Synthese und Kristallstrukturen der Seltenerd-Komplexe [LaI2(THF)5]+I3−, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]−, [ErCl3(DME)2] und [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]−

Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI₂(THF)₅]⁺I₃^?, [SmCl₃(THF)₄], [ErCl₂(THF)₅]⁺ [ErCl₄(THF)₂]^?, [ErCl₃(DME)₂], and [Na(18-Crown-6)(THF)₂]⁺[YbBr₄(THF)₂]^? [LaI₂(THF)₅]⁺I₃^? ( 1 ) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at ?83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way. [SmCl₃(THF)₄] ( 2 ) originates as colourless crystals on heating SmCl₃ with excess THF in the presence of Me₃SiNPEt₃. Space group P2₁/c, Z = 8, lattice dimensions at ?50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way. [ErCl₂(THF)₅]⁺[ErCl₄(THF)₂]^? ( 3 ). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at ?50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom. [ErC1₃(DME)₂] ( 4 ) originates as pink single crystals from ₃ with excess boiling 1,2-dimethoxyethane. Space group P2₁/c, Z = 4, lattice dimensions at ?50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions. [Na(18-Krone-6)(THF)₂]⁺ [YbBr₄(THF)₂]^? ( 5 ) is formed as by-product by the reaction of YbBr₃ with NaN(SiMe₃)₂ in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1 , Z = 1, lattice dimensions at ?70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr₄(THF)₂]^?ions, in which the THF molecules are arranged in trans-position.     

Orthorhombic HP‐REOF (RE = Pr,Nd, Sm – Gd) – High‐Pressure Syntheses and Single‐Crystal Structures (RE = Nd,Sm, Eu)

High‐pressure modifications of the rare earth oxide fluorides REOF (RE = Pr, Nd, Sm – Gd) were successfully synthesized under conditions of 11 GPa and 1200 °C applying the multianvil high‐pressure/high‐temperature technique. Single crystals of HP‐REOF (RE = Nd, Sm, Eu) were obtained making it possible to analyze the products by means of single‐crystal X‐ray diffraction. The compounds HP‐REOF (RE = Nd, Sm, Eu) crystallize in the orthorhombic α‐PbCl₂‐type structure (space group Pnma, No. 62, Z = 4) with the parameters a = 632.45(3), b = 381.87(2), c = 699.21(3) pm, V = 0.16887(2) nm³, R₁ = 0.0156, and wR₂ = 0.0382 for HP‐NdOF, a = 624.38(3), b = 376.87(2), c = 689.53(4) pm, V = 0.16225(2) nm³, R₁ = 0.0141, and wR₂ = 0.0323 for HP‐SmOF, and a = 620.02(4), b = 374.24(3), c = 686.82(5) pm, V = 0.15937(2) nm³, R₁ = 0.0177, and wR₂ = 0.0288 for HP‐EuOF. Calculations of the bond valence sums clearly showed that the oxygen atoms occupy the tetrahedrally coordinated position, whereas the fluorine atoms are fivefold coordinated in form of distorted square‐pyramids. The crystal structures and properties of HP‐REOF (RE = Nd, Sm, Eu) are discussed and compared to the isostructural phases and the normal‐pressure modifications of REOF (RE = Nd, Sm, Eu). Furthermore, results of investigations by EDX and Raman measurements including quantum mechanical calculations are presented.     

Syntheses and Crystal Structures of the Cyclotriphosphate Hydrates Nd(P3O9)·3H2O,Nd(P3O9)·4.5H2O,RE(P3O9)·5H2O (RE = Pr,Nd), and Na3RE(P3O9)2·6H2O (RE = Pr,Nd)

Several rare‐earth cyclotriphosphate hydrates were obtained from mixtures of sodium cyclotriphosphates and the respective rare‐earth chlorides. Nd(P₃O₉) · 3H₂O [P$\bar{6}$ , Z = 3, a = 677.90(9), c = 608.67(9) pm, R₁ = 0.016, wR₂ = 0.038, 312 data, 36 parameters] was obtained by a solid state reaction and is isotypic with respective rare‐earth phosphate hydrates, while all the others adopt new structure types. Nd(P₃O₉) · 4.5H₂O [C2/c, Z = 8, a = 1644.6(3), b = 756.11(15), c = 1856.1(4) pm, β = 97.25(3)°, R₁ = 0.032, wR₂ = 0.081, 1763 data, 194 parameters], Nd(P₃O₉) · 5H₂O [P2₁/c, Z = 4, a = 773.75(15), b = 1149.1(2), c = 1394.9(3) pm, β = 106.07(3)°, R₁ = 0.042, wR₂ = 0.082, 1338 data, 194 parameters], Pr(P₃O₉) · 5H₂O [P$\bar{1}$ , Z = 2, a = 745.64(15), b = 889.07(18), c = 934.55(19) pm, α = 79.00(3), β = 80.25(3), γ = 66.48(3), R₁ = 0.059, wR2 = 0.089, 1468 data, 193 parameters], Na₃Nd(P₃O₉)₂ · 6H₂O [P2₁/n, Z = 4, a = 1059.78(18), b = 1207.25(15), c = 1645.7(4) pm, β = 99.742(17), R₁ = 0.047, wR₂ = 0.119, 1109 data, 351 parameters] and Na₃Pr(P₃O₉)₂ · 6H₂O [P2₁/n, Z = 4, a = 1061.42(16), b = 1209.0(2), c = 1635.5(3) pm, β = 99.841(13), R₁ = 0.035, wR₂ = 0.062, 1323 data, 350 parameters] were obtained by careful crystallization at room temperature. A thorough structure discussion is given. The infrared spectrum of Nd(P₃O₉) · 4.5H₂O is also reported.     

Intermetallic Gold Compounds REAuMg (RE = Y,La–Nd,Sm, Eu,Gd–Yb)

New intermetallic rare earth compounds REAuMg (RE = Y, La–Nd, Sm, Eu, Gd–Yb) were synthesized by reaction of the elements in sealed tantalum tubes in a high‐frequency furnace. The compounds were investigated by X‐ray diffraction both on powders and single crystals. Some structures were refined on the basis of single crystal data. The compounds with Y, La–Nd, Sm, and Gd–Tm adopt the ZrNiAl type structure with space group P62m: a = 770.8(2), c = 419.5(1) pm, wR2 = 0.0269, 261 F² values for PrAuMg, a = 750.9(2), c = 407.7(1) pm, wR2 = 0.0561, 649 F² values for HoAuMg with 15 variables for each refinement. Geometrical motifs in HoAuMg are two types of gold centered trigonal prisms: [Au1Mg₃Ho₆] and [Au2Mg₆Ho₃]. The gold and magnesium atoms form a three‐dimensional [AuMg] polyanion in which the holmium atoms fill distorted hexagonal channels. The magnesium positions show a small degree of magnesium/gold mixing resulting in the refined compositions PrAu_1.012(2)Mg_0.988(2) and HoAu_1.026(3)Mg_0.974(3). EuAuMg and YbAuMg contain divalent europium and ytterbium, respectively. Both compounds crystallize with the TiNiSi type structure, space group Pnma: a = 760.6(3), b = 448.8(2), c = 875.8(2) pm, wR2 = 0.0491, 702 F² values, 22 variables for EuAuMg, and a = 738.4(1), b = 436.2(1), c = 864.6(2) pm, wR2 = 0.0442, 451 F² values, and 20 variables for YbAuMg. The europium position shows a small degree of europium/magnesium mixing, and the magnesium site a slight magnesium/gold mixing leading to the refined composition Eu_0.962(3)Au_1.012(3)Mg_1.026(3). No mixed occupancies were found in YbAuMg where all sites are fully occupied. In these structures the europium(ytterbium) and magnesium atoms form zig‐zag chains of egde‐sharing trigonal prisms which are centered by the gold atoms. As is typical for TiNiSi type compounds, also in EuAuMg and YbAuMg a three‐dimensional [AuMg] polyanion occurs in which the europium(ytterbium) atoms are embedded. The degree of distortion of the two polyanions, however, is different.     

Isotype Borophosphate MII(C2H10N2)[B2P3O12(OH)] (MII = Mg,Mn, Fe,Ni, Cu,Zn): Verbindungen mit Tetraeder‐Schichtverbänden

Isotypic Borophosphates M^II(C₂H₁₀N₂)[B₂P₃O₁₂(OH)] (M^II = Mg, Mn, Fe, Ni, Cu, Zn): Compounds containing Tetrahedral Layers The isotypic compounds M^II(C₂H₁₀N₂) · [B₂P₃O₁₂(OH)] (M^II = Mg, Mn, Fe, Ni, Cu, Zn) were prepared under hydrothermal conditions (T = 170 °C) from mixtures of the metal chloride (chloride hydrate, resp.), Ethylenediamine, H₃BO₃ and H₃PO₄. The orthorhombic crystal structures (Pbca, No. 61, Z = 8) were determined by X‐ray single crystal methods (Mg(C₂H₁₀N₂)[B₂P₃O₁₂(OH)]: a = 936.81(2) pm, b = 1221.86(3) pm, c = 2089.28(5) pm) and Rietveld‐methods (M^II = Mn: a = 931.91(4) pm, b = 1234.26(4) pm, c = 2129.75(7) pm, Fe: a = 935.1(3) pm, b = 1224.8(3) pm, c = 2088.0(6) pm, Ni: a = 939.99(3) pm, b = 1221.29(3) pm, c = 2074.05(7) pm, Cu: a = 941.38(3) pm, b = 1198.02(3) pm, c = 2110.01(6) pm, Zn: a = 935.06(2) pm, b = 1221.33(2) pm, c = 2094.39(4) pm), respectively. The anionic part of the structure contains tetrahedral layers, consisting of three‐ and nine‐membered rings. The M^II‐ions are in a distorted octahedral or tetragonal‐bipyramidal [4 + 2] (copper) coordination formed by oxygen functions of the tetrahedral layers. The resulting three‐dimensional structure contains channels running along [010]. Protonated Ethylenediamine ions are fixed within the channels by hydrogen bonds.     

Einkristallstrukturbestimmungen an KBiO2 und RbBiO2 und ein kristallchemischer Vergleich der Alkalimetallbismutate(III) vom Typ MBiO2 (M = Na,K, Rb,Cs)

Single Crystal Structure Determination on KBiO₂ and RbBiO₂ and a Crystal Chemical Comparison of MBiO₂ (M = Na, K, Rb, Cs) Single crystals of KBiO₂ (colourless) and RbBiO₂ (colourless) were obtained by solid state reaction of the respective binary metal oxides. Both crystal structures (KBiO₂: C2/c; a = 783.13(9), b = 790.92(1), c = 596.86(8) pm, β = 124.81(1)°; Z = 4; 445 diffractometer data; R₁ = 0.027; wR² = 0.069; RbBiO₂: C2/c; a = 806.20(5), b = 838.88(4), c = 598.14(4) pm, β = 123.68(1)°; Z = 4; 289 diffractometer data; R₁ = 0.040; wR² = 0.101) reveal infinite [BiO₂]-chains extending along the [0 0 1] direction. The compounds are isostructural with NaBiO₂ and CsBiO₂.     

Synthese und Molekülstruktur von [Al(SiMe3)3(DBU)] (DBU = 1,8-Diazabicyclo[5.4.0]undec-7-en)

Synthesis and Molecular Structure of [Al(SiMe₃)₃(DBU)] (DBU = 1,8-Diazabicyclo[5.4.0]undec-7-ene) [Al(SiMe₃)₃(OEt₂)] reacts with DBU (DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene) at 0 °C yielding [Al(SiMe₃)₃ · (DBU)] ( 1 ). 1 was characterised spectroscopically (¹H, ¹³C, ²⁹Si, ²⁷Al NMR, IR, MS) and by X-ray structure determination [monoclinic, C2/c, a = 33.053(2), b = 9.307(1), c = 20.810(1) Å, β = 124.07(2)°, V = 5302.4(5) ų, Z = 8, 218(2) K]. 1 does not react with [Cp₂ZrCl₂] even in boiling toluene.     

Syntheses and Structures of Two Selenite Chloride Hydrates: Co(HSeO3)Cl · 3 H2O and Cu(HSeO3)Cl · 2 H2O

The first selenite chloride hydrates, Co(HSeO₃)Cl · 3 H₂O and Cu(HSeO₃)Cl · 2 H₂O, have been prepared from solution and characterised by single‐crystal X‐ray diffraction. The cobalt phase adopts an unusual “one‐dimensional” structure built up from vertex‐sharing pyramidal [HSeO₃]^2–, and octahedral [CoO₂(H₂O)₄]^2– and [CoO₂(H₂O)₂Cl₂]^4– units. Inter‐chain bonding is by way of hydrogen bonds or van der Waals' interactions. The atomic arrangement of the copper phase involves [HSeO₃]^2– pyramids and Jahn‐Teller distorted [CuCl₂(H₂O)₄] and [CuO₄Cl₂]^8– octahedra, sharing vertices by way of Cu–O–Se and Cu–Cl–Cu bonds. Crystal data: Co(HSeO₃)Cl · 3 H₂O, M_r = 276.40, triclinic, space group P 1 (No. 2), a = 7.1657(5) Å, b = 7.3714(5) Å, c = 7.7064(5) Å, α = 64.934(1)°, β = 68.894(1)°, γ = 71.795(1)°, V = 337.78(7) ų, Z = 2, R(F) = 0.036, wR(F) = 0.049. Cu(HSeO₃)Cl · 2 H₂O, M_r = 263.00, orthorhombic, space group Pnma (No. 62), a = 9.1488(3) Å, b = 17.8351(7) Å, c = 7.2293(3) Å, V = 1179.6(2) ų, Z = 8, R(F) = 0.021, wR(F) = 0.024.     

Syntheses of (C_5H_9C_5H_4)_2LnCl(THF)_n (Ln=Nd, Sm, Er, Yb) and crystal structure of [(C_5H_9C_5H_4)_2-LnCl(THF)_n]_2(Ln=Sm, n=1; Ln=Er, n=0)

Reactions of lanthanoid trichlorides with sodium cyclopentylcyclopentadienyl in THFafford bis(cyclopentylcyclopentadienyl) lanthanoid chloride complexes (C_5H_9C_5H_4)_2LnCl(THF)_n (Ln=Nd, Sm, n=1; Ln= Er, Yb, n= 0). The compound [CP'_2SmCl(THF)]_2 (2) (Cp' =cyclopentylcy-clopentadienyl) crystallizes from mixed solvent of hexane and THF in monoclinic space group P_2_1/cwith a = 11.583 (3), b = 23.019(6), c = 8.227 (2), β= 90.26 (2)°, V= 2194 (1)~3, D_c= 1.59 g/cm~3.μ= 28.6 cm~(-1), F(000) = 1060, Z= 2 (dimers). Its crystal molecule is a dimer with a crystallographicsymmetry center. The central metal atom Sm is coordinated to two Cp' rings, two bridging chlorineatoms and one THF forming a distorted trigonal bipyramid. The crystal of [Cp'_2ErCl]_2 (3) belongs tothe triclinic space group P with a = 11.264 (2), b= 13.296(5), c = 14.296(6), a = 96.99 (3), β=112.47(2), γ= 102.78(2)°, V= 1865(1)~3, D_c= 1.67 g /cm~3, μ= 48.0 cm~(-1), F(000) = 924, Z = 2 (dimers).The molecule is a dimer consisting of two Cp'_2 ErCl species bridged by two Cl atoms. The centralmetal atom Er is coordinated to two Cp' rings and two bridging chlorine atoms forming a pseudo-tetrahedron. All these complexes are soluble in THF, DME, Et_2O, toluene and hexane.     

Syntheses and Crystal Structures of LaRhMg,CeRhMg, PrRhMg,and NdRhMg

New intermetallic rare earth compounds LaRhMg, CeRhMg, PrRhMg, and NdRhMg were prepared by reaction of the elements in sealed tantalum tubes in a high‐frequency furnace. The compounds were investigated by X‐ray diffraction both on powders and single crystals. LaRhMg crystallizes with the LaNiAl type structure, space group Pnma, Z = 8, a = 760.1(2), b = 419.92(8), c = 1702.6(2) pm, wR2 = 0.0482, 740 F² values and 38 variable parameters. The cerium compound adopts the ZrNiAl structure: P6¯2m, Z = 3, a = 752.3(1), c = 417.6(1) pm, wR2 = 0.0497, 250 F²2 values and 17 variable parameters. PrRhMg and NdRhMg crystallize with the TiNiSi type: Pnma, Z = 4, a = 721.62(7), b = 415.98(4), c = 869.47(8) pm, wR2 = 0.1864, 440 F² values, 20 variables for PrRhMg and a = 720.6(1), b = 417.6(1), c = 868.8(1) pm, wR2 = 0.0779, 425 F² values, 22 variables for NdRhMg. Refinements of the occupancy parameters revealed mixed Mg/Rh occupancy for the magnesium sites of the cerium and the neodymium compound leading to the compositions CeRh_1.262(8)Mg_0.738(8) and NdRh_1.114(9)Mg_0.886(9) for the investigated single crystals. From a geometrical point of view, the four crystal structures are built up from different rhodium centered trigonal prisms. The rhodium and magnesium atoms form three‐dimensional [RhMg] networks in which the rare earth metal atoms are located in different types of channels. The networks show Rh—Mg and Mg—Mg bonding.     

Rare Earth Carbodiimide Silicates: RE2(CN2)(SiO4)

Rare earth carbodiimide silicates RE₂(CN₂)(SiO₄) with RE = Y, La, and Pr were synthesised by solid state metathesis reactions of RECl₃, Li₂(CN₂), and SiO₂ or Li₂SiO₄, respectively, in silica tubes at 550 °C. All three compounds crystallise with different structures, although all of them represent distorted derivatives of the sodium chloride type structure. The structure of Y₂(CN₂)(SiO₄) was refined monoclinically (C2/m, Z = 2, a = 1301.382(5) pm, b = 377.630(1) pm, c = 527.656(2) pm, β = 93.9816(2) °) from X‐ray powder data. The crystal structure of La₂(CN₂)(SiO₄) was refined in a different monoclinic space group (P2₁/c, Z = 4, a = 660.3(1) pm, b = 1282.0(2) pm, c = 656.2(1) pm, β = 105.23(2) °), and the structure of Pr₂(CN₂)(SiO₄) was refined triclinically (P\bar{1} , Z = 2, a = 646.7(2) pm, b = 669.2(2) pm, c = 671.8(2) pm, α = 86.18(3) °, β = 73.22(3) °, γ = 74.08(3) °) from X‐ray single crystal data.     

Neue Gold‐Selen‐Komplexverbindungen: Synthesen und Strukturen von [Au10Se4(dpppe)4]Br2, [Au2Se(dppbe)]∞, [(Au3Se)2(dppbp)3]Cl2 und [Au34Se14(tpep)6(tpepSe)2]Cl6

Novel Gold Selenium Complexes: Syntheses and Structures of [Au₁₀Se₄(dpppe)₄]Br₂, [Au₂Se(dppbe)]_∞, [(Au₃Se)₂(dppbp)₃]Cl₂, and [Au₃₄Se₁₄(tpep)₆(tpep^Se)₂]Cl₆ The reaction of gold phosphine complexes [(AuX)(PR₃)] (X= halogen; R = org. group) with Se(SiMe₃)₂ yield to new chalcogeno bridged gold complexes. Especially within the use of polydentate phosphine ligands cluster complexes like [Au₁₀Se₄(dpppe)₄]Br₂ ( 1 ) (dpppe = 1, 5‐Bis(diphenylphosphino)pentane), [Au₂Se(dppbe)]_∞ ( 2 ) (1, 4‐Bis(diphenylphosphino)benzene), [(Au₃Se)₂(dppbp)₃]Cl₂ ( 3 ) (dppbp = 4, 4′‐Bis‐diphenylphosphino)biphenyl) und [Au₃₄Se₁₄(tpep)₆(tpep^Se)₂]Cl₆ ( 4 ) (tpep = 1, 1, 1‐Tris(diphenylphosphinoethyl)phosphine, tpep^Se = 1, 1‐Bis(diphenylphosphinoethyl)‐1‐(diphenylselenophosphinoethylphosphine) could be isolated and their structures could be determined by X‐ray diffraction. ( 1: Space group P1 (No. 2), Z = 2, a = 1642.1(11), b = 1713.0(9), c = 2554.0(16) pm, α = 80.41(3)°, β = 76.80(4)°, γ = 80.92(4)°; 2: Space group P2₁/n (No. 14), Z = 4, a = 947.3(2), b = 1494.9(3), c = 2179.6(7) pm, β = 99.99(3)°; 3: Space group P2₁/c (No. 14), Z = 8, a = 2939.9(6), b = 3068.4(6), c = 3114.5(6) pm, β = 109.64(3)°; 4: Space group P1 (No. 2), Z = 1, a = 2013.7(4), b = 2420.6(5), c = 2462.5(5) pm, α = 77.20(3), β = 74.92(3), γ = 87.80(3)°).     

Cobalt(II) Complexes with Dicyanamide — from Binuclear Entities to Chains

One binuclear complex [Co(bpm*)₂(dca)]₂(ClO₄)₂ ( 1 ) and two 1D chain Co^II complexes, {[Co(bpm)₂(dca)](ClO₄)}_n ( 2 ) and [Co(dmf)₂(dca)₂]_n ( 3 ), (bpm*: bis[(3, 5‐dimethyl)pyrazolyl]methane; bpm: bis(pyrazolyl)methane; dca: dicyanamide; dmf: N, N‐dimethyl formamide) have been prepared and structurally characterized. The cobalt atoms are hexa‐coordinated forming a slightly distorted octahedral coordination. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, a = 9.849(3)Å, b = 21.944(7)Å, c = 13.814(5)Å, β = 94.824(6), Z = 4, R₁ = 0.0672, wR₂ = 0.1395. 1 is a binuclear complex linked by two dca ligands, and each Co^II ion is coordinated by two terminal bpm* ligands. Compound 2 crystallizes in the orthorhombic system, space group Cmcm, a = 10.377(4)Å, b = 13.594(5)Å, c = 15.999(6)Å, Z = 4, R₁ = 0.0609, wR₂ = 0.1328. The structure of 2 can be described as a one‐dimensional zigzag chain of Co^II ions bridged by one dca ligand. Each Co^II ion in the chain is coordinated by two bpm ligands. Compound 3 crystallizes in the monoclinic system, space group C₂, a = 13.559(15)Å, b = 7.393(8)Å, c = 8.110(9)Å, β = 112.228(15), Z = 2, R₁ = 0.0260, wR₂ = 0.0760. 3 has a one‐dimensional linear chain of Co^II ions bridged by two dca ligands, in which each Co^II ion is coordinated with two dmf molecules.     

Synthese und Kristallstrukturen von (3‐Methylpyridinium)3[DyCl6] und (3‐Methylpyridinium)2[DyCl5(Ethanol)]

Preparation and Structure of (3‐Methylpyridinium)₃[DyCl₆] and (3‐Methylpyridinium)₂[DyCl₅(Ethanol)] The complex chlorides (3‐Methylpyridinium)₃[DyCl₆] ( 1 ) and (3‐Methylpyridinium)₂[DyCl₅(Ethanol)] ( 2 ) have been prepared for the first time. The crystal structures have been determined from single crystal X‐ray diffraction data. 1 crystallizes in the trigonal space group R3c (Z = 36) with a = 2953.3(3) pm, b = 2953.3(3) pm and c = 3252.5(4) pm, compound 2 crystallizes in the triclinic space group P1 (Z = 2) with a = 704.03(8) pm, b = 808.10(8) pm, c = 1937.0(2) pm, α = 77.94(1)°, β = 87.54(1)° and γ = 83.26(1)°. The structures contain isolated octahedral building units [DyCl₆]^3– and [DyCl₅(Ethanol)]^2–, respectively.     

Über röntgenographische Einkristalluntersuchungen an Na2FeAlF7, Na2MIIGaF7 (MII = Ni,Zn) und Na2ZnFeF7 und die Strukturchemie der Weberite

On X-Ray Single Crystal Studies of Na₂FeAlF₇, Na₂M^IIGaF₇ (M^II = Ni, Zn), and Na₂ZnFeF₇ and the Structural Chemistry of Weberites At single crystals of the orthorhombic weberite Na₂NiGaF₇ (a = 716.1, b = 1021.6, c = 740.9 pm; Imma, Z = 4) and of the monoclinic variants (C2/c, Z = 16) Na₂FeAlF₇ (a = 1242.6, b = 727.8, c = 2420.6 pm, β = 99.99°), Na₂ZnGaF₇ (a = 1251.9, b = 730.3, c = 2435.3 pm, β = 99.74°) and Na₂ZnFeF₇ (a = 1261.0, b = 7.359, c = 2453.8 pm, β = 99.70°) complete X-ray structure determinations were performed. The results and the influence of radii on the bridge angles M^II–F–M^II and M^II–F–M^III are discussed in connection with general features within the structural chemistry of 28 weberites.     

Quaternary indides LaTIn3Mg (T = Rh and Ir) and CeIrIn3Mg with LaCoAl4 type structure

The quaternary indides LaTIn₃Mg (T = Rh and Ir) and CeIrIn₃Mg were prepared from the elements in sealed tantalum ampoules in an induction furnace. The samples were characterized by X-ray powder and single crystal data: LaCoAl₄ type, Pmma, Z = 2, a = 830.5(1), b = 436.1(1), c = 745.1(1) pm, wR2 = 0.038, 467 F ² values for LaRhIn_3.075Mg_0.925, a = 832.9(1), b = 436.5(1), c = 746.9(1) pm, wR2 = 0.077, 471 F ² values for LaIrIn_3.091Mg_0.909, and a = 832.2(1), b = 434.1(1), c = 743.9(1) pm, wR2 = 0.066, 465 F ² values for CeIrIn_3.07Mg_0.93 with 25 variables for each refinement. The transition metal, indium, and magnesium atoms build up three-dimensional [TIn₃Mg] networks which leave pentagonal prismatic voids for the lanthanum and cerium atoms. The transition metal atoms have tricapped trigonal prismatic coordination and the magnesium atoms fill distorted square prisms. All three crystals revealed a small degree of Mg/In mixing on the latter site.     

Kristallstrukturen der Samarium-Amido-Komplexe [Sm(l-X){N(SiMe3)2}2(THF)]2 mit X = Cl,Br

Crystal Structures of the Samarium Amido Complexes [Sm(l-X){N(SiMe₃)₂}₂(THF)]₂ with X = Cl, Br The crystal structures of the title compounds have been determined by X-ray methods. [Sm(μ-Cl) · {N(SiMe₃)₂}₂(THF)]₂ ( 1 ): Space group P2₁/n, Z = 2, lattice dimensions at 223 K: a = 1429.5(2), b = 1302.3(3), c = 1658.6(3) pm, β = 114.212(10)°, R = 0.0561. [Sm(μ-Br) · {N(SiMe₃)₂}₂(THF)]₂ ( 2 ): Space group Pbca, Z = 4, lattice dimensions at 223 K: a = 1850.0(7), b = 1611.0(9), c = 1888.1(6) pm, R = 0.0497. 1 and 2 form centrosymmetric dimeric complexes via μ-X-halogeno bridges. The samarium atoms are coordinated in a distorted trigonal-bipyramidal surrounding, the THF molecule and one of the bridging halogen atoms being in axial positions.     

Synthese und Kristallstrukturen von (2‐Methylpyridinium)3[TbCl6] und (2‐Methylpyridinium)2[TbCl5(1‐Butanol)]

Preparation and Structure of (2‐Methylpyridinium)₃[TbCl₆] and (2‐Methylpyridinium)₂[TbCl₅(1‐Butanol)] The complex chlorides (2‐Methylpyridinium)₃[TbCl₆] (1) and (2‐Methylpyridinium)₂[TbCl₅(1‐Butanol)] (2) have been prepared for the first time. The crystal structures have been determinated from single crystal X‐ray diffraction data. 1 crystallizes in the monoclinic space group C2/c (Z = 8) with a = 3241,2(5) pm, b = 897,41(9) pm, c = 1774,2(2) pm and β = 97,83(2)°, 2 in the monoclinic space group P2₁/n (Z = 4) with a = 1372,96(16) pm, b = 997,57(9) pm, c = 1820,5(2) pm and β = 108,75(1)°. The structures contain isolated octahedral building units [TbCl₆]^3– and [TbCl₅(1‐Butanol)]^2–, respectively.     

Synthesen und Strukturen der polymeren Silber‐Komplexe [Ag2Cl2(dppbp)3]∞, [Ag2(SPh)2(dppe)3]∞ und [Ag2(SPh)2(triphos)]∞ sowie der Silber‐Chalkogenido‐Cluster [Ag7(SPh)7(dppm)3], {[Ag7(TePh)7(dppp)3]2(dppp)} und [Ag22Cl(SPh)10(PhCOO)11(dmf)3]∞

Syntheses and Structures of the Polymeric Silver Complexes [Ag₂Cl₂(dppbp)₃]_∞, [Ag₂(SPh)₂(dppe)₃]_∞ and [Ag₂(SPh)₂(triphos)]_∞ as well as the Silver Chalcogenido Clusters [Ag₇(SPh)₇(dppm)₃], {[Ag₇(TePh)₇(dppp)₃]₂(dppp)}, and [Ag₂₂Cl(SPh)₁₀(PhCOO)₁₁(dmf)₃]_∞ The reaction of silver carboxylate with silylated chalcogen compounds have been found to have a possibility for the synthesis of metal‐chalcogenide‐custers. Especially phosphine ligands have been found to be useful in stabilising the cluster cores. Some of the silver carboxylate phosphine complexes, which are formed in‐situ, ([Ag₂Cl₂(dppbp)₃]_∞ ( 1 )) and some silver chalcogen complexes ([Ag₂(SPh)₂(dppe)₃]_∞ ( 2 ) und [Ag₂(SPh)₂(triphos)]_∞ ( 3 )), could be isolated and characterised by X‐ray diffraction. Using special reaction conditions, it is possible to isolate cluster species like [Ag₇(SPh)₇(dppm)₃] ( 4 ), {[Ag₇(TePh)₇(dppp)₃]₂(dppp)} ( 5 ) and [Ag₂₂Cl(SPh)₁₀(PhCOO)₁₁(dmf)₃]_∞ ( 6 ) beside the complex compounds. 1: Space group P2₁/n (No. 14), Z = 2, a = 1336, 1(2), b = 2081, 2(5), c = 2015, 4(4) pm, β = 99, 87(2)°; 2: Space group P2₁/n (No. 14), Z = 2, a = 1416, 1(3), b = 1874, 7(4), c = 1444, 8(3) pm, β = 93, 26(3)°; 3: Space group P2₁/n (No. 14), Z = 4, a = 1456, 8(3, b = 1890, 2(4), c = 1916, 1(4) pm, β = 99, 11(3)°; 4: Space group P2₁/n (No. 14), Z = 4, a = 1570, 2(3), b = 2798, 5(6), c = 2752, 7(6) pm, β = 98, 02(3)°; 5: Space group P1 (No. 2), Z = 2, a = 2115, 5(4), b = 2553, 3(5), c = 3188, 7(6) pm, α = 68, 87(3)°, β = 74, 05(3)°, γ = 69, 70(3)°; 6: Space group P1 (No. 2), Z = 2, a = 1583, 0(3), b = 1709, 6(3), c = 2990, 0(6) pm, α = 80, 41(3)°, β = 88, 86(3)°, γ = 71, 10(3)°).     

THE CRYSTAL AND MOLECULAR STRUCTURE OF Ru3(CO)9(PPh3)3

Abstract

The synthesis of tertiary phosphine and phosphite substituted derivatives of M₃(CO)₁₂ {M = Ru(1a) Os(1b)} is discussed and the X-ray crystal and molecular structure of the tris-triphenylphosphine substituted ruthenium cluster Ru₃(CO)₉(PPh₃)₃ (2a) is reported. Complex 2a crystallises in the monoclinic space group P2₁/n with cell parameters a = 14.180(9), b = 21.644(14), c = 18.248(10) Å, β = 92.52(5)°, V = 5595(6) Å ³, Z = 4. The structure was solved by full-matrix least-squares methods based on F ². The refinement converged at R1 = 0.0564, wR2 = 0.2125 for 4857 observed data [F > 4σ(F)].