Germanium(II)‐, Zinn(II)‐ und Blei(II)‐Derivate des polycyclischen Alumosiloxans [Ph2SiO]8[Al(O)OH]4

Germanium(II)‐, Tin(II)‐ and Lead(II)‐Derivatives of the polycyclic Alumosiloxane [Ph₂SiO]₈[Al(O)OH]₄ Five new derivatives of the polycyclic alumosiloxane [Ph₂SiO]₈[Al(O)OH]₄ have been synthesized by replacement of the protic hydrogen atoms on the hydroxy‐groups attached to the aluminium atoms by the divalent group 14 elements germanium, tin and lead. The compounds can be divided in those with one metal atom per alumosiloxane moiety, [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]M (M=Ge, Sn), and those with complete substitution of the protic hydrogen atoms by metal atoms like [Ph₂SiO]₈[AlO₂]₄M₂ (M= Sn, Pb). Always one element of the series Ge, Sn, Pb is missing in the two types of compounds. Crystal structure analyses of [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]₂M · 2 C₄H₈O₂ (M= Ge ( 1 ), Sn ( 2a )), [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]₂Sn · 2 THF ( 2b ) and [Ph₂SiO]₈[AlO₂]₄M₂ (M= Sn ( 3 ), Pb ( 4 )) have been performed elucidating either polycyclic basket‐type ( 1 , 2a , 2b ) or closed polyhedral structures ( 3 , 4 ).     

Reactivity of [(Ph2Si)2O3]4[Al(OH)]4 and [(Ph2Si)2O3]4[Al(OLi)]4 towards NaOEt and LiOH. Synthesis of New Twelve‐membered Alumopolysiloxane Rings

The reaction between [(Ph₂Si)₂O₃]₄[Al(OH)]₄ ( 1 ) or [(Ph₂Si)₂O₃]₄[Al(OLi)]₄ ( 2 ) with sodium ethoxide, or lithium hydroxide in presence of CuI·H₂O leads to the formation of new alumopolysiloxane compounds. Indeed, transformations of 1 under the partial incorporation of the reactants are found giving rise to new heteroleptic inorganic macrocycles. The molecular structure of [(Ph₂Si)₂O₃]₄[Al(ONa)]₂[Al(OH)(NaOEt)]₂·2Et₂O ( 3 ) and [(Ph₂Si)₂O₃]₄[Al(OLi)]₂[Al(OH)(LiOH)]₂·2Et₂O·2THF ( 4 ) have been determined by single‐X‐ray diffraction analysis. Both alumosiloxanes 3 and 4 are constituted by a twelve‐membered ring.     

Two new metal derivates of the alumosiloxane [Ph2SiO]8[AlO(OH)]4: [Ph2SiO]8[AlO2(Na)]4 · 5(THF) and [Ph2SiO]8[AlO(OH)]2[AlO2]2[Zn(OH)]2 · 2(OEt2)

When the polycyclic alumosiloxane [Ph₂SiO]₈[AlO(OH)]₄ is allowed to react with either cyclopentadienyl sodium in tetrahydrofuran or with dimethyl zinc in diethyl ether the organic ligands on the metal elements are eliminated as cyclopentadiene or methane and the metals are bonded to oxygen atoms in the alumosiloxane forming [Ph₂SiO]₈[AlO₂(Na)]₄ · 5(THF) or [Ph₂SiO]₈[AlO(OH)]₂[AlO₂]₂[Zn(OH)]₂ · 2(OEt₂), respectively. X-ray structure determinations reveal that in the sodium derivative the original polycycle rests almost unchanged while in the zinc derivative the inner skeleton is rearranged.     

Eine alternative Synthese des Oligoalumosiloxans [Ph2SiO]8[Al(O)OH]4 und seiner Alkohol‐Addukte

The oligoalumosiloxanes {[Ph₂SiO]₈[Al(O)OH]₄·2,5Et₂O·HOtBu} ( 6 ) and {[Ph₂SiO]₈[Al(O)OH]₄·2Et₂O·2HOiPr} ( 7 ) have been obtained from the reaction of diphenylsilanediol with aluminium‐tri‐tert‐butoxide and aluminium‐tri‐iso‐propoxide in ethyl ether with reasonable yields. In a 1:1 molar mixture of toluene and the respective alcohol (iso‐propanol or tert‐butanol), the ethyl ether molecules in {[Ph₂SiO]₈[Al(O)OH]₄·4Et₂O}, in 6 or 7 can be completely displaced forming the compounds [Ph₂SiO]₈[Al(O)OH]₄·4HOiPr ( 8 ) and [Ph₂SiO]₈[Al(O)OH]₄·nHOtBu ( 9 ). Whereas 6 , 7 and 8 are crystalline, 9 is obtained as a viscous liquid. An X‐ray structure determination on {[Ph₂SiO]₈[Al(O)OH]₄·3Et₂O·HOtBu} reveals different bonding modes of the diethyl ether molecules to the oligoalumosiloxane compared to the tert‐butanol, which forms two hydrogen bonds (one to the OH‐group of the inner Al₄(OH)₄ cycle and one through the alcohol OH‐group to a Si–O–Al moiety. The alcohol adducts have been characterized in solution through ¹H‐, ¹³C‐ and ²⁹Si‐NMR and show dynamic equilibria between the oligoalumosiloxane [Ph₂SiO]₈[Al(O)OH]₄ and the alcohol molecules.     

Die Kristallstrukturen von [Ph3PMe]Cl·CH2Cl2, [Ph4P]NO3·CH2Cl2 und [Ph4P]2[SiF6]·CH2Cl2

Crystal Structures of [Ph₃PMe]Cl·CH₂Cl₂, [Ph₄P]NO₃·CH₂Cl₂, and [Ph₄P]₂[SiF₆]·CH₂Cl₂ The crystal structures of the title compounds are determined by X‐ray diffraction. In all cases, the included dichloromethane molecules as well as the phosphonium cations are involved to form hydrogen bridges with the anions. [Ph₃PMe]Cl·CH₂Cl₂ ( 1 ): Space group , Z = 2, lattice dimensions at 100 K: a = 890.3(1), b = 988.0(1), c = 1162.5(1) pm, α = 106.57(1)°, β = 91.79(1)°, γ = 92.60(1)°, R₁ = 0.0253. [Ph₄P]NO₃·CH₂Cl₂ ( 2 ): Space group P2₁/n, Z = 4, lattice dimensions at 193 K: a = 1057.0(1), b = 1666.0(1), c = 1358.9(1) pm, β = 100.10(1)°, R₁ = 0.0359. [Ph₄P]₂[SiF₆]·CH₂Cl₂ ( 3 ): Space group , Z = 2, lattice dimensions at 193 K: a = 1063.9(1), b = 1233.1(1), c = 1782.5(2) pm, α = 76.88(1)°, β = 83.46(1)°, γ = 72.29(1)°, R₁ = 0.0332.     

Die Kristallstrukturen von (Ph4P)2[HfCl6]·2CH2Cl2 und (Ph4P)2[Hf2Cl10]·CH2Cl2

Crystal Structures of (Ph₄P)₂[HfCl₆]·2CH₂Cl₂ and (Ph₄P)₂[Hf₂Cl₁₀]·CH₂Cl₂ Colourless single crystals of (Ph₄P)₂[HfCl₆]·2CH₂Cl₂ ( 1 ) and (Ph₄P)₂[Hf₂Cl₁₀]·CH₂Cl₂ ( 2 ) were obtained from hafniumtetrachloride and tetraphenylphosphonium chloride in dichloromethane solution, using the corresponding stoichiometry of the educts. Both compounds were characterized by X‐ray structure determinations. 1 : Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1018.3(1), b = 1121.0(1), c = 1240.1(1) pm, α = 70.55(1)°, β = 81.38(1)°, γ = 80.02(1)°, R₁ = 0.0374. 2 : Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1124.4(1), b = 1141.9(1), c = 1281.4(1) pm, α = 63.80(1)°, β = 68.15(1)°, γ = 86.33(1)°, R₁ = 0.0208.     

Synthese und Kristallstrukturen der mehrkernigen Rhenium–Nitrido‐Komplexe [Re2N2Cl4(PMe2Ph)4(MeCN)] und [Re4N3Cl9(PMe2Ph)6]

Synthesis and Structures of the Multinuclear Rhenium Nitrido Complexes [Re₂N₂Cl₄(PMe₂Ph)₄(MeCN)] and [Re₄N₃Cl₉(PMe₂Ph)₆] The binuclear rhenium complex [Re₂N₂Cl₄(PMe₂Ph)₄(MeCN)] ( 1 ) is obtained as a byproduct of the synthesis of [(Me₂PhP)₃(MeCN)ClReNZrCl₅] from [ReNCl₂(PMe₂Ph)₃] and [ZrCl₄(MeCN)₂] in toluene. It crystallizes as 1 · 2 toluene in the monoclinic space group P2₁/n with a = 1517.0(3); b = 1847.7(2); c = 1952.4(6) pm; β = 106.44(1)° and Z = 4. The two Re atoms are connected by an asymmetric nitrido bridge Re≡N–Re with distances Re–N of 169.9(5) and 208.7(5) pm. In course of the reaction of [ReNCl₂(PMe₂Ph)₃] with [ZrCl₄(THF)₂] in CH₂Cl₂ hydrochloric acid is formed by acting of the Lewis acid on the solvent. HCl protonates and eliminates phosphine ligands of the educt [ReNCl₂(PMe₂Ph)₃] to form the phosphonium salt [PMe₂PhH]₂[ZrCl₆] ( 2 ). It crystallizes in the monoclinic space group C2/c with a = 1536.9(3); b = 1148.8(1); c = 1402.2(3) pm, β = 100.70(2)° and Z = 4. The remaining fragments of the rhenium complex combine to yield the tetranuclear mixed valent complex [Re₄N₃Cl₉(PMe₂Ph)₆] ( 3 ), crystallizing as 3 · CH₂Cl₂ in the triclinic space group P 1 with a = 1312.9(19); b = 1661.4(2); 1897.1(2) pm; α = 78.62(1)°; β = 86.77(1)°; γ = 68.28(1)° and Z = 2. The four Re atoms occupy the corners of a tetrahedron. Its edges are formed by three nitrido and three chloro bridges. The asymmetric nitrido bridges Re≡N–Re are characterized by short distances in the range of 172(2) to 176(3) pm and long distances of 194(3) to 204(2) pm. The angles Re–N–Re are between 154(1) and 160(1)°.     

Ho2O[SiO4] und Ho2S[SiO4]: Zwei Chalkogenid‐Derivate von Holmium(III)‐ortho‐ Oxosilicat

Ho₂O[SiO₄] and Ho₂S[SiO₄]: Two Chalcogenide Derivatives of Holmium(III) ortho‐Oxosilicate Ho₂O[SiO₄] crystallizes monoclinically with the space group P2₁/c (a = 904.15(9), b = 688.93(7), c = 667.62(7) pm, β = 106.384(8)°, Z = 4) in the A‐type structure of rare‐earth(III) oxide oxosilicates. Yellow platelet‐shaped single crystals were obtained as by‐product during an experiment to synthesize Ho₃Cl[SiO₄]₂ by reacting Ho₂O₃ and SiO₂ in the ratio 4 : 6 with an excess of HoCl₃ as flux at 1000 °C for seven days in evacuated silica ampoules. Both crystallographically different Ho³⁺ cations show coordination numbers of 8+1 and 7 with coordination figures of 2+1‐fold capped trigonal prisms and octahedra, in which one of the vertices changes to an edge by two instead of one coordinating atoms, respectively. The O^2— anion not linked to silicon is surrounded tetrahedrally by four Ho³⁺ cations which built a layer parallel (100) by vertex‐ and edge‐sharing of the [OHo₄]¹⁰⁺ units according to {[(O5)(Ho1)_1/1(Ho2)_3/3]⁴⁺}. Within rhombic meshes of these layers the isolated oxosilicate tetrahedra [SiO₄]^4— come to lie. Ho₂S[SiO₄] crystallizes orthorhombically in the space group Pbcm (a = 605.87(5), b = 690.41(6), c = 1064.95(9) pm, Z = 4). It also emerged as a single‐crystalline by‐product obtained during the synthesis of Ho₂OS₂ by reaction of a mixture of Ho₂O₃, Ho and S with the wall of the evacuated silica tube used as container with an excess of CsCl as flux at 800 °C. The structure of the yellow platelet‐shaped, air and water resistant crystals also distinguishes two Ho³⁺ cations with bicapped trigonal prisms and trigondodecahedra as coordination polyhedra for CN = 8. The S^2— anions are almost square planar surrounded by four Ho³⁺ cations, but situated completely outside this plane. The [SHo₄]¹⁰⁺ squares form strongly corrugated layers perpendicular to [100] by corner‐sharing according to {[(S)(Ho1)_2/2(Ho2)_2/2]⁴⁺}. Contrary to the oxide oxosilicates the isolated oxosilicate tetrahedra [SiO₄]^4— do not lie within the rhombic meshes of these layers, but above and below the (Ho2)³⁺ cations while viewing along [100].     

Das unterschiedliche Reaktionsverhalten von basefreiem Tris(trimethylsilyl)methyl‐Lithium gegenüber den Trihalogeniden der Erdmetalle und des Eisens

The Variable Reaction Behaviour of Base‐free Tris(trimethylsilyl)methyl Lithium with Trihalogenides of Earth‐Metals and Iron Base‐free tris(trimethylsilyl)methyl Lithium, Tsi–Li, reacts with the earth‐metal trihalogenides (MHal₃ with M = Al, Ga, In and Hal = Cl, Br, I) primarily to give the metallates [Tsi–MHal₃]Li. Simultaneous to this simple metathesis a methylation also takes place, mainly with heavier halogenides of Ga and In with excess Tsi–Li, forming the mono and dimethyl compounds Tsi–M(Me)Hal (M = Ga, In; Hal = I), Tsi–MMe₂ (M = Ga), and the bis(trisyl)derivative (Tsi)₂InMe, respectively and the main by‐product 1,3‐disilacyclobutane. Representatives of each type of compound have been isolated by fractionating crystallizations or sublimations and characterized by spectroscopic methods (¹H, ¹³C, ²⁹Si NMR, IR, Raman) and X‐ray elucidations. Reduction takes place, when FeCl₃ reacts with Tsi–Li (1 : 3 ratio) in toluene at 55–60 °C, yielding red‐violet Fe(Tsi)₂, 1,1,1‐tris(trimethylsilyl)‐2‐phenyl ethane and low amounts of Tsi–Cl. Fe(Tsi)₂ is monomeric, crystallizes in the monoclinic space group C2/c and consists of a linear C–Fe–C skeleton with d(Fe–C) of 204,5(4) pm.     

Zwei Chloridsilicate des Yttriums: Y3Cl[SiO4]2 und Y6Cl10[Si4O12]

Two Chloride Silicates of Yttrium: Y₃Cl[SiO₄]₂ and Y₆Cl₁₀[Si₄O₁₂] The chloride‐poor yttrium(III) chloride silicate Y₃Cl[SiO₄]₂ crystallizes orthorhombically (a = 685.84(4), b = 1775.23(14), c = 618.65(4) pm; Z = 4) in space group Pnma. Single crystals are obtained by the reaction of Y₂O₃, YCl₃ and SiO₂ in the stoichiometric ratio 4 : 1 : 6 with ten times the molar amount of YCl₃ as flux in evacuated silica tubes (7 d, 1000 °C) as colorless, strongly light‐reflecting platelets, insensitive to air and water. The crystal structure contains isolated orthosilicate units [SiO₄]^4– and comprises cationic layers {(Y2)Cl}²⁺ which are alternatingly piled parallel (010) with anionic double layers {(Y1)₂[SiO₄]₂}^2–. Both crystallographic different Y³⁺ cations exhibit coordination numbers of eight. Y1 is surrounded by one Cl^– and 7 O^2– anions as a distorted trigonal dodecahedron, whereas the coordination polyhedra around Y2 show the shape of bicapped trigonal prisms consisting of 2 Cl^– and 6 O^2– anions. The chloride‐rich chloride silicate Y₆Cl₁₀[Si₄O₁₂] crystallizes monoclinically (a = 1061,46(8), b = 1030,91(6), c = 1156,15(9) pm, β = 103,279(8)°; Z = 2) in space group C2/m. By the reaction of Y₂O₃, YCl₃ and SiO₂ in 2 : 5 : 6‐molar ratio with the double amount of YCl₃ as flux in evacuated silica tubes (7 d, 850 °C), colorless, air‐ and water‐resistant, brittle single crystals emerge as pseudo‐octagonal columns. Here also a layered structure parallel (001) with distinguished cationic double‐layers {(Y2)₅Cl₉}⁶⁺ and anionic layers {(Y1)Cl[Si₄O₁₂]}^6– is present. The latter ones contain discrete cyclo‐tetrasilicate units [Si₄O₁₂]^8– of four cyclically corner‐linked [SiO₄] tetrahedra in all‐ecliptical arrangement. The coordination sphere around (Y1)³⁺ (CN = 8) has the shape of a slightly distorted hexagonal bipyramid comprising 2 Cl^– and 6 O^2– anions. The 5 Cl^– and 2 O^2– anions building the coordination polyhedra around (Y2)³⁺ (CN = 7) form a strongly distorted pentagonal bipyramid.     

Zum Komplexbildungsverhalten der 5,6-Dihydroxy-7-oxa-bicyclo[2.2.1]heptan-2,3-dicarbonsäure gegenüber 3 d-Übergangsmetallen

Complex Formation of 5,6-Dihydroxy-7-oxa-bicyclo[2.2.1]heptane-2,3-dicarboxylic Acid with 3 d-Transition Elements Binary carboxylate complexes of bivalent 3 d-transition metal ions with 5-exo,6-cis-dihydroxy-7-oxabicyclo[2.2.1]heptane-2-exo,3-cis-dicarboxylic acid ( 2 ) have been synthesized in aqueous solution and characterized by elementary analysis, infrared and electronic spectra and magnetic susceptibility measurements. The coordination compounds have been found to undergo thermal decomposition with loss of water molecules, followed by the organic ligand to give metal oxides. The stability constants of the complexes have been determined by potentiometric measurements. It could be shown by X-ray analysis, that the dicarboxylate anion of 2 has different coordination behaviour in complexes [NiL²(H₂O)₃] · H₂O ( 2 c ) and [CuL²(H₂O)₂] · 2 H₂O ( 2 d ), respectively. In 2 c it acts as a tridentate chelating ligand forming together with three water molecules an only slightly distorted octahedral coordination sphere and its hydroxyl groups are coordinatively inactive. In 2 d , however, the oxygen atom of one hydroxyl group is included in coordination and by its interaction with a Cu atom of a neighboring molecule a polymeric chain structure is built up in the crystal. Two corners of the tetragonally extended coordination octahedron are occupied by water molecules. In both complexes the molecular packing is stabilized by a network of hydrogen bonds in which also the crystal water molecules are included.     

RbFe[BP2O8(OH)]: Ein neues Borophosphat mit offen-verzweigten Vierer-Einfach-Tetraederketten

RbFe[BP₂O₈(OH)]: A New Borophosphate Containing Open-Branched Tetrahedral Vierer-Einfach Chains RbFe[BP₂O₈(OH)] is formed under mild hydrothermal conditions (T = 165–170 °C) from a mixture of RbOH_(aq), FeCl₂ · 4 H₂O, H₃BO₃ and H₃PO₄. The crystal structure of the monoclinic compound was solved by x-ray single crystal methods (space group P2₁/c, No. 14): a = 935.8(5) pm, b = 833.9(6) pm, c = 965.6(5) pm; β = 101.69(4)°; Z = 4. The anionic partial structure contains open-branched vierer-einfach chains [BP₂O₈(OH)]^4–, which are formed by alternating borate and phosphate tetrahedra sharing common corners. Fe³⁺ is in an octahedral coordination (FeO₅(OH)), while Rb⁺ is irregularly coordinated by ten oxygen-functions of neighbouring tetrahedra.     

Iodoplumbate mit polymeren Anionen – Synthese und Kristallstrukturen von [Na3(OCMe2)12][Pb4I11(OCMe2)], (Ph4P)2[Pb5I12] und (Ph4P)4[Pb15I34(dmf)6]

Iodoplumbates with Polymeric Anions – Synthesis and Crystal Structures of [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)], (Ph₄P)₂[Pb₅I₁₂], and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] Reactions of PbI₂ with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 , (Ph₄P)₂[Pb₅I₁₂] 4 and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 contain one-dimensional infinite anionic chains of face- or edge-sharing PbI₆ or PbI₅L (L = acetone, DMF) octahedra. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 : Space group P1 (No. 1), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, α = 74.64(4), β = 70.40(4), γ = 85.24(4)°, V = 2071(2) · 10⁶ pm³; (Ph₄P)₂[Pb₅I₁₂] 4 : Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, β = 96.240(13)°, V = 6885(2) · 10⁶ pm³; (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 : Space group P2₁/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4) pm, β = 114.432(13)°, V = 9678(3) · 10⁶ pm³.     

Von kleinen Bausteinen zu neuen Poly‐alkoxo‐oxometallat‐Derivaten: Synthese und Strukturaufklärung von K4[VIV12O12(OCH3)16(C4O4)6], Cs10[VIV24O24(OCH3)32(C4O4)12][VIV8O8(OCH3)16(C2O4)] und M2[VIV8O8(OCH3)16(VIVOF4)] (M = [N(nBu)4] bzw. [NEt4])

>From Small Fragments to New Poly‐alkoxo‐oxo‐metalate Derivatives: Syntheses and Crystal Structures of K₄[V^IV₁₂O₁₂(OCH₃)₁₆(C₄O₄)₆], Cs₁₀[V^IV₂₄O₂₄(OCH₃)₃₂(C₄O₄)₁₂][V^IV₈O₈(OCH₃)₁₆(C₂O₄)], and M₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] (M = [N(nBu)₄] or [NEt₄]) By solvothermal reaction of ortho‐vanadicacid ester [VO(OMe)₃] with squaric acid and potassium or caesium hydroxide the compounds K₄[V^IV₁₂O₁₂(OCH₃)₁₆(C₄O₄)₆] ( 2 ) and Cs₁₀[V^IV₂₄O₂₄(OCH₃)₃₂(C₄O₄)₁₂][V^IV₈O₈(OCH₃)₁₆(C₂O₄)] ( 3 ) could be syntesized. With tetra‐n‐butyl‐ or tetra‐n‐ethylammonium fluoride [N(nBu)₄]₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] ( 4 ) and [N(Et)₄]₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] ( 5 ) could be isolated. In 2 and 3 the corners of a tetrahedron or cube resp. are occupied by {(VO)₃(OMe)₄} groups and connected along the edges of the tetrahedron resp. cube by six or twelve resp. squarato‐groups. The octanuclear anions in the compounds 3 , 4 , and 5 are assumedly built up by fragments of the ortho‐vanadicacid ester [VO(OMe)₃]. Around the anions C₂O₄^2— or VOF₄^— these oligormeric chains are closed to a ring . Crystal data: 2 , tetragonal, P4₃, a = 18.166(3)Å, c = 29.165(7)Å, V = 9625(3)ų, Z = 4, d_c = 1.469 gcm^—3; 3 , orthorhombic, Pbca, a = 29.493(5)Å, b = 25.564(4)Å, c = 31.076Å, V = 23430(6)ų, Z = 4, d_c = 1.892 gcm^—3; 4 , monoclinic, P2₁/n, a = 9.528(1)Å, b = 23.021(2)Å, c = 19.303(2)Å, β = 92.570(2)°, V = 4229.8(5)ų, Z = 2, d_c = 1.391 gcm^—3; 5 , monoclinic, P2₁/n, a = 16.451(2)Å, b = 8.806(1)Å, c = 23.812(1)Å, β = 102.423(2)°, V = 3368.7(6)ų, Z = 2, d_c = 1.534 gcm^—3.     

LuF[SeO3] und LuCl[SeO3]: Zwei nicht‐isotype Halogenid‐Oxoselenate(IV) des Lutetiums

LuF[SeO₃] and LuCl[SeO₃]: Two Non‐Isotypic Halide Oxoselenates(IV) of Lutetium Despite the formal similarity of LuF[SeO₃] and LuCl[SeO₃] both compounds show significant structural differences due to the different positions of the halide anions (X⁻) within the pentagonal bipyramids [LuO₅X₂]⁹⁻. However, both oxoselenates(IV) have these pentagonal bipyramids as basic modules in common that are connected via O²⁻ edges to chains. LuCl[SeO₃] crystallizes orthorhombically in space group Pnma (no. 62; a = 714.63(7), b = 681.76(7) and c = 864.05(9) pm; Z = 4). The structure is isotypic to that one recently presented for ErCl[SeO₃]. With a single Cl⁻ anion in each an apical and an equatorial position, the chains have to be inclined with an angle of about 54° relative to each other to get connected alternately by common Cl⁻ corners and bridging [SeO₃]²⁻ pyramids. In contrast to that, LuF[SeO₃] which crystallizes triclinically in space group (no. 2; a = 644.85(6), b = 684.41(7), c = 427.98(4) pm, α = 94.063(5), β = 96.484(5) and γ = 91.895(5)°; Z = 2) takes a structural motif already known from CsTmCl₂[SeO₃]. Owing to the apical position of both halide anions it is now possible to connect the chains directly via discrete Ψ¹‐tetrahedral [SeO₃]²⁻ groups to layers. The same layers are present in LuF[SeO₃] and without the formal alkali‐metal halide unit (CsCl) of the CsTmCl₂[SeO₃]‐type compounds, the layers can also be connected directly by common F⁻ corners to a three‐dimensional array. Torch‐sealed evacuated silica ampoules were used for the synthesis of both lutetium(III) halide oxoselenates(IV). For LuF[SeO₃] these vessels have been graphitized before to prevent them from oxosilicate‐producing side‐reactions with the applied fluoride. The synthesis of LuCl[SeO₃] required Lu₂O₃ and SeO₂ in a molar ratio of 1 : 6 with a surplus of an eutectic RbCl/LiCl mixture as fluxing agent and an annealing period of five weeks at a temperature of 500 °C, whereas Lu₂O₃, LuF₃ and SeO₂ (in a molar ratio of 1 : 1 : 3) with CsBr as flux were converted to LuF[SeO₃] at 750 °C within six days.     

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.     

Synthese und Kristallstruktur der Molybdännitrido‐Komplexe [MoNCl3(MeCN)]4 und [MoNCl2(bipy)]4

Syntheses and Crystal Structures of the Nitrido Complexes [MoNCl₃(MeCN)]₄ and [MoNCl₂(bipy)]₄ [MoNCl₃(MeCN)]₄ ( 1 ) is obtained by the reaction of MoCl₄(MeCN)₂ with Me₃SiN₃ in CH₂Cl₂ as a sparingly soluble and water sensitive red compound. It crystallizes as 1 · 3 CH₂Cl₂ in the triclinic space group P 1 with a = 889.7(1), b = 1004.8(1), c = 1270.4(2) pm; α = 71.69(1)°; β = 73.63(1)°; γ = 86.32(1)°, and Z = 1. It forms centrosymmetric tetranuclear complexes, in which the Mo atoms are connected by asymmetric and linear nitrido bridges with distances Mo–N of 167.5 and 214.3 pm. The acetonitrile molecules are coordinated with a long bond length Mo–N of 241 pm in trans position to the Mo–N triple bond. The reaction of 1 with 2,2′‐bipyridine in CH₂Cl₂/THF yields the tetranuclear molybdenum(V) complex [MoNCl₂(bipy)]₄ ( 2 ) as main product. It crystallizes in the tetragonal space group P4₂/n with a = 1637.5(2), c = 1018.3(2) pm, and Z = 2. In the tetranuclear complexes with the symmetry S₄ linear and asymmetric nitrido bridges connect the Mo atoms to form an almost planar eight membered Mo–N ring with distances Mo–N of 173 and 203 pm. The bipyridine molecules coordinate as chelates in cis and trans position to the Mo–N triple bond. In this case the trans influence causes different Mo–N distances of 219 and 232 pm.     

Die Kristallstrukturen der Hexachlorometallate NH4[SbCl6], NH4[WCl6], [K(18‐Krone‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 und (PPh4)2[WCl6]·4CH3CN

Crystal Structures of the Hexachlorometalates NH₄[SbCl₆], NH₄[WCl₆], [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ and (PPh₄)₂[WCl₆]·4CH₃CN The crystal structures of the title compounds were determined by single crystal X‐ray methods. NH₄[SbCl₆] and NH₄[WCl₆] crystallize isotypically in the space group C2/c with four formula units per unit cell. The NH₄⁺ ions occupy a twofold crystallographic axis, whereas the metal atoms of the [MCl₆]^— ions occupy a centre of inversion. There exist weak interionic hydrogen bridges. [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ crystallizes in the orthorhombic space group R3¯/m with Z = 3. The compound forms centrosymmetric ion triples, in which the potassium ions are coordinated with a WCl₃ face each. In trans‐position to it the chlorine atom of a CH₂Cl₂ molecule is coordinated so that, together with the oxygen atoms of the crown ether, coordination number 10 is achieved. (PPh₄)₂[WCl₆]·4CH₃CN crystallizes in the monoclinic space group P2₁/c with Z = 4. This compound, too, forms centrosymmetric ion triples, in which in addition the acetonitrile molecules are connected with the [WCl₆]^2— ion via weak C—H···Cl contacts.     

Über die komplexen Hydroxide des Chroms: Na9[Cr(OH)6]2(OH)3 · 6 H2O und Na4[Cr(OH)6]X · H2O (X = Cl, (S2)1/2) – Synthese,Kristallstruktur und thermisches Verhalten

Complex Hydroxides of Chromium: Na₉[Cr(OH)₆]₂(OH)₃ · 6 H₂O and Na₄[Cr(OH)₆]X · H₂O (X = Cl, (S₂)_1/2) – Synthesis, Crystal Structure, and Thermal Behaviour Green plate‐like crystals of Na₉[Cr(OH)₆]₂(OH)₃ · 6 H₂O (triclinic, P1, a = 872.9(1) pm, b = 1142.0(1) pm, c = 1166.0(1) pm, α = 74.27(1)°, β = 87.54(1)°, γ = 70.69(1)°) are obtained upon slow cooling of a hot saturated solution of Cr^III in conc. NaOH (50 wt%) at room temperature. In the presence of chloride or disulfide the reaction yields green prismatic crystals of Na₄[Cr(OH)₆]Cl · H₂O (monoclinic, C2/c, a = 1138.8(2) pm, b = 1360.4(1) pm, c = 583.20(7) pm, β = 105.9(1)°) or green elongated plates of Na₄[Cr(OH)₆](S₂)_1/2 · H₂O (monoclinic, P2₁/c, a = 580.8(1) pm, b = 1366.5(3) pm, c = 1115.0(2) pm, β = 103.71(2)°), respectively. The latter compounds crystallize in related structures. All compounds can be described as distorted cubic closest packings of the anions and the crystal water molecules with the cations occupying octahedral sites in an ordered way. The thermal decomposition of the compounds was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In all cases the final decomposition product is NaCrO₂.     

Die Kristallstrukturen von trans‐[NiBr2(Pyridin)4] und [Ni(HNPEt3)4]I2

Crystal Structures of trans ‐[NiBr₂(pyridine)₄] and [Ni(HNPEt₃)₄]I₂ Turquoise single crystals of trans‐[NiBr₂(pyridine)₄] have been obtained by the reaction of excess pyridine with nickel(II) bromide/diacetonealcohol. According to the crystal structure determination the nickel atom is octahedrally coordinated by the two bromine atoms in trans‐position and by the nitrogen atoms of the pyridine molecules. Space group Pna2₁, Z = 4, lattice dimensions at 20 °C: a = 1592.9(2), b = 943.8(1), c = 1413.0(2) pm, R₁ = 0.0492. Dark blue single crystals of the phosphoraneimine complex [Ni(HNPEt₃)₄]I₂ have been obtained from NiI₂/H₂O with excess Me₃SiNPEt₃ and subsequent recrystallization from acetonitrile. According to the crystal structure determination the nickel atom is tetrahedrally coordinated by the nitrogen atoms of the HNPEt₃ molecules. The iodide ions are connected via N–H…I contacts with the cation to form an ion triple. Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1934.9(2), b = 1078.3(1), c = 1966.3(2) pm, β = 111.040(8)°; R₁ = 0.043.