Die KristallStrukturen von K6[Ge2Te6] und K6[Sn2Te6] und ihre kristall-chemische Beziehung zum K6[Si2Te6]-Typ

Crystal Structures of K₆[Ge₂Te₆] and K₆[Sn₂Te₆] and their Relations to the K₆[Si₂Te₆] Type K₆[Ge₂Te₆] and K₆[Sn₂Te₆], the first members of the families of telluro-digermanates and telluro-distannates have been prepared and their structures determined. The space group is C 2/c with cell constants a = 16.010(8), b = 13.619(8), c = 9.713(5) Å, β = 95.19(5)° and Z = 4 for the Ge compound. The Sn compound has space group P 2₁/c, a = 9.590(5), b = 13.654(8), c = 9.606(5) Å, β = 116.84(5) and Z = 2. The structures were established by direct methods, using four-circle diffractometer data. The final R value for 828 (1677) independent reflexions is 0.068 (0.047) for the Ge (Sn) compound. Both structures have discrete X₂Te₆ groups (X = Ge, Sn) in staggered conformation connected by K atoms in distorted octahedral or trigonal prismatic environments and bear direct subgroup relationships to that of K₆[Si₂Te₆]. The average X? Te distance is 2.579 (2.724) Å and the X? X distance 2.492 (2.814) Å.     

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.     

Stannylierungsexperimente mit NH-funktionellen Aminoiminophosphoranen. Synthese und Struktur der tricyclischen Stannaphosphazene [Me2Sn(tBu2PN)NH]2 und [nBu2Sn(Ph2PN)2NH]2

Stannylation Experiments with NH-functional Aminoiminophosphoranes. Synthesis and Structure of the Tricyclic Stannaphosphazenes [Me₂Sn(^tBu₂PN)NH]₂ and [ⁿBu₂Sn(Ph₂PN)₂NH]₂ Aminoiminophosphoranes ^tBu₂P(NH)NH₂ ( 1 ) and (H₂NPPh₂)N(Ph₂PNH) ( 2 ) react with diaminostannanes R₂Sn(NEt₂)₂ by cyclocondensation to give cyclostannaphosphazenes [Me₂Sn(^tBu₂PN)NH]₂ ( 3 ) and [R₂Sn(Ph₂PN)₂NH]₂ ( 4 a , b ) ( a : R = Me, b : R = ⁿBu). With 2 and Me₃SnNEt₂ the ring compound Me₂Sn(Ph₂PN)₂NSnMe₃ ( 5 ) besides Me₄Sn is formed by per-N-stannylation and Sn-methyl group transfer. The crystal structures of 3 and 4 b were determined by X-ray structure analysis. 3 forms a planar heterotricyclus containing three four-membered rings with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1). 4 b consists of a tricyclic molecule with two puckered six-membered rings and one planar four membered tin-nitrogen ring with two pentacoordinated tin atoms (space group P 1 (No. 2); Z = 1).     

Synthesen und Charakterisierung von [Ni(tBuAs)6] und [Pd(tBuAs)6]

Syntheses and Characterization of [Ni(tBuAs)₆] and [Pd(tBuAs)₆] The reduction of tBuAsCl₂ with magnesium in the presence of NiCl₂ or PdCl₂ yields the complexes [Ni(tBuAs)₆] ( 2 ) and [Pd(tBuAs)₆] ( 3 ). The structure of ( 2 ) was determined by X-ray single crystal structure analysis. ( 2 ) consists of the sixmembered ring (tBuAs)₆ in chair conformation with the nickel atom in the center of this ring.     

[Cd(Sn9)2]6− and [Cd(Ni@Sn9)2]6−: Reactivity and coordination chemistry of empty and Ni-centered [Sn9]4− Zintl ions

To investigate the reactivity of homoatomic clusters [E₉]^4? (E = Si-Pb) and intermetalloid clusters [M@E₉]^q?, the reactions of the Zintl anions [Sn₉]^4? and [Ni@Sn₉]^4? with the CdMes₂ (Mes = Mesitylene) in the presence of 2.2.2-crypt were carried out. Two new compounds [K(2.2.2-crypt)]₆[(Sn₉)Cd(Sn₉)]·en (1) and [K(2.2.2-crypt)]₆[(Ni@Sn₉)Cd(Ni@Sn₉)]·en (2) were afforded. Both 1 and 2 were characterized by single-crystal X-ray diffraction, energy dispersive X-ray (EDX), and electrospray ionization mass spectrometry (ESI-MS), and can be viewed as two [Sn₉]^4? or [Ni@Sn₉]^4? subunits bridged by Cd ion in an η³:η³ coordination mode. Quantum chemical calculations reveal the relationships between the geometries and electronic structures of clusters 2a, [Ni₃Ge₁₈]^4? and [Cu₄@Sn₁₈]^4?. Further electron localization technique (AdNDP method) was performed to explain chemical bonding patterns of 1a.     

Über Sn[OCH(CF3)2]2 und Sn (OCH2CF3)2 (n = 1, 2)

On S_n[OCH(CF₃)₂]₂ and S_n(OCH₂CF₃)₂ (n = 1, 2) The sulfoxylates S[OCH(R)CF₃]₂, 1 and 2 and the disulfides S₂[OCH(R)CF₃]₂, 5 and 6 (R = CF₃, H) are obtained by reacting SCl₂ or S₂Cl₂, respectively, and the lithium alcoxides LiOCH(R)CF₃. Chlorine and compound 2 give ClS(O)OCH₂F₃ and CF₃CH₂Cl, whereas the sulfur-sulfur bound is cleaved in 5 and 6 furnishing SCI₂, 1 and 2 , respectively. The ¹⁹F n.m.r. spectrum of 5 and the ¹H n.m.r. spectrum of 6 are interpreted in terms of hindered rotation about the sulfur-sulfur axis.     

Alkoxo‐Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe2(OtBu)6], [Fe2Cl2(OtBu)4], [Fe2Cl4(OtBu)2] und [N(nBu)4]2[Fe6OCl6(OMe)12]

Alkoxo Compounds of Iron(III): Syntheses and Characterization of [Fe₂(OtBu)₆], [Fe₂Cl₂(OtBu)₄], [Fe₂Cl₄(OtBu)₂] and [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] The reaction of iron(III)chloride in diethylether with sodium tert‐butylat yielded the homoleptic dimeric tert‐‐butoxide Fe₂(OtBu)₆ ( 1 ). The chloro‐derivatives [Fe₂Cl₂(OtBu)₄] ( 2 ), and [Fe₂Cl₄(OtBu)₂] ( 3 ) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1 , 2 , and 3 consists of two edge‐sharing tetrahedrons, with two tert‐butoxo‐groups as μ₂‐bridging ligands. For the synthesis of the alkoxides 1 , 2 , and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl₃(OEt₂)₂ ( 4 ) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo‐chloro‐oxo‐hexairon cluster [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] ( 5 ). Crystal structure data: 1 , triclinic, P1¯, a = 9.882(2) Å, b = 10.523(2) Å, c = 15.972(3) Å, α = 73.986(4)°, β = 88.713(4)°, γ = 87.145(4)°, V = 1594.4(5) ų, Z = 2, d_c = 1.146 gcm^—1, R₁ = 0.044; 2 , monoclinic, P2₁/n, a = 11.134(2) Å, b = 10.141(2) Å, c = 12.152(2) Å und β = 114.157(3)°, V = 1251.8(4) ų, Z = 2, d_c = 1.377 gcm^—1, R₁ = 0.0581; 3 , monoclinic, P2₁/n, a = 6.527(2) Å, b = 11.744(2) Å, c = 10.623(2), β = 96.644(3)°, V = 808.8(2) ų, Z = 2, d_c = 1.641 gcm^—1, R₁ = 0.0174; 4 , orthorhombic, Iba2, a = 23.266(5) Å, b = 9.541(2) Å, c = 12.867(3) Å, V = 2856(2) ų, Z = 8, d_c = 1.444 gcm^—1, R₁ = 0.0208; 5 , trigonal, P3₁, a = 13.945(2) Å, c = 30.011(6) Å, V = 5054(2) ų, Z = 6, d_c = 1.401 gcm^—1; R_c = 0.0494.     

Hydroxoverbindungen. 10. Über die Natriumoxohydroxostannate(II) Na4[Sn4O(OH)10] und Na2[Sn2O(OH)4]

Hydroxo Compounds. 10. The Sodium Oxohydroxostannates(II) Na₄[Sn₄O(OH)₁₀] and Na₂[Sn₂O(OH)₄] Na₄[Sn₄O(OH)₁₀] = Na₄[Sn(OH)₃]₂[Sn₂O(OH)₄] ( I ) and Na₂[Sn₂O(OH)₄] ( II ) have now been doubtlessly characterized as the first Na-hydroxostannates(II). I crystallizes monoclinic in P2₁/n (a = 1522.4(5) pm, b = 830.0(2) pm, c = 1276.0(3) pm, β = 104.8(2)°, Z = 4, R = 0.047, 1137 I_hkl); II crystallizes orthorhombic in P2₁2₁2₁ (a = 1450(2) pm, b = 1665(2) pm, c = 590.7(8) pm, Z = 8, R = 0.042, 1208 I_hkl). II is identical with the compound which was described up to now as “Na[Sn(OH)₃]”. The new compounds contain the complex anions [Sn(OH)₃]^? and [Sn₂O(OH)₄]^2?, whose structures are now proved. The oxotetrahydroxo-distannate(II) anion [Sn₂O(OH)₄]^2? exhibits a syn-conformation with respect to the projection along the (Sn? Sn) vector. The two compounds crystallize with pronounced layer structures, which show direct topotactical relations with one another as well as with SnO. This relates closely to the fast formation of SnO from crystals of I and II .     

Neubestimmung der Kristallstrukturen der Hexahydroxometallate Na2Sn(OH)6, K2Sn(OH)6 und K2Pb(OH)6

Redetermination of the Crystal Structures of the Hexahydroxometallates Na₂Sn(OH)₆, K₂Sn(OH)₆, and K₂Pb(OH)₆ Slow cooling down of hot saturated hydroxo stannate‐ resp. ‐plumbate solutions gives crystals of Na₂Sn(OH)₆, K₂Sn(OH)₆, and K₂Pb(OH)₆ well suited for an X‐ray structure determination. With these crystals the so far known crystal data were verified, determined more precisely and H‐positions found for the first time. The compounds crystallize rhombohedral in the space group R 3. The hexagonal unit cells contain three formula units with Na₂Sn(OH)₆: a = 5.951(1) Å, c = 14.191(2) Å, c/a = 2.384 K₂Sn(OH)₆: a = 6.541(1) Å, c = 12.813(4) Å, c/a = 1.959 K₂Pb(OH)₆: a = 6.625(1) Å, c = 12.998(2) Å, c/a = 1.962 The compounds are not isotypic whereas the atoms occupy in all three cases the same Wyckoff positions. Na₂Sn(OH)₆ has with an hcp packing of O a CdI₂ like superstructure with Na and Sn in octahedral interstices. Hydrogen bonds O–H…O–H play a role in solid K₂Sn(OH)₆ and K₂Pb(OH)₆. In these compounds the potassium ions are shifted from an octahedral coordination in an hcp packing of O. They have nine nearest O‐neighbours. The hydrogen bonds are investigated by Raman spectroscopy.     

Darstellung und Kristallstruktur von K6[Al2O6] und Rb6[Al2O6]

Preparation of Crystal Structure of K₆[Al₂O₆] and Rb₆[Al₂O₆] Colourless single crystals of K₆[Al₂O₆] have been prepared from intimate mixtures of KAlO₂ and K₂O (550°C, 90 d). The structure determination from four-circle diffractometer data (MoKα , 742 I_o(hkl), R = 2.2%, R_w = 2.1%) confirms the space group C2/m with Z = 2; a = 698.25 pm, b = 1 103.54 pm, c = 646.49 pm, β = 102.49°. Colourless single crystals of hitherto unknown Rb₆[Al₂O₆] have been prepared from intimate mixtures of RbAlO₂ and Rb₂O (520°C, 120 d). The structure determination from four-circle diffractometer data (MoKα , 1 240 I_o(hkl)) results in the residual values R = 7.2%, R_w = 4.9%; space group C2/m; a = 725.92 pm, b = 1 143.33 pm, c = 678.06 pm, β = 104.05°; Z = 2. K₆[Al₂O₆] and Rb₆[Al₂O₆] are isostructural with K₆[Fe₂O₆]. A characteristic structure unit is the anion [Al₂O₆]^6? consisting of two edge-sharing [AlO₄] tetrahedra. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), the Madelung Part of Lattice Energy (MAPLE) and the Charge Distribution (CHARDI) are calculated and discussed.     

Die Struktur der Hydrate von Co3[Co(CN)6]2 und Cd3[Co(CN)6]2

The crystal structures of Co₃[Co(CN)₆]₂, 12 H₂O (a, = 10.210 ± 0.005 Å) and Cd₃[Co(CN)₆]₂, 12 H₂O (a = 10.590 ± 0.005 Å) have been determined by X-ray powder methods. According to the measured density the unit cell contains 1 1/3 formula units with 4 Co²⁺ (Cd²⁺) in 4a, 2 2/3 Co³⁺ in 4b, 16 C and 16 N in 24e, 8 H₂O_I near 24e, (96k) and 8 H₂O_II near 8 _c (192 l). Structure factor calculations based on the space group O_h⁵ - F m 3 m lead to the following final values of the reliability index R: 0.038 (Co₃[Co(CN)₆]₂, 12 H₂O) and 0.037 (Cd₃[Co(CN)₆]₂, 12 H₂O). The interatomic distances for the cobaltous compound (in parentheses for the cadmium compound) are: Co³⁺-C: 1.88 Å (1.89); C-N: 1.15 Å (1.17); Co²⁺-N: 2.08 Å (2.24); Co²⁺-O_I: 2.10 Å (2.27); shortest O_I-H-O_II-bonds: 2.89 Å (2.82). Co³⁺ is octahedrally coordinated by six carbon atoms, the divalent metal ion by four nitrogen atoms and two water molecules. The two different metal ions are connected by M²⁺-N-C-Co³-bonds to a threedimensional network. The infrared and electronic spectra are shown to be in agreement with the results of the structure analyses of these compounds. The observed positions of the OH-stretching vibrations lead to a hydrogenbond-length of 2.8–2.95 Å.     

Isotype Strukturen einiger Hexaamminmetall(II)-halogenide von 3d-Metallen: [V(NH3)6]I2, [Cr(NH3)6]I2, [Mn(NH3)6]Cl2, [Fe(NH3)6]Cl2, [Fe(NH3)6]Br2, [Co(NH3)6]Br2 und [Ni(NH3)6]Cl2

The Structures of some Hexaammine Metal(II) Halides of 3 d Metals: [V(NH₃)₆]I₂, [Cr(NH₃)₆]I₂, [Mn(NH₃)₆]Cl₂, [Fe(NH₃)₆]Cl₂, [Fe(NH₃)₆]Br₂, [Co(NH₃)₆]Br₂ and [Ni(NH₃)₆]Cl₂ Crystals of yellow [V(NH₃)₆]I₂ and green [Cr(NH₃)₆]I₂ were obtained by the reaction of VI₂ and CrI₂ with liquid ammonia at room temperature. Colourless crystals of [Mn(NH₃)₆]Cl₂ were obtained from Mn and NH₄Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH₃)₆]Cl₂ and [Fe(NH₃)₆]Br₂ were obtained by the reaction of FeCl₂ and FeBr₂ with supercritical ammonia at 400°C. Under the same conditions orange crystals of [Co(NH₃)₆]Br₂ were obtained from [Co₂(NH₂)₃(NH₃)₆]Br₃. Purple crystals of [Ni(NH₃)₆]Cl₂ were obtained by the reaction of NiCl₂ · 6H₂O and NH₄Cl with aqueous NH₃ solution. The structures of the isotypic compounds (Fm3 m, Z = 4) were determined from single crystal diffractometer data (see “Inhaltsübersicht”). All compounds crystallize in the K₂[PtCl₆] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.     

Synthese und Kristallstrukturen von [Ti(NPh2)4] und [Ti2(μ-O)(NPh2)6]

Crystal Structures of [Ti(NPh₂)₄] and [Ti₂(μ-O)(NPh₂)₆] [Ti(NPh₂)₄] has been prepared from TiCl₃(THF)₃ and LiNPh₂, the μ-oxo complex [Ti₂(μ-O)(NPh₂)₆] results from partial hydrolysis of [Ti(NPh₂)₄] in toluene solution. Both complexes are characterized by crystal structure determinations. In [Ti(NPh₂)₄] the titanium atom is coordinated by the four nitrogen atoms in a distorted tetrahedral fashion with Ti–N bond lengths of 193.8 pm in average. In [Ti₂(μ₂-O)(NPh₂)₆] the μ-oxo ligand forms a linear symmetric TiOTi bridge with rTiO = 181.2 pm and TiN = 193.4 pm in average.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Synthese und Strukturen der selenolatoverbrückten Quecksilbercluster [Hg6(SePh)12(PtBu3)2] und (HPtBu3)2[Hg6(SePh)14]

Synthesis and Structures of the Selenolato-Bridged Mercury Clusters [Hg₆(SePh)₁₂(P t Bu₃)₂] and (HP t Bu₃)₂[Hg₆(SePh)₁₄] The reaction of HgCl₂ with PtBu₃ and PhSeSiMe₃ yields [Hg₆(SePh)₁₂(PtBu₃)₂] ( 1 ) and (HPtBu₃)₂[Hg₆(SePh)₁₄] ( 2 ). X-ray structural analysis of the compounds shows them to have similar Hg–Se cages with distorted tetrahedral coordination around mercury. The cages are built up from edge- and vertex-sharing distorted tetrahedra.     

Halogenomercurate: Darstellung und Strukturen von [Cu(en)2][Hg2Cl6], [Cu(en)2][Hg2Br6] und [Cu(en)2][HgBr4]

Halomercurates: Syntheses and Crystal Structures of [Cu(en)₂][Hg₂Cl₆], [Cu(en)₂][Hg₂Br₆], and [Cu(en)₂][HgBr₄] Crystals of [Cu(en)₂][Hg₂Cl₆] ( 1 ) have been obtained by layering a solution of Hg(NO₃)₂ and NaCl with a solution of [Cu(en)₂]SO₄. An analogous procedure, using NaBr instead of NaCl, gave crystals of [Cu(en)₂][HgBr₄] ( 3 ). Crystals of [Cu(en)₂][Hg₂Br₆] ( 2 ) were obtained by gel crystallization using the same starting materials as for 3 . The complexes show very low solubility. The dinuclear anions of 1 consist of two nearly planar HgCl₃ units related by a center of symmetry. In 2 infinite anionic chains are present, made up of parallel HgBr₃ units. These units are packed in such a way as to produce a trigonal bipyramidal configuration around the Hg atoms. 3 contains mononuclear deformed tetrahedral [HgBr₄]^2– anions. In all three complexes the packing of the ions is such that halogen atoms of halomercurate anions complete a tetragonal bipyramidal coordination at Cu. The resulting Cu–Halogen distances are 2.924 Å for 1 , 3.036 Å for 2 and 3.085 and 3.119 Å for 3 . 1 : Space group P 1, Z = 1, lattice constants at 20 °C: a = 7.000(2), b = 7.526(2), c = 8.239(2) Å; α = 88.39(2), β = 86.06(2), γ = 86.10(3)°; R₁ = 0.040. 2 : Space group P2₁/c, Z = 2, lattice constants at –50 °C: a = 7.185(1), b = 16.338(2), c = 7.814(1) Å; β = 94.88(2)°; R₁ = 0.033. 3 : Space group P2₁/n, Z = 4, lattice constants at 20 °C: a = 8.055(3), b = 13.101(3), c = 13.814(3) Å; β = 91.24(3)°; R₁ = 0.092.