Synthese und Kristallstrukturen der Samarium-Komplexe [SmI2(DME)3] und [Sm2I(NPPh3)5(DME)]

Synthesis and Crystal Structures of the Samarium Complexes [SmI₂(DME)₃] and [Sm₂I(NPPh₃)₅(DME)] When treated with ultrasound, the reaction of samarium metal with N-iodine-triphenylphosphaneimine in 1,2-dimethoxyethane (DME) leads to the two samarium complexes [SmI₂(DME)₃] ( 1 ) and [Sm₂I(NPPh₃)₅(DME)] ( 2 ), which are separated from each other by fractional crystallization. 1 could be isolated in two different crystallographic forms, namely as brownish black crystals ( 1 a ) and as violet-black crystals ( 1 b ), both of them are characterized by crystal structure analyses. 1 a : Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1459.4(1), b = 1314.4(1), c = 2293.6(2) pm, β = 99.245(8)°, R = 0.0344. The structure of 1 a holds two crystallographically independent molecules [SmI₂(DME)₃], in which the samarium atoms have coordination number eight. The two individuals differ from each other particularly in their I–Sm–I bond angles, which are 157.94 and 178.45°. 1 b : Space group P2₁, Z = 2, lattice dimensions at –80 °C: a = 849.4(3), b = 1060.1(3), c = 1235.1(6) pm, b = 93.86(5)°, R = 0.0251. 1 b has a molecular structure similar to that of 1a with a bond angle I–Sm–I of 158.40°. The phosphoraneiminato complex [Sm₂I(NPPh₃)₅(DME)] ( 2 ) forms colourless, moisture sensitive crystals which contain two molecules DME per formula unit. 2 · 2 DME: Space group P1, Z = 2, lattice dimensions at –80 °C: a = 1405.0(4), b = 1656.5(3), c = 2208.3(7) pm, α = 89.60(3)°, β = 72.96(4)°, γ = 78.70(3)°, R = 0.0408. In 2 the two samarium atoms are linked via the μ-N atoms of two phosphoraneiminato ligands to form a planar Sm₂N₂ four-membered ring. One of the Sm atoms is terminally coordinated by the N atoms of two (NPPh₃)^– groups, thus achieving a distorted tetrahedral surrounding. The second Sm atom is coordinated by the N atom of one (NPPh₃)^– group, by the terminally bonded iodine atom, and by the O atoms of the DME chelate, thus achieving a distorted octahedral surrounding.     

Synthese und Kristallstruktur des Aminoimino‐Phosphinat–Kupfer(I)‐Komplexes [Cu(Me3SiNP(Ph)2NSiMe3)]2

Synthesis and Crystal Structure of the Aminoiminophosphinate Copper(I) Complex [Cu(Me₃SiNP(Ph)₂NSiMe₃)]₂ The title compound 1 was prepared by the reaction of Me₃SiNP(Ph)₂N(SiMe₃)₂ with copper(I) chloride at 120 °C to give colourless crystals which were characterized by a crystal structure determination. Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1854.0(3), b = 1256.2(3), c = 1969.9(3) pm, β = 106.30(2)°; R₁ = 0.063. 1 forms dimeric molecules with a nonplanar Cu₂N₄P₂ eight‐membered ring of symmetry C₂ and a rather long Cu…Cu distance of 262.1(1) pm.     

Synthese und Kristallstruktur des gemischt‐valenten Komplexes [Sn2I3(NPPh3)3]

Synthesis and Crystal Structure of the Mixed Valent Complex [Sn₂I₃(NPPh₃)₃] The mixed valent phosphoraneiminato complex [Sn₂I₃(NPPh₃)₃] ( 1 ) was prepared by the reaction of the tin(II) complex [SnI(NPPh₃)]₂ with sodium in tetrahydrofuran. 1 crystallizes with two formula units of THF to form yellow, moisture sensitive single crystals, which were characterized by a crystal structure determination. 1 · 2 THF: Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1964.5(2), b = 1766.0(2), c = 2058.6(2) pm; β = 118.33(1)°, R = 0.052. 1 forms dimeric molecules in which the tin atoms are linked by two nitrogen atoms of two (NPPh₃^–) groups to form a planar Sn₂N₂ four‐membered ring. The Sn^IV atom is additionally coordinated by a terminal iodine atom and by a terminal (NPPh₃^–) group, whereas the Sn^II atom is additionally coordinated by two iodine atoms forming a ψ trigonal‐bipyramidal surrounding.     

Die Kristallstruktur des Oxophosphazens [Ph3PNPPh2NP(O)Ph2]

Crystal Structure of the Oxophosphazene [Ph₃PNPPh₂NP(O)Ph₂] Single crystals of [Ph₃PNPPh₂NP(O)Ph₂] were obtained as a by‐product from the synthesis of [NaNPPh₃]₆ as a result of partial hydrolysis. According to the crystal structure determination the compound forms a molecular structure with a PNPNP chain with PN distances between 155.3(6) and 159.8(5) pm and PNP bond angles of 143.2(4) and 140.7(4)°. Space group P1¯, Z = 2, lattice dimensions at 213 K: a = 922.7(1); b = 1040.1(1); c = 1908.0(1) pm; α = 90.55(1)°; β = 103.01(1)°; γ = 92.87(1)°; R = 0.0859.     

Die Kristallstruktur von (Ph4P)2[Be4Cl4(μ‐N3)6]

Suitable single crystals for X‐ray analysis of the recently published azido beryllate (Ph₄P)₂[Be₄Cl₄(μ‐N₃)₆] ( 1 ) [1] were obtained by a modified synthetic route, and the crystal structure of 1 was determined. The compound crystallizes isotypically with the corresponding bromo derivative [1] in the space group C2/c with 12 formula units per unit cell. Lattice dimensions at 193 K: a = 4125.5(1), b = 2001.7(1), c = 2050.4(1) pm, β = 101.05 (1)°, R₁ = 0.0359. The structure contains adamantanlike dianions [Be₄Cl₄(μ‐N₃)₆]^2? with a Be₄N₆ core forming by the bridging function of the α‐nitrogen atoms of the azido groups.     

Die Kristallstruktur des Diacetonalkohol‐Komplexes [Mn(DAA)3]2+[MnI4]2– · DAA

Crystal Structure of the Diacetone Alcohol Complex [Mn(DAA)₃]²⁺[MnI₄]^2– · DAA The title compound has been prepared from MnI₂ and excess diacetone alcohol (4‐hydroxy‐4‐methyl‐2‐pentanon) to give brown single crystals which were suitable for a crystal structure determination. Space group P2₁/c, Z = 4, lattice dimensions at 157 K: a = 1158.3(1), b = 1806.0(1), c = 1846.5(2) pm, β = 97.421(8)°, R₁ = 0.0381. The structure consists of [Mn(DAA)₃]²⁺ ions with distorted octahedral environment of the manganese atom, tetrahedral [MnI₄]^2– ions and a diacetone alcohol molecule which is connected by two hydrogen bridges with the complex cation.     

Sm2As4O9: Ein ungewöhnliches Samarium(III)‐Oxoarsenat(III) gemäß Sm4[As2O5]2[As4O8]

Sm₂As₄O₉: An Unusual Samarium(III) Oxoarsenate(III) According to Sm₄[As₂O₅]₂[As₄O₈] Pale yellow single crystals of the new samarium(III) oxoarsenate(III) with the composition Sm₄As₈O₁₈ were obtained by a typical solid‐state reaction between Sm₂O₃ and As₂O₃ using CsCl and SmCl₃ as fluxing agents. The compound crystallizes in the triclinic crystal system with the space group (No. 2, Z = 2; a = 681.12(5), b = 757.59(6), c = 953.97(8) pm, α = 96.623(7), β = 103.751(7), γ = 104.400(7)°). The crystal structure of samarium(III) oxoarsenate(III) with the formula type Sm₄[As₂O₅]₂[As₄O₈] (≡ 2 × Sm₂As₄O₉) contains two crystallographically different Sm³⁺ cations, where (Sm1)³⁺ is coordinated by eight, but (Sm2)³⁺ by nine oxygen atoms. Two different discrete oxoarsenate(III) anions are present in the crystal structure, namely [As₂O₅]^4? and [As₄O₈]^4?. The [As₂O₅]^4? anion is built up of two Ψ¹‐tetrahedra [AsO₃]^3? with a common corner, whereas the [As₄O₈]^4? anion consists of four Ψ¹‐tetrahedra with ring‐shaped vertex‐connected [AsO₃]^3? pyramids. Thus at all four crystallographically different As³⁺ cations stereochemically active non‐binding electron pairs (“lone pairs”) are observed. These “lone pairs” direct towards the center of empty channels running parallel to [010] in the overall structure, where these “empty channels” being formed by the linkage of layers with the ecliptically conformed [As₂O₅]^4? anions and the stair‐like shaped [As₄O₈]^4? rings via common oxygen atoms (O1 – O6, O8 and O9). The oxygen‐atom type O7, however, belongs only to the cyclo‐[As₄O₈]^4? unit as one of the two different corner‐sharing oxygen atoms.     

Kristallstruktur des Zinkamids Zn[N(SiMe3)2]2

Crystal Structure of the Zinc Amide Zn[N(SiMe₃)₂]₂ X‐ray quality crystals of Zn[N(SiMe₃)₂]₂ (monoclinic, P2₁/c) are obtained by sublimation of the zinc amide Zn[N(SiMe₃)₂]₂ at —30 °C in vacuo (300 torr). According to the result of the X‐ray structural analysis, Zn[N(SiMe₃)₂]₂ contains an almost linear N‐Zn‐N unit with two short N‐Zn bonds.     

Synthese und Kristallstruktur des Azidoberyllats (Ph4P)2[Be(μ‐OSiMe3)(N3)2]2

Synthesis and Crystal Structure of the Azido Beryllate (Ph₄P)₂[Be(μ‐OSiMe₃)(N₃)₂]₂ (Ph₄P)₂[Be₂F₆] reacts with excess trimethylsilylazide in acetonitrile solution, accompanied by a hydrolytic side‐reaction to give the azido beryllate (Ph₄P)₂[Be(μ‐OSiMe₃)(N₃)₂]₂ ( 1 ) as colourless, non‐explosive crystals. 1 was characterized by IR spectroscopy and by single crystal X‐ray determination. 1 : Space group , Z = 1, lattice dimensions at 193 K: a = 1026.9(1), b = 1184.0(1), c = 1352.1(1) pm, α = 73.50(1)°, β = 74.35(1)°, γ = 64.66(1)°, R₁ = 0.0543. The complex anion of 1 forms centrosymmetric units with symmetry C_i via Be₂O₂ four‐membered rings with Be–O distances of 159.2(7) and 168.7(7) pm, and terminally bonded azide groups.     

trans‐[TcNCl2(Ph3PNH)2] — Synthesis and Structure

The neutral technetium(V) phosphoraneimine complex [TcNCl₂(Ph₂PNH)₂] is formed when (Bu₄N)[TcOCl₄] reacts with Me₃SiNPPh₃ in dichloromethane. Distances of 2.078(4) and 2.102(4) Å have been found between Tc and the neutral triphenylphosphoraneimine ligands. The Tc‐N‐P angles are 133.7(3) and 134.8(3)°. The terminal nitrido ligand is formed by decomposition of an additional molecule of Me₃SiNPPh₃. The protons which are used for the protonation of the organic ligands are released during the decomposition of CH₂Cl₂. The same reaction yields the [TcNCl₄]^— anion when it is performed in acetonitrile.     

Kristallstrukturen,Schwingungsspektren und Normalkoordinatenanalyse von (n‐Bu4N)2[Os(NCS)6] und (n‐Bu4N)3[Os(NCS)6]

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[Os(NCS)₆] and ( n ‐Bu₄N)₃[Os(NCS)₆] By tempering the solid mixture of the linkage isomers (n‐Bu₄N)₃[Os(NCS)_n(SCN)_6–n] n = 0–5 for a longer time at temperatures increasing from 60 to 140 °C the homoleptic (n‐Bu₄N)₃[Os(NCS)₆] is formed, which on oxidation with (NH₄)₂[Ce(NO₃)₆] in acetone yields the corresponding Os^IV complex (n‐Bu₄N)₂[Os(NCS)₆]. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Os(NCS)₆] (1) (triclinic, space group P 1, a = 12.596(5), b = 12.666(5), c = 16.026(5) Å, α = 88.063(5), β = 80.439(5), γ = 88.637(5)°, Z = 2) and (n‐Bu₄N)₃[Os(NCS)₆] ( 2 ) (cubic, space group Pa 3, a = 24.349(4) Å, Z = 8) have been performed. The nearly linear thiocyanate groups are coordinated with Os–N–C angles of 172.3–177.7°. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constant f_d(OsN) is 2.3 ( 1 ) and 2.10 mdyn/Å ( 2 ).     

Einkristalle von La[AsO4] im Monazit‐ und Sm[AsO4] im Xenotim‐Typ

Single Crystals of La[AsO₄] with Monazite‐ and Sm[AsO₄] with Xenotime‐Type Structure Brick‐shaped, transparent single crystals of colourless monazite‐type La[AsO₄] (monoclinic, P2₁/n, a = 676.15(4), b = 721.03(4), c = 700.56(4) pm, β =104.507(4)°, Z = 4) and pale yellow xenotime‐type Sm[AsO₄] (tetragonal, I4₁/amd, a = 718.57(4), c = 639.06(4) pm, Z = 4) emerge as by‐products from alkali and rare‐earth metal chloride fluxes whenever the synthesis of lanthanide(III) oxoarsenate(III) derivatives from admixtures of the corresponding sesquioxides in sealed, evacuated silica ampoules is accompanied by air intrusion and subsequent oxidation. Nine oxygen atoms from seven discrete [AsO₄]^3? tetrahedra recruit the rather irregular coordination sphere of La³⁺ (d(La³⁺?O^2?) = 248 – 266 pm plus 291 pm) and even a tenth ligand could be considered at a distance of 332 pm. The trigonal dodecahedral figure of coordination consisting of eight oxygen atoms at distances of 236 and 248 pm (4× each) about Sm³⁺ is provided by only six isolated tetrahedral [AsO₄]^3? units. Alternating trans‐edge condensation of the latter with the [LaO₉₊₁] polyhedra of monazite‐type La[AsO₄] and the [SmO₈] polyhedra of xenotime‐type Sm[AsO₄] constitutes the main structural chain features along [100] or [001], respectively. The bond distances and angles of the complex [AsO₄]^3? anions range within common intervals (d(As⁵⁺?O^2?) = 167 – 169 pm, ?(O–As–O) = 100 – 116°) for both lanthanide(III) oxoarsenates(V) presented here.     

Synthesis,Crystal Structure and Thermal Decomposition Process of Complex [Sm(BA)3phen]2

A binuclear samarium(III) complex with benzoic acid and 1,10‐phenanthroline, [Sm(BA)₃phen]₂ was synthesized and characterized by elemental analysis, UV, IR and TG‐DTG techniques. The structure of the title complex was established by single crystal X‐ray diffraction. The crystal is triclinic, space group P1 with a = 10.8216(11) Å, b = 11.9129(13) Å, c = 12.425(2) Å, α = 105.007(2)°, β = 93.652(2)°, γ = 113.2630(10)°, Z = 1, D_c = 1.650 mg·m^?3, F(000) = 690. The carboxylate groups are bonded to the samarium ion in three modes: bidentate chelating, bidentate bridging, and tridentate chelating‐bridging. Each Sm³⁺ ion is coordinated to one bidentate chelating carboxylate group, two bidentate bridging and two tridentate chelating‐bridging carboxylate groups, as well as one 1,10‐phenanthroline molecule, forming a nine‐coordinate metal ion. Based on thermal analysis, the thermal decomposition process of [Sm(BA)₃phen]₂ has been derived.     

Darstellung und Kristallstruktur von [Li(DME)2I]

Synthesis and Crystal Structure of [Li(DME)₂I] . LiI can be dissolved at 50°C in toluene/DME (2:1). At - 20°C [Li(DME)₂I] ( 1 ) was isolated in 75% yield. 1 was characterized by NMR techniques as well as an X-Ray structure determination. 1 crystallizes in the space group C2/c with a = 1 356.9(2), b = 813.2(1), c = 1 259.1(2) pm, and β = 99.74(1)°.     

Azidokomplexe von Vanadium(IV) und Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 und (Ph4P)2[VOCl(μ‐N3)(N3)2]2

Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ and (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ (Ph₄P)₂[VOCl₂(μ‐N₃)]₂ ( 1 ) was prepared by reaction of (Ph₄P)[VO₂Cl₂] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph₄P)₂[VOCl(μ‐N₃)(N₃)₂]₂ ( 2a ), which can be obtained as the main product by application of a large excess of Me₃SiN₃. Dark blue needles of 2a crystallize spontaneously from the CH₂Cl₂ solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P2₁/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R₁ = 0.0672. The complex anion forms centrosymmetric units with V₂N₂‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) ų, d_calc. = 1.440 g·cm^?3, R₁ = 0.0384. The complex anion forms centrosymmetric units of symmetry C_i with V₂N₂ four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) ų, d_calc. = 1.471 g·cm^?3, R₁ = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V₂N₂ ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm.     

Diacetonalkohol‐Komplexe von Lanthanoid‐Trichloriden. Die Kristallstrukturen von [LnCl3(DAA)2] mit Ln = Sm und Eu

Diacetone Alcohol Complexes of Lanthanide Trichlorides. Crystal Structures of [LnCl₃(DAA)₂] with Ln = Sm and Eu The diacetone alcohol complexes [LnCl₃(DAA)₂] with Ln = samarium ( 1 ) and europium ( 2 ) are obtained from the waterfree metal trichlorides with excess diacetone alcohol (4‐hydroxy‐4‐methyl‐2‐pentanone = DAA) forming colourless ( 1 ) and pale yellow crystals ( 2 ), respectively, which are characterized by crystal structure determinations. The europium compound 2 is additionally described by its vibrational spectra (IR, Raman). 1 and 2 crystallize isotypically with one another. The metal atoms of the molecular complex units are unusually coordinated in a distorted pentagonal‐bipyramdial fashion by the three chlorine atoms and by the two alcoholic oxygen atoms of the DAA molecules in the equatorial plane. The apical positions are occupied by the carbonyl oxygen atoms of the chelating DAA molecules. The complex units [LnCl₃(DAA)₂] are associated along [100] by bifurcated —OH···Cl···HO— bridges to form chains. 1 : Space group P2₁, Z = 2, lattice dimensions at —80 °C: : a = 710.2(1), b = 1617.6(2), c = 827.3(1) pm; β = 106.36(1)°; R₁ = 0.026. 2 : Space group P2₁, Z = 2, lattice dimensions at —80 °C: a = 709.7(1), b = 1614.5(2), c = 825.7(1) pm; β = 106.40(1)°; R₁ = 0.0303.     

Darstellung und Kristallstruktur eines Ditelluridovanadium(IV)‐Komplexes: [(μ‐η1‐Te2)(μ‐NtBu)2V2Cp2]

Synthesis and Crystal Structure of a Ditelluridovanadium(IV) Complex: [(μ‐η¹‐Te₂)(μ‐N^tBu)₂V₂Cp₂] [(μ‐η¹‐Te₂)(μ‐N^tBu)₂V₂Cp₂] ( 2 ) is formed from [^tBuN = VCp(PMe₃)₂] ( 1 ) upon reaction with elemental tellurium. 1 and 2 are characterized by spectroscopic methods (MS; ¹H, ¹³C, ⁵¹V NMR), in addition 2 by single crystal X‐ray diffraction. The crystal structure indicates a folded cyclodivanadazen ring bridged by a bidentated ditellurido ligand, the first example of this structure type.     

Cs[Yb(NPPh3)4] – ein homoleptischer Phosphaniminato‐Komplex des Ytterbiums

Cs[Yb(NPPh₃)₄] – a Homoleptic Phosphoraneiminato Complex of Ytterbium Cesium tetrakis(phosphoraneiminato)ytterbate, Cs[Yb(NPPh₃)₄] ( 1 ) has been prepared by the reaction of the dimeric complex [Yb(NPPh₃)₃]₂ with CsNPPh₃ in thf solution. 1 crystallizes from thf solution to give colourless moisture sensitive crystals which contain three molecules thf per asymmetric unit. According to the crystal structure determination 1 forms a dimeric ion ensemble [Cs{Yb(NPPh₃)₄}]₂ in which the Cs⁺ ions connect the [Yb(NPPh₃)₄]^– ions via Cs…N bridges. The ytterbium atoms are distorted tetrahedrally coordinated by the nitrogen atoms of the phosphoraneiminato ligands (NPPh₃^–) with short Yb–N‐bond lengths between 212.1 and 221.9(8) pm. The included thf molecules are without bonding contacts with the complex. [Cs{Yb(NPPh₃)₄}]₂ · 6 thf: Space group P 1, Z = 2, lattice dimensions at 193 K: a = 1837.2(2), b = 2041.5(2), c = 2095.8(2) pm, α = 79.953(13)°, β = 79.364(11)°, γ = 88.239(12)°, R = 0.0625.     

Synthese und Kristallstruktur des Kalium‐Iminophosphanids [K4(THF)3(Me3SiNPEt2)2(OSiMe2OSiMe2O)]2

The potassium iminophosphanide complex [K₄(thf)₃(Me₃SiNPEt₂)₂(OSiMe₂OSiMe₂O)]₂ has been obtained by a melt reaction of Me₃SiNPEt₃ with potassium hydride at 140 °C in the presence of silicon grease (—OSiMe₂—)_n and subsequent crystallization from thf solution. The colourless moisture sensitive single crystals are characterized by X‐ray diffraction: Space group P1¯, Z = 1, lattice dimensions at —70 °C: a = 1135.9(3), b = 1250.0(3), c = 1866.1(4) pm, α = 92.65(1)°, β = 100.80(1)°, γ = 93.57(1)°, R₁ = 0.0604. The centrosymmetric dimeric cluster aggregate is formed by two of the eight potassium ions which are connected with the central oxygen atom of both the (OSiMe₂OSiMe₂O)^2— chains as well as with one of their terminal O atoms each. The remaining potassium ions are connected with the phosphorus atoms of the iminophosphanide groups (Me₃SiNPEt₂)^— as well as with its nitrogen atoms. They are terminally solvated by thf molecules.