Synthese und Koordinationsverhalten von (Ph3SnO)3As. Die Kristallstrukturen von (Ph3SnO)3As und [{(Ph3SnO)3As}Fe(CO)4]

Synthesis and Coordination Behaviour of (Ph₃SnO)₃As. The Crystal Structures of (Ph₃SnO)₃As and [{(Ph₃SnO)₃As}Fe(CO)₄] (Ph₃SnO)₃As ( 1 ) was obtained from the reaction of Ph₃SnOH with As₂O₃ in a dichloromethane/water mixture as solvent. Upon recrystallization from DMF 1 forms orthorhombic crystals, space group P2₁2₁2₁, with a = 977.3(2), b = 1903.5(3) and c = 2600.9(5) pm (at 220 K). In 1 the As atom is bound to three OSnPh₃ groups with As–O distances of 171.9(3)–174.9(3) pm. Reaction of 1 with Fe₂(CO)₉ gives [{(Ph₃SnO)₃As}Fe(CO)₄] ( 2 ). 2 crystallizes monoclinic, space group P2₁/n with a = 2242.3(5), b = 1112.6(2), c = 2353.0(5) pm and β = 111,46(2)° (at 220 K). In 2 the iron atom exhibits a trigonal bipyramidal coordination with the (Ph₃SnO)₃As ligand in an axial position. The Fe–As bond length is 230.5(1) pm.     

Synthese und Kristallstrukturen von [Cu4(As4Ph4)2(PRR′2)4], [Cu14(AsPh)6(SCN)2(PEt2Ph)8], [Cu14(AsPh)6Cl2(PRR′2)8], [Cu12(AsPh)6(PPh3)6], [Cu10(AsPh)4Cl2(PMe3)8], [Cu12(AsSiMe3)6(PRR′2)6] und [Cu8(AsSiMe3)4(PtBu3)4] (R,R′ = organische Gruppen)

Syntheses and Crystal Structures of [Cu₄(As₄Ph₄)₂(PRR′₂)₄], [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈], [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈], [Cu₁₂(AsPh)₆(PPh₃)₆], [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈], [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆], and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] (R, R′ = Organic Groups) Through the reaction of CuSCN with AsPh(SiMe₃)₂ in the presence of tertiary phosphines the compounds [Cu₄(As₄Ph₄)₂(PRR′₂)₄] ( 1 – 3 ) ( 1 : R = R′ = ⁿPr, 2 : R = R′ = Et; 3 : R = Me, R′ = ⁿPr) and [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈] ( 4 ) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈] ( 5–6 ) ( 5 : R = R′ = Et; 6 : R = Me, R′ = ⁿPr), [Cu₁₂(AsPh)₆(PPh₃)₆] ( 7 ) and [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈] ( 8 ). Through reactions of CuOAc with As(SiMe₃)₃ in the presence of tertiary phosphines the compounds [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆] ( 9 – 11 ) ( 9 : R = R′ = Et; 10 : R = Ph, R′ = Et; 11 : R = Et, R′ = Ph) and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] ( 12 ) can be obtained. In each case the products were characterised by single‐crystal‐X‐ray‐structure‐analyses. As the main structure element 1 – 3 each have two As₄Ph₄^2–‐chains as ligands. In contrast 4 – 12 contain discrete AsR^2–ligands.     

Silylierte Phosphanimin-Komplexe von Chrom(II), Palladium(II) und Kupfer(II). Die Kristallstrukturen von [CrCl2(Me3SiNPMe3)2], [PdCl2(Me3SiNPEt3)2] und [CuCl2(Me3SiNPMe3)]2

Silylated Phosphaneimine Complexes of Chromium(II), Palladium(II), and Copper(II). The Crystal Structures of [CrCl₂(Me₃SiNPMe₃)₂], [PdCl₂(Me₃SiNPEt₃)₂], and [CuCl₂(Me₃SiNPMe₃)]₂ The title compounds have been prepared by the reaction of the silylated phosphaneimines Me₃SiNPR₃ (R = CH₃, C₂H₅) with CrCl₂(THF)₂, PdCl₂ and CuCl₂, respectively, in dichloromethane suspensions. All donor-acceptor complexes were characterized by IR spectroscopy and by crystal structure determinations. [ CrCl₂(Me₃SiNPMe₃ )₂]: Space group Pccn, Z = 4, structure determination with 2104 observed unique reflections, R = 0.045. Lattice dimensions at ?70°C: a = 1326.3, b = 1562.5, c = 1171.5 pm. Within the monomeric molecular structure the chromium atom is planarly coordinated within the trans-configuration of the Cl atoms and the N atoms with distances of Cr? Cl = 235.94 pm and Cr? N = 211.7 pm. [ PdCl₂(Me₃SiNPEt₃)₂ ]: Space group P2₁/n, Z = 2, structure determination with 2412 observed unique reflections, R = 0.031. Lattice dimensions at 20°C: a = 917.3, b = 1390.2, c = 1161.7 pm, β = 95.80°. Within the monomeric molecular structure the palladium atom is planarly coordinated within the trans-configuration of the Cl atoms and the N atoms with distances of Pd? Cl = 222.9 pm and Pd? N = 209.5 pm. [ CuCl₂(Me₃SiNPMe₃)₂ ]: Space group Pbca, Z = 4, structure determination with 1861 observed unique reflections, R = 0.067. Lattice dimensions at ?70°C: a = 1440.2, b = 1205.1, c = 1536.5 pm. The compound forms centrosymmetric dimeric molecules, in which the Cu atoms are linked via almost symmetrical chloro-bridges with Cu? Cl distances of 231.4 pm. The distance Cu? N is 196.7 pm.     

Die Reaktion von Cyanid-Ionen mit Trimethylgallium. Die Kristallstrukturen von [Cs{CN(GaMe3)2}]n und [Cs(Toluol)2{CN(GaMe3)2}]n

The Reaction of Cyanide Ions with Trimethylgallium. The Crystal Structures of [Cs{CN(GaMe₃)₂}]_n (1) and [Cs(toluene)₂{CN(GaMe₃)₂}]_n (2) CsCN reacts with GaMe₃ in the molar ratio of 1 : 2 in the absence of additional solvent to the metalate [Cs{CN(GaMe₃)₂}] ( 1 ). 1 can be recrystallized from MeCN/toluene, forming [Cs(toluene)₂{CN(GaMe₃)₂}] ( 2 ). If CsCN is treated with one equivalent GaMe₃ in Et₂O at 20 °C, the metalate [Cs(NCGaMe₃)] can be isolated. 1 – 3 were characterized by NMR, IR, and MS techniques. In addition, X-ray structure analyses of 1 and 2 were prepared. According to the structural characterization 1 consists of a helix of Cs⁺ ions and side-on coordinated anions [Me₃GaCNGaMe₃]^–, running along [010]. π-Electron-Cs⁺ contacts between Cs cations and toluene molecules are dominating the structure of 2 . The residual equatorial positions at the [Cs(toluene)₂]⁺ sandwich-ion are occupied by Cs⁺-hydrogen(methyl) interactions. A three-dimensional network is the result of the contacts between cations and anions.     

[PdCl(TeMe2)3](BArF) – The First Structurally Characterized Palladium(II) Complex with TeMe2 Ligands

[PdCl(TeMe₂)₃]BAr^F ( 4 ) forms as the major tellurium containing product from the reaction of [(4‐Mebti)PdCl] with TeMe₂ and Na(BAr^F) and is isolated by crystallization from the reaction mixture. At ?20 °C, the compound forms orange columns from toluene/pentane, space group , with Z = 2. In the solid, the cationic [PdCl(TeMe₂)₃]⁺ complex ions show a non‐planar PdClTe₃ coordination unit and are associated to dimers via weak Pd···Te interactions.     

Die Kristallstrukturen von (NBu4)[(Ph3Sn)3(MoO4)2] und (NBu4)[(Ph3Sn)3(MoO4)2]·CH3CN: Organozinnmolybdate mit neuartigen 3D‐Netzwerken

The Crystal Structures of (NBu₄)[(Ph₃Sn)₃(MoO₄)₂] and (NBu₄)[(Ph₃Sn)₃(MoO₄)₂]·CH₃CN: Organotin Molybdates with Novel 3D Networks The reaction of (NBu₄)₂[Mo₆O₁₉] with Ph₃SnCl and NBu₄OH in acetonitrile as solvent leads to the formation of (NBu₄)[(Ph₃Sn)₃(MoO₄)₂] ( 5 ). 5 and (NBu₄)[(Ph₃Sn)₃(MoO₄)₂]· CH₃CN 6 have been characterized by single crystal structure analysis at 220 K. 5 crystallizes monoclinic with a = 1429.5(4) pm, b = 2292.2(3) pm, c = 2269.7(5) pm, β = 107.42(3)°, space group Cc, 6 crystallizes orthorhombic with a = 1820.5(1) pm, b = 1848.6(2) pm and c = 2143.9(1) pm, space group P2₁2₁2₁. The crystal structures of 5 and 6 consist of isolated (NBu₄)⁺ cations and anionic 3D networks of Ph₃SnO₂ trigonal bipyramides and MoO₄ tetrahedra which are linked by common oxygen atoms.     

Die Kristallstrukturen einer Serie von Verbindungen mit Kationen des Typs [R3PNH2]+, [R3PN(H)SiMe3]+ und [R3PN(SiMe3)2]+

Crystal Structures of a Series of Compounds with Cations of the Type [R₃PNH₂]⁺, [R₃PN(H)SiMe₃]⁺, and [R₃PN(SiMe₃)₂]⁺ The crystal structures of a series of compounds with cations of the type [R₃PNH₂]⁺, [R₃PN(H)SiMe₃]⁺, and [R₃PN(SiMe₃)₂]⁺, in which R represents various organic residues, are determined by means of X‐ray structure analyses at single crystals. The disilylated compounds [Me₃PN(SiMe₃)₂]⁺I^–, [Et₃PN(SiMe₃)₂]⁺I^–, and [Ph₃PN(SiMe₃)₂]⁺I₃^– are prepared from the corresponding silylated phosphaneimines R₃PNSiMe₃ with Me₃SiI. [Me₃PNH₂]Cl (1): Space group P2₁/n, Z = 4, lattice dimensions at –71 °C: a = 686.6(1), b = 938.8(1), c = 1124.3(1) pm; β = 103.31(1)°; R = 0.0239. [Et₃PNH₂]Cl (2): Space group Pbca, Z = 8, lattice dimensions at –50 °C: a = 1272.0(2), b = 1147.2(2), c = 1302.0(3) pm; R = 0.0419. [Et₃PNH₂]I (3): Space group P2₁2₁2₁, Z = 4, lattice dimensions at –50 °C: a = 712.1(1), b = 1233.3(2), c = 1257.1(2) pm; R = 0.0576. [Et₃PNH₂]₂[B₁₀H₁₀] (4): Space group P2₁/n, Z = 4, lattice dimensions at –50 °C: a = 809.3(1), b = 1703.6(1), c = 1800.1(1) pm; β = 96.34(1)°; R = 0.0533. [Ph₃PNH₂]ICl₂ (5): Space group P1, Z = 2, lattice dimensions at –60 °C: a = 825.3(3), b = 1086.4(3), c = 1241.2(4) pm; α = 114.12(2)°, β = 104.50(2)°, γ = 93.21(2)°; R = 0.0644. In the compounds 1–5 the cations are connected with their anions via hydrogen bonds of the NH₂ groups with 1–3 forming zigzag chains. [Me₃PN(H)SiMe₃][O₃S–CF₃] (6): Space group P2₁/c, Z = 8, lattice dimensions at –83 °C: a = 1777.1(1), b = 1173.6(1), c = 1611.4(1) pm; β = 115.389(6)°; R = 0.0332. [Et₃PN(H)SiMe₃]I (7): Space group P2₁/n, Z = 4, lattice dimensions at –70 °C: a = 1360.2(1), b = 874.2(1), c = 1462.1(1) pm; β = 115.19(1)°; R = 0.066. In 6 and 7 the cations form ion pairs with their anions via NH … X hydrogen bonds. [Me₃PN(SiMe₃)₂]I (8): Space group P2₁/c, Z = 8, lattice dimensions at –60 °C: a = 1925.4(9), b = 1269.1(1), c = 1507.3(4); β = 111.79(3)°; R = 0.0581. [Et₃PN(SiMe₃)₂]I (9): Space group Pbcn, Z = 8, lattice dimensions at –50 °C: a = 2554.0(2), b = 1322.3(1), c = 1165.3(2) pm; R = 0.037. [Ph₃PN(SiMe₃)₂]I₃ (10): Space group P2₁, Z = 2, lattice dimensions at –50 °C: a = 947.7(1), b = 1047.6(1), c = 1601.6(4) pm; β = 105.96(1)°; R = 0.0334. 8 to 10 are built up from separated ions.     

Die Kristallstrukturen der Azido‐Platinate (AsPh4)2[Pt(N3)4] und (AsPh4)2[Pt(N3)6]

Crystal Structures of the Azido Platinates (AsPh₄)₂[Pt(N₃)₄] and (AsPh₄)₂[Pt(N₃)₆] The crystal structures of the two homoleptic azido platinates (AsPh₄)₂[Pt(N₃)₄] ( 1 ) and (AsPh₄)₂[Pt(N₃)₆] ( 2 ) were determined by X‐ray diffraction at single crystals. In 1 the [Pt(N₃)₄]^2– ions are without crystallographic site‐symmetry, and the platinum atoms show a planar surrounding. The [Pt(N₃)₆]^2– ions in 2 are centrosymmetric (C_i) with an octahedral surrounding at the platinum atoms. While 1 is highly explosive, 2 is of significantly greater stability. This behaviour is explained by the packing conditions. 1 : Space group P2₁/n, Z = 6, lattice dimensions at –80 °C: a = 1045.3(1), b = 1620.2(1), c = 4041.0(3) pm; β = 96.70(1)°; R₁ = 0.0654. 2 : Space group P1, Z = 1, lattice dimenstions at –80 °C: a = 1027.6(1), b = 1049.1(2), c = 1249.9(3) pm; α = 88.27(1)°, β = 74.13(1)°, γ = 67.90(1)°; R₁ = 0.0417.     

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.     

Iod‐katalysierte Herstellung von intermetallischen Verbindungen der Edelmetalle: Die Kristallstrukturen von BePd2 und BePd3

Iodine‐Catalyzed Production of Noble Metal‐Rich Intermetallics: The Crystal Structures of BePd₂ and BePd₃ The two Pd‐richest phases of the Be—Pd system are accessible 400 °C below the eutectic temperature within 48 h through an iodine‐catalyzed reaction of the metals. The crystal structures of BePd₂ and BePd₃ have been determined by means of X‐ray powder diffractometry. BePd₃ is isotypic to BRe₃. BePd₂ adopts a MoSi₂ type related structure.     

Die Reaktion des tert.Butyl-lithiums mit Aluminiumtribromid; Molekülstrukturen von [HAl(CMe3)2]3 und [LiHAl(CMe3)3]2

Reaction of tert.Butyl-lithium with Aluminiumtribromide; Molecular Structures of [HAl(CMe₃)₂]₃ and [LiHAl(CMe₃)₃]₂ The reaction of tert.butyl-lithium with aluminiumtrihalide at low temperatures was reinvestigated. Four compounds were isolated: trimeric di(tert.butyl)alane(III) 1 , monomeric (solution in benzene)/dimeric (solid state) lithium-tri(tert.butyl)alanate(III) 2 , tri(tert.butyl)alane 3 and lithium-tetra(tert.butyl)alanate 4 . X-ray structure analyses gave a planar sixmembered Al? H heterocycle for 1 and a Li? H-bridged dimer showing intramolecular interactions of lithium with C? H σ-bonds for 2 .     

Phosphaniminato‐Komplexe des Zirconiums: Die Kristallstrukturen von [ZrCl3(NPPh3)(HNPPh3)2] und [ZrCl2(NPPh3)2(HNPPh3)2]

Phosphoraneiminato Complexes of Zirconium: Crystal Structures of [ZrCl₃(NPPh₃)(HNPPh₃)₂] and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] The phosphoraneiminato complexes [ZrCl₃(NPPh₃)(HNPPh₃)₂] ( 1 ) and [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] ( 2 ) have been obtained by reaction of [ZrCl₄(THF)₂] with [CsNPPh₃]₄ in THF solution to give colourless moisture sensitive crystals which are characterized by X‐ray structure determinations. [ZrCl₃(NPPh₃)(HNPPh₃)₂] ( 1 ): Space group P 1, Z = 2, lattice dimensions at 193 K: a = 1209.4(2); b = 1480.8(2); c = 1814.2(2) pm; α = 71.203(13)°, β = 71.216(13)°, γ = 74.401(13)°; R = 0.0476. The zirconium atom of 1 is oktahedrally coordinated by the three chlorine atoms in meridional arrangement and by the three nitrogen atoms of the (NPPh₃^–) ligand and of the two phosphane imine molecules HNPPh₃. The ZrN bond distance of the (NPPh₃^–) group (193.5 pm) corresponds with a double bond. [ZrCl₂(NPPh₃)₂(HNPPh₃)₂] ( 2 ): Space group P 1, Z = 4, lattice dimensions at 193 K: a = 1447.6(2); b = 1925.7(2), c = 2457.0(2) pm; α = 67.317(12)°, β = 87.376(12)°, γ = 87.103(13)°; R = 0.0408. The zirconium atom in 2 is octahedrally coordinated by the two chlorine atoms in trans position, and by the nitrogen atoms of the two (NPPh₃^–) groups as well as by the two HNPPh₃ molecules. The ZrN distance of the (NPPh₃^–) ligands (198.9 and 202.0 pm) suggest some π‐interaction between the zirconium and the nitrogen atoms.     

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.     

Einfluß der Ringatome auf die Struktur von Triel‐Pentel‐Heterozyklen – Synthese und Molekülstrukturen von [Me2InAs(SiMe3)2]2 und [Me2InSb(SiMe3)2]3

Influence of the Ring Atoms on the Structure of Triel‐Pentel Heterocycles – Synthesis and X‐Ray Crystal Structures of [Me₂InAs(SiMe₃)₂]₂ and [Me₂InSb(SiMe₃)₂]₃ Triel‐pentel heterocycles [Me₂InE(SiMe₃)₂]_x have been prepared by dehalosilylation reactions from Me₂InCl and E(SiMe₃)₃ (E = As, x = 2; E = Sb, x = 3) and characterised by NMR spectroscopy and by X‐ray crystal structure analyses. In addition the X‐ray crystal structures of [Me₂GaAs(SiMe₃)₂]₂ and [Me₂InP(SiMe₃)₂]₂ are reported. The compounds complete a family of 13 identically substituted heterocycles [Me₂ME(SiMe₃)₂]_x (M = Al, Ga, In; E = N, P, As, Sb, Bi; x = 2, 3), whose structures were investigated depending on the ring atoms M and E. The tendencies that have been observed concerning the ring sizes can be explained by the interplay of the atomic radii of the central atoms and the sterical demand of the ligands. After a formal separation of the M–E bonds in σ bonds and dative bonds the characteristic differences and trends in the endocyclic and exocyclic bond angles of both centres M and E can be interpreted on the basis of a simple Lewis acid/base adduct model.     

Synthese und Kristallstrukturen von [(Ph3As)2CCN–MnBr3], [(Ph3As)2CCN–CoBr3] und [(Ph3As)2CCN]+CuBr2–

Syntheses and Crystal Structures of [(Ph₃As)₂CCN–MnBr₃], [(Ph₃As)₂CCN–CoBr₃], and [(Ph₃As)₂CCN]⁺CuBr₂^– The di(arsa)acetonitrilium bromide [(Ph₃As)₂CCN]Br reacts with the anhydrous dibromides of manganese and cobalt in acetonitrile to form the molecular complexes [(Ph₃As)₂CCN–MBr₃] [M = ( 1 ), Co( 2 )] with zwitterionic structures. With copper(I)bromide, however, the ionic compound [(Ph₃As)₂CCN]⁺CuBr₂^– ( 3 ) is formed. All complexes are characterized by IR spectroscopy and by crystal structure analyses. 1 and 2 crystallize isotypically with each other in the space group P 1 with two formula units per unit cell. The MBr₃^– fragments in the molecular complexes are connected to the N atom of the [(Ph₃As)₂CCN]⁺ cation showing bond angles C–N–Mn of 156.9° and C–N–Co of 161°, and distances Mn–N of 215.6 pm and Co–N of 201 pm. In 3 , on the other hand, (space group C2/c, Z = 4) the ions [(Ph₃As)₂CCN]⁺ and the linear Br–Cu–Br^– ion are to be found concurrent but separate.     

Reaktionen silylierter Phosphanimine mit Iodmonochlorid und Iodtrichlorid. Die Kristallstrukturen von [Me3SiNPMe3 · ICl], [Ph3PNCl · ICl] und [Me3PN(H)PMe3] [ICl2]2

Reactions of Silylated Phosphorane Imines with Iodine Monochloride and Iodine Trichloride. The Crystal Structures of [Me₃SiNPMe₃ · ICl], [Ph₃PNCl · ICl], and [Me₃PN(H)PMe₃][ICl₂]₂ The donor-acceptor complex [Me₃SiNPMe₃ · ICl] has been prepared from Me₃SiNPMe₃ and ICl in acetonitrile solution forming yellow-orange crystals. [Ph₃PNCl · ICl] can be prepared by the reaction of Me₃SiNPPh₃ with ICl₃ in dichloromethane solution forming pale yellow crystals. [Me₃PN(H)PMe₃][ICl₂]₂ is formed in a small amount by a slow reaction of Me₃SiNPMe₃ with ICl₃ in CCl₄ suspension in the presence of traces of moisture. All samples are characterized by IR spectroscopy and by X-ray structure analyses. [Me₃SiNPMe₃ · ICl] (1) : Space group Iba2, Z = 8, structure solution with 1 727 observed unique reflections, R = 0.051. Lattice dimensions at ?60°C: a = 1 510.7, b = 1 862.8, c = 988.9 pm. 1 has a molecular structure in which the N atom of the phosphorane imine is connected with the iodine atom of the ICl molecule in a linear arrangement N? I? Cl. Bond lengths N? I = 222.7 pm, I? Cl = 265.1 pm. [Ph₃PNCl · ICl] (2) : Space group Pna2₁, Z = 4, structure solution with 1 530 observed unique reflections, R = 0.030. Lattice dimensions at 20°C: a = 1 522.8, b = 1 408.3, c = 865.8 pm. 2 has a molecular structure in which the N atom of the N chlorophosphorane imine is connected with the iodine atom of the ICl molecule in a linear arrangement. Bond lengths N? Cl = 174.4 pm, N? I = 229.5 pm, I? Cl = 251.2 pm. [Me₃PN(H)PMe₃][ICl₂]₂ (3) : Space group P2₁/c, Z = 4, structure solution with 1 989 observed unique reflections, R = 0.029. Lattice dimensions at ?50°C: a = 1 223.1, b = 1 090.2, c = 1 482.8 pm, β = 112.21°. 3 consists of [Me₃PN(H)PMe₃]²⁺ ions and ICl₂^? anions. The PNP bond angle of the dication amounts to 134.4° with PN distances of 165.6 and 166.1 pm, approximately according to double bonds.     

Synthese und Eigenschaften von Triphenylzinnmolybdaten mit kettenförmigen Anionen des Typs 1∞[(Ph3Sn)MoO4]–. Die Kristallstrukturen von (nPr4N)[(Ph3Sn)MoO4]·CH3CN, (nBu4N)[(Ph3Sn)MoO4], [Zn(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH und [Cu(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH

The reaction of Ph₃SnCl, (R₄N)₂[Mo₆O₁₉] and (R₄N)OH in a molar ratio of 6:1:10 leads to the formation of (R₄N)[(Ph₃Sn)MoO₄] (R = ⁿPr ( 1 ), ⁿBu ( 2 )). Compounds 1· CH₃CN and 2 have been charactarized by IR spectroscopy and single crystal X‐ray diffraction. 1· CH₃CN forms orthorhombic crystals, space group P2₁2₁2₁ with a = 1339.9(2), b = 1508.9(2), c = 1733.2(3) pm. 2 crystallizes in the monoclinic space group P2₁ with a = 1342.6(2), b = 2280.3(4), c = 1344.0(2) pm, β = 118.34(1). Both compounds 1 and 2 consist of isolated R₄N⁺ cations and polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains with an alternating arrangement of Ph₃Sn⁺ and MoO₄^2– groups. Treatment of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)copper(II) succinate yields [Cu(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 3 ). The zinc derivative [Zn(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 4 ) is obtained similarly by reaction of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)zinc(II) formiate. Compounds 3· 2DMF · EtOH and 4· 2DMF · EtOH crystallize in the monoclinic space group P2₁/n with a = 1998.0(2), b = 1313.3(1), c = 2181.6(2) pm, β = 90.97(1)° for 3 and a = 2015.4(1), b = 1316.7(1), c = 2157.0(1) pm, β = 90.40(1)° for 4 . Like in the cases of 1 and 2, polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains are observed. The [M(en)₂]²⁺ units (M = Cu, Zn) act as linkers between the $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains to give 2D layer structures with (6, 3) net topology.     

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.     

Trichloropalladate(II) Complexes with Pyridine Ligands – Molecular Structure and Conformational Analysis of [K(18C6)][PdCl3(py)]

[K(18C6)]₂[Pd₂Cl₆] ( 1 ) (18C6 = 18‐crown‐6) was found to react with pyridines in a strictly stoichiometric ratio 1 : 2 in methylene chloride or nitromethane to yield trichloropalladate(II) complexes [K(18C6)][PdCl₃(py*)] (py* = py, 2a ; 4‐Bnpy, 2b ; 4‐tBupy, 2c ; Bn = benzyl; tBu = tert‐butyl). The reaction of 1 with pyrimidine (pyrm) in a 1 : 1 ratio led to the formation of the pyrimidine‐bridged bis(trichloropalladate) complex [K(18C6)]₂[(PdCl₃)₂(μ‐pyrm)] ( 3 ). The identities of the complexes were confirmed by means of NMR spectroscopy (¹H, ¹³C) and microanalysis. The X‐ray structure analysis of 2a reveals square‐planar coordination of the Pd atom in the [PdCl₃(py)]^? anion. The pyridine plane forms with the complex plane an angle of 55.8(2)°. In the [K(18C6)]⁺ cation the K⁺ lies outside the mean plane of the crown ether (defined by the 6 O atoms) by 0.816(1) Å. There are tight K···Cl contacts between the cation and the anion (K···Cl1 3.340(2) Å, K···Cl2 3.166(2) Å). To gain an insight into the conformation of the [PdCl₃(py)]^? anion, DFT calculations were performed showing that the equilibrium structure ( 6eq ) has an angle between the pyridine ligand and the complex plane of 35.3°. Rotation of the pyridine ligand around the Pd–N vector exhibited two transition states where the pyridine ligand lies either in the complex plane ( 6TS _pla, 0.87 kcal/mol above 6eq ) or is perpendicular to it ( 6TS _per, 3.76 kcal/mol above 6eq ). Based on an energy decomposition analysis the conformation of the anion is discussed in terms of repulsive steric interactions and of stabilizing σ and π orbital interactions between the PdCl₃^? moiety and the pyridine ligand.     

Die Kristallstrukturen von Triphenylarsin-p-toluolsulfonylimin und seines Donor-Akzeptorkomplexes [ZrCl4(Ph3AsNSO2Tol)]2

The Crystal Structures of Triphenylarsin-p-toluene Sulfonylimine and of its Donor-Acceptor Complex [ZrCl₄(Ph₃AsNSO₂Tol)]₂ The molecular structures of the title compounds are reported. In the donor-acceptor complex [ZrCl₄(Ph₃AsNSO₂Tol)]₂ the zirconium atoms are bridged by the oxygen atoms of the triphenylarsin-p-toluene sulfonylimine molecules, forming a centrosymmetric dimer with a puckered Zr₂O₄S₂ eight-membered ring in the chair conformation. Ph₃AsNSO₂Tol: Space group P1 , Z = 2, structure determination with 4 010 observed unique reflections, R = 0.036. Lattice dimensions at 19°C: a = 897.52(4), b = 1 071.82(6), c = 1 337,49(5) pm, α = 110.280(4)°, β = 98.814(4)°, γ = 109.872(4)°. [ZrCl₄(Ph₃AsNSO₂Tol)]₂: Space group P2₁/n, Z = 4, structure determination with 3 762 observed unique reflections, R = 0.078. Lattice dimensions at ?60°C: a = 1 387.3(4), b = 1 434.9(2), c = 1 404.7(4) pm, β = 92.71(1)°.