃AuGe₄: a = 6.655(1)Å, b = 11.911(2)Å, c = 6.081(1)Å; Rb₃AuGe₄: a = 6.894(1)Å, b = 12.421(1)Å, c = 6.107(1)Å; Cs₃AuGe₄: a = 7.179(1)Å, b = 12.993(2)Å, c = 6.112(2)Å) were determined from X‐ray single‐crystal diffractometry data. The semiconducting compounds contain equation/tex2gif-stack-2.gif[AuGe₄]‐chains with P₄‐analogous Ge₄‐tetrahedra which are connected by μ₂‐bridging gold atoms in a distorted tetrahedral Ge‐coordination.     

Synthese und Eigenschaften von cis-Diacidophthalocyaninato(2–)thallaten(III); Kristallstruktur von Tetra(n-butyl)ammonium-cisdinitrito(O,O′)- und -cis-dichlorophthalocyaninato(2–)thallat(III)

Syntheses and Properties of cis -Diacidophthalocyaninato(2–)thallates(III); Crystal Structure of Tetra(n-butyl)ammonium cis -dinitrito(O,O ′)- and cis -dichlorophthalocyaninato(2–)thallate(III) Blue green cis-diacidophthalocyaninato(2–)thallate(III), ^cis[Tl(X)₂pc^2–]^– (X = Cl, ONO′, NCO) is prepared from iodophthalocyaninato(2–)thallium(III) and the corresponding tetra(n-butyl)ammonium salt, (ⁿBu₄N)X in dichloromethane, and isolated as (ⁿBu₄N)^cis[Tl(X)₂pc^2–]. (ⁿBu₄N)^cis[Tl(ONO′)₂pc^2–] ( 1 ) and (ⁿBu₄N)^cis[Tl(X)₂pc^2–] · 0,5 (C₂H₅)₂O ( 2 ) crystallize in the monoclinic space group P2₁/n with cell parameters for 1: a = 14.496(2) Å, b = 17.293(5) Å, c = 18.293(2) Å, β = 98.76(1)° resp. for 2 : a = 13.146(1) Å, b = 14.204(5) Å, c = 24.900(3) Å, β = 93.88(1)°; Z = 4. In 1 , the octa-coordinated Tl atom is surrounded by four isoindole-N atoms (N_iso) and four O atoms of the bidental nitrito(O,O′) ligands in a distorted antiprism. The Tl–N_iso distances vary between 2.257(3) and 2.312(3) Å, the Tl–O distances between 2.408(3) and 2.562(3) Å. In 2 , the hexa-coordinated Tl atom ligates four N_iso atoms and two Cl atoms in a typical cis-arrangement. The average Tl–N_iso distance is 2.276 Å, the average Tl–Cl distance is 2.550 Å. In 1 and 2 , the Tl atom is directed out of the centre of the (N_iso)₄ plane (Ct_N) towards the acido ligands (d(Tl–Ct_N) = 1.144(1) Å in 1 , 1.116(2) Å in 2 ), and the phthalocyaninato ligand is concavely distorted. The vertical displacements of the periphereal C atoms amounts up to 0.82 Å. The optical and vibrational spectra as well as the electrochemical properties are discussed.     

Syntheses and Crystal Structures of Rb2B2Se7, Tl2B2Se7, Cs3B3Se10, and Tl3B3Se10: New Perseleno‐selenoborates with Polymeric Anionic Chains

The perseleno‐selenoborates Rb₂B₂Se₇ and Cs₃B₃Se₁₀ were prepared from the metal selenides, amorphous boron and selenium, the thallium perseleno‐selenoborates Tl₂B₂Se₇ and Tl₃B₃Se₁₀ directly from the elements in evacuated carbon coated silica tubes by solid state reactions at temperatures between 920 K and 950 K. All structures were refined from single crystal X‐ray diffraction data. The isotypic perseleno‐selenoborates Rb₂B₂Se₇ and Tl₂B₂Se₇ crystallize in the monoclinic space group I 2/a (No. 15) with lattice parameters a = 12.414(3) Å, b = 7.314(2) Å, c = 14.092(3) Å, β = 107.30(3)°, and Z = 4 for Rb₂B₂Se₇ and a = 11.878(2) Å, b = 7.091(2) Å, c = 13.998(3) Å, β = 108.37(3)° with Z = 4 for Tl₂B₂Se₇. The isotypic perseleno‐selenoborates Cs₃B₃Se₁₀ and Tl₃B₃Se₁₀ crystallize in the triclinic space group P1 (Cs₃B₃Se₁₀: a = 7.583(2) Å, b = 8.464(2) Å, c = 15.276(3) Å, α = 107.03(3)°, β = 89.29(3)°, γ = 101.19(3)°, Z = 2, (non‐conventional setting); Tl₃B₃Se₁₀: a = 7.099(2) Å, b = 8.072(2) Å, c = 14.545(3) Å, α = 105.24(3)°, β = 95.82(3)°, γ = 92.79(3)°, and Z = 2). All crystal structures contain polymeric anionic chains of composition ([B₂Se₇]^2–)_n or ([B₃Se₁₀]^3–)_n formed by spirocyclically fused non‐planar five‐membered B₂Se₃ rings and six‐membered B₂Se₄ rings in a molar ratio of 1 : 1 or 2 : 1, respectively. All boron atoms have tetrahedral coordination with corner‐sharing BSe₄ tetrahedra additionally connected via Se–Se bridges. The cations are situated between three polymeric anionic chains leading to a nine‐fold coordination of the rubidium and thallium cations by selenium in M₂B₂Se₇ (M = Rb, Tl). Coordination numbers of Cs⁺ (Tl⁺) in Cs₃B₃Se₁₀ (Tl₃B₃Se₁₀) are 12(11) and 11(9).     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.     

Synthesis, crystal structure, and vibrational spectra of MVO(SO4)2 (M = Rb, Cs, or Tl)

A series of MVO(SO₄)₂ vanadium complexes, where M = Rb, Cs, or Tl, were prepared, and their crystal structures and physicochemical properties studied. The rubidium and thallium compounds of this series were found to be isostructural to each other and to crystallize, like KVO(SO₄)₂ and NH₄VO(SO₄)₂, in orthorhombic system (space group P2₁2₁2₁, No. 19, Z = 4) with the unit cell parameters a = 4.9735(2) Å, b=8.7894(4) Å, c = 16.6968(8) Å, V = 729.88 ų (Rb); and a = 4.9636(1) Å, b = 8.7399(2) Å, c = 16.8598(4) Å, V = 731.39 ų (Tl). The cesium compound was found to crystallize in monoclinic system (space group P2₁/a, No. 14-2, Z = 4): a = 10.0968(6) Å, b = 8.9131(4) Å, c = 9.8675(5) Å, β = 114.640(2)°, V = 807.16 ų. The MVO(SO₄)₂ crystal structure is built of VO₆ octahedra, which are linked into layers by bridging SO₄ groups. At the apex of each VO₆ octahedron, there is a short V-O terminal bond having a length of 1.54(1) Å (Rb), 1.57(2) Å (Tl), and 1.52(4) Å (Cs).     

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.     

Bis(phthalocyaninato(2–)rhenium(II)): Synthesis,Properties, and Crystal Structure

Blue, paramagnetic bis(phthalocyaninato(2–)rhenium(II)) (μ_eff = 0,88 μ_B, per Re, at 300 K) is prepared by thermal decomposition of trans-bis(triphenylphosphine)phthalocyaninato(2–)rhenium(II), in boiling triphenylphosphine. It crystallizes in the triclinic space group P 1 with cell parameters as follows: a = 7.799(3) Å, b = 12.563(7) Å, c = 12.69(1) Å, α = 89.97(5)°, β = 94.14(5)°, γ = 106.39(4)°; Z = 1. Two cofacial phthalocyaninates are bonded together by a Re–Re bond with a Re–Re distance of 2.285(2) Å. The Re atoms are located distinctly outside the centre of the (N_iso)₄ planes by 0.426(3) Å. The Re–N_iso distance varies from 1.99(1) to 2.04(1) Å (average 2.02 Å). The pc^2– ligands are in an eclipsed conformation and concavely distorted. In the UV-VIS-NIR spectrum the B region is split into two bands of comparable intensity due to strong excitonic coupling. The Re–Re stretching vibration at 240 cm^–1 is selectively enhanced in the resonance Raman spectrum (λ_exc = 488 nm).     

Hydrothermal Synthesis of Rare Earth Iodates from the Corresponding Periodates: Structures of Sc(IO3)3, Y(IO3)3 · 2 H2O,La(IO3)3 · 1/2 H2O and Lu(IO3)3 · 2 H2O

Hydrothermal syntheses of single crystals of rare earth iodates, by decomposition of the corresponding periodate, are presented. This appears to be a generic method for making rare earth iodate crystals in a short period of time. Single crystal X‐ray diffraction structures of the four title compounds are presented. Sc(IO₃)₃: Space group R3, Z = 6, lattice dimensions at 100 K; a = b = 9.738(1), c = 13.938(1) Å; R₁ = 0.0383. Y(IO₃)₃ · 2 H₂O: Space group P1, Z = 2, lattice dimensions at 100 K: a = 7.3529(2), b = 10.5112(4), c = 7.0282(2) Å, α = 105.177(1)°, β = 109.814(1)°, γ = 95.179(1)°; R₁ = 0.0421. La(IO₃)₃ · ? H₂O: Space group Pn, Z = 2, lattice dimensions at 100 K: a = 7.219(2), b = 11.139(4), c = 10.708(3) Å, β = 91.86(1)°; R₁ = 0.0733. Lu(IO₃)₃ · 2 H₂O: Space group P1, Z = 2, lattice dimensions at 120 K: a = 7.2652(9), b = 7.4458(2), c = 9.3030(3) Å, α = 79.504(1)°, β = 84.755(1)°, γ = 71.676(2)°; R₁ = 0.0349.     

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.     

Kristallstrukturen und thermisches Verhalten von Metalldihydrogenphosphat‐HF‐Addukten MH2PO4 · HF (M = K,Rb, Cs) mit Wasserstoffbrückenbindungen vom Typ F–H…O

Structures and Thermal Behaviour of Alkali Metal Dihydrogen Phosphate HF Adducts, MH₂PO₄ · HF (M = K, Rb, Cs), with Hydrogen Bonds of the F–H…O Type Three HF adducts of alkali metal dihydrogen phosphates, MH₂PO₄ · HF (M = K, Rb, Cs), have been isolated from fluoroacidic solutions of MH₂PO₄. KH₂PO₄ · HF crystallizes monoclinic: P2₁/c, a = 6,459(2), b = 7,572(2), c = 9,457(3) Å, β = 101,35(3)°, V = 453,5(3) ų, Z = 4. RbH₂PO₄ · HF and CsH₂PO₄ · HF are orthorhombic: Pna2₁, a = 9,055(3), b = 4,635(2), c = 11,908(4) Å, V = 499,8(3) ų, Z = 4, and Pbca, a = 7,859(3), b = 9,519(4), c = 14,744(5) Å, V = 1102,5(7) ų, Z = 8, respectively. The crystal structures of MH₂PO₄ · HF contain M⁺ cations, H₂PO₄^– anions and neutral HF molecules. The H₂PO₄^– anions are connected to layers by O–H…O hydrogen bonds (2,53–2,63 Å), whereas the HF molecules are attached to the layers via very short hydrogen bonds of the F‐H…O type (2,36–2,38 Å). The thermal decomposition of the adducts proceeds in three steps. The first step corresponds to the release of mainly HF and a smaller quantity of water. In the second and third steps, water evolution caused by condensation of dihydrogen phosphate is the dominating process whereas smaller amounts of HF are also released.     

Synthese,Struktur und Reaktionen von Vanadiumsäureestern VO(OR)3: Umesterung und Reaktion mit Oxalsäure

Synthesis, Structure, and Reactions of Vanadium Acid Esters VO(OR)₃: Transesterification and Reaction with Oxalic Acid The reaction of tert.‐Butyl Vanadate VO(O‐tert.Bu)₃ ( 1 ) with H₂C₂O₄ in the primary alcohols ethanol and propanol results in the formation of (ROH)(RO)₂OV^V(C₂O₄)V^VO(OR)₂(HOR) (with R = C₂H₅ 2 and R = C₃H₇ 3 ). Compounds 2 and 3 are the first structurally characterized neutral, binuclear oxo‐oxalato‐complexes with pentavalent vanadium. The two vanadium atoms are connected by a bisbidentate oxalate group. The {VO₆} coordination at each vanadium site is completed by a terminal oxo group, an alcohol ligand and two alcoxide groups. The binuclear molecules are connected to chains by hydrogen bonding. In the case of 2 a reversible isomorphic phase transition in the temperature range of –90 °C to –130 °C is observed. From methanolic solution the polymeric Methyl Vanadate [VO(OMe)₃] ( 4 ) was obtained by transesterification. A report on the crystal structures of 1 , 2 and 3 as well as a redetermination of the structure of 4 is given. Crystal data: 1, orthorhombic, Cmc2₁, a = 16.61(2) Å, b = 9.274(6) Å, c = 10.784(7) Å, V = 1662(2) ų, Z = 4, d_c = 1.144 gcm^–1; 2 (–90 ° C) , monoclinic, I2/a, a = 33.502(4) Å, b = 7.193(1) Å, c = 15.903(2) Å und β = 143.060(3)°, V = 2303(1) ų, Z = 4, d_c = 1.425 gcm^–1; 2 (–130 ° C) , monoclinic, I2/a, a = 33.274(4) Å, b = 7.161(1) Å, c = 47.554(5) Å, β = 142.798(2)°, V = 6851(1) ų, Z = 12, d_c = 1.438 gcm^–1; 3 , triklinic, P1, a = 9.017(5) Å, b = 9.754(5) Å, c = 16.359(9) Å, α = 94.87(2)°, β = 93.34(2)°, γ = 90.42(2)°, V = 1431(1) ų, Z = 2, d_c = 1.340 gcm^–1; 4 , triklinic, P1, a = 8.443(2) Å, b = 8.545(2) Å, c = 9.665(2) Å, α = 103.202(5)°, β = 96.476(5)°, γ = 112.730(4)°, V = 610.2(2)ų, Z = 4, d_c = 1.742 gcm^–1.     

Mixed‐Valence Thallium(I,III) Bromides The Crystal Structure of α—Tl2Br3

Thallium sesquibromide Tl₂Br₃ is dimorphic. Scarlet coloured crystals of α‐Tl₂Br₃ were obtained by reactions of aqueous solutions of TlBr₃ and Tl₂SO₄ in agarose gel. In case of rapid crystallisation of hydrous TlBr₃/TlBr solutions and from TlBr/TlBr₂ melts ß‐Tl₂Br₃ is formed as scarlet coloured, extremely thin lamellae. The crystal structures of both forms are very similar and can be described as mixed‐valence thallium(I)‐hexabromothallates(III) Tl₃[TlBr₆]. In the monoclinic unit cell of α‐Tl₃[TlBr₆] (a = 26.763(7) Å; b = 15.311(6) Å; c = 27.375(6) Å; β = 108.63(2)°, Z = 32, space gr. C2/c) the 32 Tl^III‐cations are found in strongly distorted octahedral TlBr₆ groups. The 96 Tl^I cations are surrounded either by four or six TlBr₆ groups with contacts to 8 or 9 Br neighbors. Crystals of β‐Tl₃[TlBr₆] by contrast show almost hexagonal metrics (a = 13.124(4) Å, b = 13.130(4) Å, c = 25.550(7) Å, γ = 119.91(9)°, Z = 12, P2₁/m). Refinements of the parameters revealed structural disorder of TlBr₆ units, possibly resulting from multiple twinning. Both structures are composed of Tl₂[TlBr₆]^— and Tl₄[TlBr₆]⁺ multilayers, which alternate parallel (001). The structural relationships of the complicated structures of α‐ and β‐Tl₃[TlBr₆] to the three polymorphous forms of Tl₂Cl₃ as well as to the structures of monoclinic hexachlorothallates M₃TlCl₆ (M = K, Rb) and the cubic elpasolites are discussed.     

A new diaza‐18‐crown‐6 ligand containing two quinolin‐8‐ylmethyl side arms: Crystal structures and characterization of the ligand,the protonated ligand and its mononuclear barium(II) and dinuclear copper(II) complexes

A new 7,16‐bis(quinolin‐8‐ylmethyl)‐1,4,10,13‐tetraoxa‐7,16‐diazacyclooctadecane ligand, L, has been prepared and its crystal structure reported. In addition, the structure of the protonated ligand H₂L has been determined. H₂L is of interest because of interatomic interactions between the ligand and perchlorate ions. The mononuclear Ba(II) (Ba L ), and dinuclear Cu(II) (Cu₂L) complexes of L have been prepared and their crystal structures determined. Stability constants and other thermodynamic data valid in methanol at 23 or 25° for these and several other complexes of L have been obtained. Among the metal ions studied, L forms the most stable complex with Ba²⁺. In addition, L selectively binds Cu²⁺ over Ni²⁺ by about 3 orders of magnitude. Some of the complexes have been studied using nmr and uv‐vis spectroscopic techniques. Crystal data are given for L, space group, P2₁c, a = 8.8325(14) Å, b = 13.808(3) Å, c = 13.310(3) Å; β = 94.72(2)° Z=2, R = 0.0727; for H₂ L , space group, P2₁/c, a = 14.685(3) Å, b = 15.035(6) Å, c = 17.369(4) Å, β = 90.366(12)°, Z = 4, R = 0.0781; for Ba L , space group, Pbcn, a = 17.314(3) Å, b = 9.539(2) Å, c = 22.081(3) Å, Z = 4, R = 0.0354; and for Cu₂ L , space group, Cc, a = 19.762(2) Å, b = 14.413(2) Å, c = 14.935(2) Å, β = 98.753(12)°, Z = 4, R = 0.0564. Cu²⁺ forms a hydroxo‐bridged dinuclear complex with L while Ba²⁺ forms a mononuclear complex with L in which its two side arms are not involved in complexation.     

Kristallstrukturen von Verbindungen A2[MnF3(SO4)] (A = Rb,NH4, Cs): Jahn‐Teller‐Ordnung in Mangan(III)‐fluoridsulfaten. I.

Jahn‐Teller Ordering in Manganese(III) Fluoride Sulphates. I. Crystal Structures of A₂[MnF₃(SO₄)] (A = Rb, NH4, Cs) The three isostructural fluorosulphatomanganates(III) A₂[MnF₃(SO₄)] (A = Rb, NH₄, Cs) crystallize in space group P2₁/c, Z = 4. Rb₂[MnF₃(SO₄)]: a = 7.271, b = 11.091, c = 8.776Å, β = 92.26°, R = 0.033; (NH₄)₂[MnF₃(SO₄)]: a = 7.299, b = 10.157, c = 8.813Å, β = 91.51°, R = 0.025; Cs₂[MnF₃(SO₄)]: a = 7.365, b = 11.611, c = 9.211, β = 92.30°, R = 0.029. In the chain anions [MnF₃(SO₄)]^2— manganese(III) is coordinated by two trans‐terminal and two trans‐bridging fluorine ligands, and by the O‐atoms of two briding sulphate ligands in trans position. The Jahn‐Teller effect induces a variety of antiferrodistortive ordering resulting in distorted [MnF₄O₂] octahedra with alternating elongation of F—Mn—F — and O—Mn—O — axes, respectively. Thus, only asymmetrical bridges are formed.     

Synthesis of trans‐disubstituted cyclam ligands appended with two 6‐hydroxymethylpyridin‐2‐ylmethyl sidearms: Crystal structures of the 1,8‐dimethyl‐4,ll‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)cylam ligand and its Co(II) and Ni(II) complexes

Two new trans‐disubstituted cyclam ligands; 1,8‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)‐1,4,8,11‐tetra‐azacyclotetradecane ( 5 ) and 1,8‐dimethyl‐4, 11‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)‐1,4,8,11 ‐tetraaza‐cyclotetradecane ( 6 ); have been synthesized and characterized. The crystal structures of ligand 6 and its Ni(II) and Co(II) complexes have been determined. Crystal data are given for 6 , space group, P2₁/c, a = 11.095 (6) Å, b = 9.467 (5) Å, c = 13.283 (8) Å; β = 106.95 (5)°, Z = 2, R = 0.0715; for [Ni 6 ](C10₄)₂, space group P2₁/c, a = 9.4848 (14) Å, b = 33.941(6) Å, c = 9.793(2) A, β = 95.264(14)°, Z = 4, R = 0.0567; for [Co 6 ](C10₄)₂, space group, P2₁/c, a = 9.440 (6) Å, b = 33.848 (13) Å, c = 9.820 (3) Å, β = 95.16(3)°, Z = 4, R = 0.0718. In both complexes, the metal atoms are six‐coordinate with only one of the pendants interacting with the central metal atom and the other pendant remaining uncoordinated.     

Ein Beitrag zu Rhenium(II)‐, Osmium(II)‐ und Technetium(II)‐Thionitrosylkomplexen vom Typ [M(NS)Cl4py]—: Darstellung,Strukturen und EPR‐Spektren

A Contribution to Rhenium(II)‐, Osmium(II)‐, and Technetium(II)‐Thionitrosyl‐Complexes: Preparation, Structures, and EPR‐Spectra The reaction of [Re^VINCl₄]^— and [Os^VINCl₄]^— with S₂Cl₂ leads to the formation of the thionitrosyl complexes [M^II(NS)Cl₄]^— (M = Re, Os) which could not be isolated as pure compounds. Addition of pyridine to the reaction mixture results in the formation of the stable compounds trans‐(Ph₄P)[Os^II(NS)Cl₄py], trans‐(Hpy)[Os^II(NS)Cl₄py], trans‐(Ph₄P)[Re^II(NS)Cl₄py], and cis‐(Ph₄P)[Re^II(NS)Cl₄py]. The crystal structure analyses show for trans‐(Ph₄P)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 12.430(3)Å, b = 18.320(4)Å, c = 15.000(3)Å, β = 114.20(3)°, Z = 4), trans‐(Hpy)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 7.689(1)Å, b = 10.202(2)Å, c = 20.485(5)Å, β = 92.878(4)°, Z = 4), trans‐(Ph₄P)[Re^II(NS)Cl₄py] (triclinic, P1¯, a = 9.331(5)Å, b = 12.068(5)Å, c = 15.411(5)Å, α = 105.25(1)°, β = 90.23(1)°, γ = 91.62(1)°, Z = 2), and cis‐(Ph₄P)[Re^II(NS)Cl₄py] (monoclinic, P2₁/c, a = 10.361(1)Å, b = 16.091(2)Å, c = 17.835(2)Å, β = 90.524(2)°, Z = 4) M‐N‐S angles in the range 168‐175°. This indicates a nearly linear coordination of the NS ligand. The metal atom is octahedrally coordinated in all cases. The rhenium(II) thionitrosyl complexes (5d⁵ “low‐spin” configuration, S = 1/2) are studied by EPR in the temperature range 295 > T > 130 K. In addition to the detection of the complexes formed during the reaction of [Re^VINCl₄]^— with S₂Cl₂ EPR investigations on diamagnetically diluted powders and single crystals of the system (Ph₄P)[Re^II/Os^II(NS)Cl₄py] are reported. The ^{185, 187}Re hyperfine parameters are used to get information about the spin‐density distribution of the unpaired electron in the complexes under study. [Tc^VINCl₄]^— reacts with S₂Cl₂ under formation of [Tc^II(NS)Cl₄]^— which is not stable and decomposes under S₈ elimination and rebuilding of [Tc^VINCl₄]^— as found by EPR monitoring of the reaction.     

Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.     

Die Reaktionen von M[BF4] (M = Li,K) und (C2H5)2O·BF3 mit (CH3)3SiCN. Bildung von M[BFx>(CN)4—x] (M = Li,K; x = 1, 2) und (CH3)3SiNCBFx(CN)3—x, (x = 0, 1)

The Reactions of M[BF₄] (M = Li, K) and (C₂H₅)₂O·BF₃ with (CH₃)₃SiCN. Formation of M[BF_x(CN)_4—x] (M = Li, K; x = 1, 2) and (CH₃)₃SiNCBF_x(CN)_3—x, (x = 0, 1) The reaction of M[BF₄] (M = Li, K) with (CH₃)₃SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BF_x(CN)_4—x] (x = 1, 2; M = Li, K). By using (C₂H₅)₂O·BF₃ the synthesis yields the compounds (CH₃)₃SiNCBF_x(CN)_3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF₂(CN)₂]·2Me₃SiCN Cmc2₁, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) ų, Z = 12, R₁ = 4.7%; K[BF₂(CN)₂] P4₁2₁2, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) ų, Z = 48, R₁ = 2.5%; K[BF(CN)₃] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) ų, Z = 2, R₁ = 3.6%; Me₃SiNCBF(CN)₂ Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) ų, Z = 8, R₁ = 4.4%     

Bis(1,2‐diselenoquadratato)metallate

Bis(1,2‐diselenosquarato) Metalates A series of 1,2‐diselenosquarato metalates [M(dssq)₂]^2– (M = Pd²⁺, Pt²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Cd²⁺, Pb²⁺, VO²⁺) was available by direct synthesis from the appropriate metal salt with dipotassium 1,2‐diselenosquarate in deoxygenized water under an argon athmosphere. The copper(II)complex, [Cu(dssq)₂]^2–, and the oxovanadium(IV)complex, [VO(dssq)₂]^2–, were identified in solution by EPR spectroscopy (parameters: [Cu(dssq)₂]^2–: g₀ = 2.073; a = –76.0 · 10^–4 cm^–1, a = 47.0 · 10^–4 cm^–1; [VO(dssq)₂]^2–: g₀ = 1.986; a = 74.9 · 10^–4 cm^–1). The complexes bis(tetraphenylphosphonium)[bis(1,2‐diselenosquarato)nickelate(II)], (Ph₄P)₂[Ni(dssq)₂], and bis(tetraphenylphosphonium)[bis(1,2‐diselenosquarato)zincate(II)], (Ph₄P)₂[Zn(dssq)₂], were characterized by X‐ray structure analysis. The square‐planar Ni^II complex (Ph₄P)₂[Ni(dssq)₂] crystallizes in the monoclinic spacegroup P2₁/n with the unit cell parameters a = 11.1472(8) Å, b = 15.331(1) Å, c = 14.783(1) Å, β = 94.441(1)° and Z = 2. The Zn^II‐complex (Ph₄P)₂[Zn(dssq)₂] is tetrahedral coordinated and crystallizes in the monoclinic spacegroup P2₁/c with the unit cell parameters a = 9.4238(1) Å, b = 18.5823(3) Å, c = 29.5309(5) Å, β = 96.763(1)° and Z = 4.