Iodostannate mit polymeren Anionen: (Me3PhN)4 [Sn3I10], [Me2HN–(CH2)2–NMe2H]2 [Sn3I10] und [Me2HN–(CH2)2–NMe2H][Sn3I8]

Iodostannates with Polymeric Anions: (Me₃PhN)₄ [Sn₃I₁₀], [Me₂HN–(CH₂)₂–NMe₂H]₂ [Sn₃I₁₀], and [Me₂HN–(CH₂)₂–NMe₂H] [Sn₃I₈] The polymeric iodostannate anions in (Me₃PhN)₄ [Sn₃I₁₀] ( 1 ) and [Me₂HN–(CH₂)₂–NMe₂H]₂ [Sn₃I₁₀] ( 2 ) consist of Sn₃I₁₂‐trioctahedra, which share four common iodine atoms with adjacent units to form infinite layers in 1 and polymeric chains in 2 . In the anion of [Me₂HN–(CH₂)₂–NMe₂H] [Sn₃I₈] ( 3 ) distorted SnI₆ octahedra sharing common edges and vertices form a two‐dimensional network. (Me₃PhN)₄ [Sn₃I₁₀] ( 1 ): Space group C2/c (No. 15), a = 2406.9(2), b = 968.26(7), c = 2651.7(2) pm, β = 111.775(9), V = 5738.9(8) · 10⁶ pm³; [Me₂HN–(CH₂)₂–NMe₂H]₂ [Sn₃I₁₀] ( 2 ): Space group P2₁/n (No. 14), a = 1187.2(1), b = 1554.4(1), c = 1188.9(1) pm, β = 116.620(8), V = 1961.4(3) · 10⁶ pm³; [Me₂HN–(CH₂)₂–NMe₂H] [Sn₃I₈] ( 3 ): Space group P2₁/c (No. 14), a = 1098.9(2), b = 803.93(7), c = 1571.5(2) pm, β = 102.96(1), V = 1352.9(2) · 10⁶ pm³.     

Iodostannate(II) mit kettenförmigen [SnI3]–‐Anionen – der Übergang von fünffach zu sechsfach koordinierten SnII‐Zentralatomen

Iodostannates(II) with Anionic [SnI₃]^– Chains – the Transition from Five to Six‐coordinated Sn^II The iodostannates (Me₄N) [SnI₃] ( 1 ), [Et₃N–(CH₂)₄–NEt₃] [SnI₃]₂ ( 2 ), [EtMe₂N–(CH₂)₂–NEtMe₂] [SnI₃]₂ ( 3 ), [Me₂HN–(CH₂)₂–NH–(CH₂)₂–NMe₂H] [SnI₃]₂ ( 4 ), [Et₃N–(CH₂)₆–NEt₃] [SnI₃]₂ ( 5 ) and [Pr₃N–(CH₂)₄–NPr₃]‐ [SnI₃]₂ · 2 DMF ( 6 ) with the same composition of the anionic [SnI₃]^– chains show differences in the coordination of the Sn^II central atoms. Whereas the Sn atoms in 1 and 2 are coordinated in an approximately regular octahedral fashion, in compounds 3 – 6 the continuous transition to coordination number five in (Pr₄N) [SnI₃] ( 7 ) or [Fe(dmf)₆] [SnI₃]₂ ( 8 ) can be observed. Together with the shortening of two or three Sn–I bonds, the bonds in trans position are elongated. Thus weak, long‐range Sn…I interactions complete the distorted octahedral environment of SnI₄ groups in 3 and 4 and SnI₃ groups in 5 and 6 . Obviously the shape, size and charge of the counterions and the related cation‐anion interactions are responsible for the variants in structure and distortion.     

Polymere Iodoplumbate – Synthese und Kristallstrukturen von (Pr3N–C2H4–NPr3)[Pb6I14(dmf)2] · 4 DMF, (Pr3N–C2H4–NPr3)[Pb(dmf)6][Pb5I14] · DMF und (Me3N–C2H4–NMe3)2[Pb2I7]I

Polymeric Iodoplumbates – Synthesis and Crystal Structures of (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF, (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄] · DMF, and (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ) and (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄] · DMF ( 2 ) have almost the same composition, but completely different structures. Both compounds are formed selectively depending on the reaction and crystallization conditions. In 2 the Pb^II atoms are coordinated either by six bridging I^– ligands in the two-dimensional [Pb₅I₁₄]^4– network or by six DMF ligands in the [Pb(dmf)₆]²⁺ cations. In contrast, (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I ( 3 ) contains non-coordinating I^– anions between the iodoplumbate layers. The iodoplumbate anions in 2 and 3 consist of face and corner sharing PbI₆ octahedra, whereas in 1 PbI₆ and PbI₅(dmf) octahedra share common edges to form a one-dimensional polymeric section of the PbI₂ structure. (Pr₃N–C₂H₄–NPr₃)[Pb₆I₁₄(dmf)₂] · 4 DMF ( 1 ): Space group P1, a = 920.1(3), b = 1597.2(5), c = 1613.9(4) pm, α = 66.02(2), β = 84.53(2), γ = 85.99(2)°, V = 2156(1) · 10⁶ pm³; (Pr₃N–C₂H₄–NPr₃)[Pb(dmf)₆][Pb₅I₁₄]·DMF ( 2 ): Space group P2₁, a = 1201.21(9), b = 3031.1(2), c = 1294.96(9) pm, β = 108.935(7)°, V = 4459.8(5) · 10⁶ pm³; (Me₃N–C₂H₄–NMe₃)₂[Pb₂I₇]I ( 3 ): Space group Pnma, a = 2349.9(2), b = 1623.83(9), c = 980.75(7) pm, V = 3742.4(5) · 10⁶ pm³.     

Synthese und Kristallstrukturen der Phosphaniminato-Komplexe [SnI(NPPh3)]2 und [SnI3(NPPh3)]2

Synthesis and Crystal Structures of the Phosphoraneiminato Complexes [SnI(NPPh₃)]₂ and [SnI₃(NPPh₃)]₂ The phosphoraneiminato complex of the divalent tin, [SnI(NPPh₃)]₂ ( 1 ), originates from the reaction of metallic tin with N-iodine triphenylphosphaneimine, INPPh₃, in dichloromethane suspension. 1 forms yellow, moisture sensitive crystals, which can be converted into the red phosphoraneiminato complex of the tetravalent tin, [SnI₃(NPPh₃)]₂ ( 2 ), by oxidation with iodine. According to the crystal structure analyses 1 and 2 have centrosymmetric dimeric molecular structures in which the tin atoms are linked via the N atoms of the NPPh₃^– groups. The tin atoms in 1 have a ψ-tetrahedral coordination, those in 2 a trigonal-bipyramidal one. 1 : Space group P 1, Z = 1, lattice dimensions at –80 °C: a = 779.0(1), b = 1080.1(1), c = 1170.4(1) pm, α = 64.49(1)°, β = 88.42(1)°, γ = 79.13(1)°, R = 0.0293. 2 : Space group P2₁/n, Z = 2, lattice dimensions at –80 °C: a = 1252.4(1), b = 1421.3(3), c = 1260.1(1) pm, β = 108.50(1)°, R = 0.0518.     

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 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.     

Neue Phosphaniminato‐Komplexe von Molybdän und Wolfram. Die Kristallstrukturen von [(μ‐S2N2){MoCl4(NPPh3)}2], [Mo(NPPh3)4][BF4]2, [W(S)2(NPPh3)2] und [Ph3PNH2]+[SCN]–

New Phosphoraneiminato Complexes of Molybdenum and Tungsten. Crystal Structures of [(μ‐S₂N₂){MoCl₄(NPPh₃)}₂], [Mo(NPPh₃)₄][BF₄]₂, [W(S)₂(NPPh₃)₂], and [Ph₃PNH₂]⁺[SCN]^– The binuclear molybdenum(V)phosphoraneiminato complex [(μ‐S₂N₂){Mo^VCl₄(NPPh₃)}₂] ( 1 ) has been prepared by the reaction of the chlorothionitreno complex [Mo^VICl₄(NSCl)]₂ with Me₃SiNPPh₃ in dichloromethane forming green crystals. The temperature dependent magnetic susceptibility in the range of 2–30 K shows ideal behaviour according to the Curie law with a magnetic moment of 1.60 B.M. According to the crystal structure determination 1 forms centrosymmetric molecules in which the molybdenum atoms are connected by the nitrogen atoms of the S₂N₂ molecule. In trans‐position to it the nitrogen atoms of the phosphoraneiminato groups (NPPh₃^–) are coordinated with Mo–N bond lengths of 171(1) pm. The tetrakis(phosphoraneiminato) complex [Mo(NPPh₃)₄]‐ [BF₄]₂ ( 2 ) has been obtained as colourless crystal needles by the reaction of MoN(NPPh₃)₃ with boron trifluoride etherate in toluene solution. In the dication the molybdenum atom is tetrahedrally coordinated by the nitrogen atoms of the (NPPh₃^–) groups with Mo–N bond lengths of 179,8–181,0(3) pm. The dithio‐bis(phosphoraneiminato) tungsten complex [W(S)₂(NPPh₃)₂] ( 3 ) is formed as yellow crystals as well as [Ph₃PNH₂]⁺[SCN]^– ( 4 ) from the reaction of WN(NPPh₃)₃ with carbon disulfide in tetrahydrofurane in the presence of traces of water. 3 has a monomeric molecular structure with tetrahedrally coordinated tungsten atom with bond lengths W–S of 214.5(5) pm and W–N of 179(1) pm. In the structure of 4 the thiocyanate ions are associated by hydrogen bonds of the NH₂ group of the [Ph₃PNH₂]⁺ ion to give a zigzag chain. 1 : Space group Pbca, Z = 4, lattice constants at –80 °C: a = 1647.9(3), b = 1460.8(2), c = 1810.4(4) pm; R₁ = 0.0981. 2 : Space group P1, Z = 2, lattice constants at –80 °C: a = 1162.5(1), b = 1238.0(1), c = 2346.2(2) pm; α = 103.14(1)°, β = 90.13(1)°, γ = 97.66(1)°; R₁ = 0.0423. 3 : Space group Fdd2, Z = 8, lattice constants at –80 °C: a = 3310.1(4), b = 2059.7(2), c = 966,7(1) pm; R₁ = 0.0696. 4 : Space group P2₁2₁2₁, Z = 4, lattice constants at –80 °C: a = 1118.4(1), b = 1206.7(1), c = 1279.9(1) pm; R₁ = 0.0311.     

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)°.     

Das SCN–-Ion als ambidenter Ligand – Synthese und Kristallstrukturen von (Bu4N)4[Ag2Fe2(SCN)12] und (Et4N)2 [Ag2Fe(SCN)6]

The SCN^– Ion as an Ambidentate Ligand – Synthesis and Crystal Structures of (Bu₄N)₄[Ag₂Fe₂(SCN)₁₂] and (Et₄N)₂ [Ag₂Fe(SCN)₆] In (Bu₄N)₄[Ag₂Fe₂(SCN)₁₂] · 2 CH₃NO₂ ( 1 ) and (Et₄N)₂[Ag₂Fe(SCN)₆] ( 2 ) the ambidentate SCN^– anions link Ag⁺ with Fe³⁺ and Fe²⁺ centers, respectively. The tetranuclear anions in 1 are built from [Fe(NCS)₆]^3– groups connected by Ag⁺ ions. In 2 the same bridging pattern leads to polymeric anionic chains containing [Fe(NCS)₆]^4– groups linked by Ag⁺ ions. (Bu₄N)₄[Ag₂Fe₂(SCN)₁₂] · 2 CH₃NO₂ ( 1 ): a = 1184.10(10), b = 1370.80(10), c = 1776.5(2) pm, α = 99.090(10), β = 102.100(10), γ = 100.360(10)°, V = 2715.5(4) · 10⁶ pm³, space group P1; (Et₄N)₂[Ag₂Fe(SCN)₆] ( 2 ): a = 1607.0(2), b = 1006.92(9), c = 1096.13(9) pm, V = 1773.7(3) · 10⁶ pm³, space group Pnnm.     

Molybdän‐ und Wolfram‐Komplexe mit MNS‐Sequenzen. Die Kristallstrukturen von [MoCl3(N3S2)(1,4‐Dioxan)2] und [Mo2Cl2(μ‐NSN)2(μ‐O)(NCMe3)(OCMe3)2]2

Molybdenum and Tungsten Complexes with MNS Sequences. Crystal Structures of [MoCl₃(N₃S₂)(1,4‐dioxane)₂] and [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ The cyclo‐thiazeno complexes [Cl₃MNSNSN]₂ of molybdenum and tungsten react with 1,4‐dioxane in dichloromethane suspension to give the binuclear donor‐acceptor complexes [μ‐(1,4‐dioxane){MCl₃(N₃S₂)}₂] which are characterized by IR spectroscopy. With excess 1,4‐dioxane the molybdenum compound forms the complex [MoCl₃(N₃S₂)(1,4‐dioxane)₂] in which, according to the crystal structure determination, one of the dioxane molecules coordinates at the molybdenum atom, the other one at one of the sulfur atoms of the cyclo‐thiazeno ring. The μ‐(NSN^2–) complex [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ has been obtained by the reaction of [MoN(OCMe₃)₃] with trithiazyle chloride in carbontetrachloride solution. According to the crystal structure determination this compound forms centrosymmetric dimeric molecules via two of the nitrogen atoms of two of the μ‐(NSN) groups to give a Mo₂N₂ fourmembered ring. [MoCl₃(N₃S₂)(1,4‐dioxane)₂]: Space group P2₁/c, Z = 4, lattice dimensions at –70 °C: a = 1522.9(2); b = 990.3(1); c = 1161.7(1) pm; β = 106.31(1)°, R₁ = 0.0317. [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ · 4 CCl₄: Space group P2₁/c, Z = 2, lattice dimensions at –83 °C: a = 1216.7(1); b = 2193.1(2); c = 1321.8(1) pm; β = 98.23(1)°; R₁ = 0.0507.     

(PPh4)2[Cl2Re(N3S2)(μ‐NSN)(μ‐N≡ReCl3)]2 – ein Rhenium(VII)‐Komplex mit einer Nitrido‐, einer Dinitridosulfato(II)‐ und einer Rhena‐3,5‐dithia‐2,4,6‐triazino‐Funktion

(PPh₄)₂[Cl₂Re(N₃S₂)(μ‐NSN)(μ‐N≡ReCl₃)]₂ – a Rhenium(VII) Complex with a Nitrido, a Dinitridosulfato(II), and a Rhena‐3,5‐dithia‐2,4,6‐triazino Function The title compound has been prepared from PPh₄[Re^VIICl₄(NSCl)₂] with N(SiMe₃)₃ in dichloromethane solution to give red‐brown single crystals, which were suitable for a crystal structure determination. As a by‐product PPh₄[ReNCl₄] is formed. (PPh₄)₂[Cl₂Re^VII(N₃S₂)(μ‐NSN)(μ‐N≡Re^VIICl₃)]₂ ( 1 ): Space group P2₁/c, Z = 2, lattice dimensions at –80 °C: a = 1280.8(2), b = 1017.5(1), c = 2467.8(3) pm, β = 95.04(1)°, R = 0.049. The complex anion of 1 consists of a planar ReN₃S₂‐heterocycle which is connected with the second rhenium atom by a μ‐nitrido bridge as well as by a μ‐dinitridosulfato(II) ligand to form a planar Re₂(N)(NSN) six‐membered heterocycle. This [Cl₂Re(N₃S₂)(μ‐NSN)(μ‐N≡ReCl₃)]^– unit dimerizes via one of the N‐atoms of the (NSN)^4– ligand to give a centrosymmetric Re₂N₂ four‐membered ring.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂ReCl₄, [(Me₂PhP)₃Cl₂ReN]₂ReCl₄ · 2 SbCl₃ and [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] The reaction of ReNCl₂(PMePh)₃ with SbCl₅ in toluene yields the trinuclear complex [(Me₂PhP)₃Cl₂Re≡N]₂ReCl₄ · 2 SbCl₃ ( 1 · 2 SbCl₃). It forms triclinic crystals with the composition 1 · 2 SbCl₃, as well as monoclinic crystals 1 · 2 SbCl₃ · 4 C₇H₈. The monoclinic crystals with the space group P2₁/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, β = 95.51(1)°, Z = 2, have been used for a crystal structure determination. In the centrosymmetric complex 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit ReCl₄. The SbCl₃ molecules are coordinated by chlorine bridges to Cl atoms of 1 , and, in addition, connect the complexes 1 with each other. The SbCl₃ free compound 1 is obtained in good yield by the reaction of ReNCl₂(PMePh)₃ with ReCl₄(NCEt)₂. It crystallizes in the triclinic space group P1 with a = 1037.7(3), b = 1153.0(2), c = 1393.8(3) pm, α = 72.31(2)°, β = 74.06(2)°, γ = 67.94(2)°, and Z = 1. The bond lengths of the Re–N triple bonds are 172 pm in 1 and 170 pm in 1 · 2 SbCl₃. By the reaction of ReNCl₂(PMePh)₃ with SbCl₅ in CH₂Cl₂ the solvent is decomposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] ( 2 ) crystallizing in the monoclinic space group P2₁/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, β = 92,72(1)° and Z = 4. The Re–N distance in the almost linear unit Re≡N–H is 169,1 pm.     

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.     

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.     

Alkalimetall‐Phosphaniminate. Neue Synthesen und die Kristallstrukturen von [RbNPPh3]6 und [CsNPPh3]4

Alkali Metal Phosphoraneiminates. New Syntheses and Crystal Structures of [RbNPPh₃]₆ and [CsNPPh₃]₄ The alkali‐metal phosphoraneiminates MNPPh₃ with M = Na, K, Rb, Cs have been synthesized by reactions of Ph₃PI₂ with the alkali‐metal amides in liquid ammonia and were obtained as pure samples by subsequent extraction with toluene. The ethyl derivative KNPEt₃ has been prepared by an analogous route from Et₃PBr₂ and extraction with hexane. Single crystals of the phosphoraneiminates of rubidium and cesium are obtainable by crystallization from toluene and toluene/hexane, respectively. They were suitable for crystal structure determinations. [RbNPPh₃]₆ · 4¹/₂ toluene ( 1 ): space group P1, Z = 2, lattice dimensions at 193 K: a = 1525.5(2); b = 1902.9(2); c = 2178.3(2) pm; α = 95.435(12)°; β = 91.145(12)°; γ = 90.448(12)°; R₁ = 0.0529. The compound forms a Rb₆N₆ skeleton of a double cube with a common face of two rubidium and two nitrogen atoms, the latter being fivefold coordinated by four rubidium atoms and the phosphorus atom. [CsNPPh₃]₄ · 2 toluene · 3³/₄ hexane ( 2 a ): space group Fd3, Z = 8, lattice dimensions at 123 K: a = b = c = 2679.7(1) pm; R₁ = 0.0405. [CsNPPh₃]₄ · 2 toluene ( 2 b ): space group P2₁/n, Z = 4, lattice dimensions at 193 K: a = 1418.9(1); b = 2258.9(1); c = 2497.6(1) pm; β = 91.055(6)°; R₁ = 0.0278. Both cesium compounds form Cs₄N₄ heterocubane structures which are different by means of the packing and by different bond angles at the cesium and nitrogen atoms.     

Ligandenaustauschreaktionen von Bis(acetylacetonato)dioxo-molybdän(VI). Kristallstrukturen von [Salicylaldehyd-benzoylhydrazonato(2–)]dioxo-methanol-molybdän(VI) und [Benzoylaceton-benzoylhydrazonato(2–)] dioxo-triphenylphosphanoxid-molybdän(VI)

Ligand Exchange Reactions of Bis(acetylacetonato)dioxo-molybdenum(VI). Crystal Structures of [Salicylaldehyde-benzoylhydrazonato(2–)]dioxo-methanol-molybdenum(VI) and [Benzoylacetone-benzoylhydrazonato(2–)]dioxo-triphenylphosphaneoxide-molybdenum(VI) The products of ligand exchange reactions between bis(acetylacetonato)dioxo-molybdenum(VI) and tridentate diacidic ligands H₂L in the presence of triphenylphosphane were found by mass spectrometry to be complexes of the type MoO₂L. In the case of salicylaldehyde 2-hydroxyanil MoL₂ could also be identified. The compounds MoO₂L were crystallized as complexes with methanol or triphenylphosphane oxide. Crystallographic data see “Inhaltsübersicht”.     

Pyridin‐Komplexe von Seltenerd‐Trichloriden. Synthese und Kristallstrukturen von [YCl3(Py)4] und [LnCl3(Py)4] · 0,5 Py mit Ln = La und Er

Pyridine Complexes of Rare Earth Element Trichlorides. Syntheses and Crystal Structures of [YCl₃(py)₄] and [LnCl₃(py)₄] · 0.5 py with Ln = La and Er The pyridine complexes [YCl₃(py)₄] ( 1 ), [LaCl₃(py)₄] · 0.5 py ( 2 · 0.5 py), and [ErCl₃(py)₄] · 0.5 py ( 3 · 0.5 py) have been prepared from the diacetone‐alcohol complexes [LnCl₃(DAA)₂] or directly from the metal trichlorides with excess pyridine to give colourless, only sparingly moisture sensitive crystals. They were characterized by IR spectroscopy and by crystal structure determinations. 1 : Space group Pbca, Z = 16, lattice dimensions at –80 °C: a = 1647.4(1), b = 1743.1(1), c = 3190.5(1) pm, R₁ = 0.031. 2 · 0,5 Py: Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 978.9(1), b = 1704.5(1), c = 1589.5(1) pm, β = 103.61(1)°, R₁ = 0.0281. 3 · 0,5 Py: Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 970.1(1), b = 1706.4(1), c = 1566.1(1) pm, β = 103.46(1)°, R₁ = 0.0232. All complexes realize monomeric molecular structures with the metal atom in a distorted pentagonal‐bipyramidal coordination. One of the chlorine atoms and the four pyridine molecules are in the equatorial plane.     

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.     

Destruktive Komplexierung des dimeren Diorganylzinn(IV)‐hydroxids [Me2Sn(A)(μ‐OH)]2 (HA = Benzol‐1,2‐disulfonsäureimid): Bildung und Strukturen der Einkernkomplexe [Me2Sn(A)2(OPPh3)2] und [Me2Sn(phen)2]2⊕ · 2 A⊖ · MeCN

Polysulfonylamines. CXVI. Destructive Complexation of the Dimeric Diorganyltin(IV) Hydroxide [Me₂Sn(A)(μ‐OH)]₂ (HA = Benzene‐1,2‐disulfonimide): Formation and Structures of the Mononuclear Complexes [Me₂Sn(A)₂(OPPh₃)₂] and [Me₂Sn(phen)₂]^2⊕ · 2 A^⊖ · MeCN Destructive complexation of the dimeric hydroxide [Me₂Sn(A)(μ‐OH)]₂, where A^⊖ is deprotonated benzene‐1,2‐disulfonimide, with two equivalents of triphenylphosphine oxide or 1,10‐phenanthroline in hot MeCN produced, along with Me₂SnO and water, the novel coordination compounds [Me₂Sn(A)₂(OPPh₃)₂] ( 3 , triclinic, space group P 1) and [Me₂Sn(phen)₂]^2⊕ · 2 A^⊖ · MeCN ( 4 , monoclinic, P2₁/c). In the uncharged all‐trans octahedral complex 3 , the heteroligands are unidentally O‐bonded to the tin atom, which resides on a crystallographic centre of inversion [Sn–O(S) 227.4(2), Sn–O(P) 219.6(2) pm, cis‐angles in the range 87–93°; anionic ligand partially disordered over two equally populated sites for N, two S and non‐coordinating O atoms]. The cation occurring in the crystal of 4 has a severely distorted cis‐octahedral C₂N₄ coordination geometry around tin and represents the first authenticated example of a dicationic tin(IV) dichelate [R₂Sn(L–L′)₂]^2⊕ to adopt a cis‐structure [C–Sn–C 108.44(11)°]. The five‐membered chelate rings are nearly planar, with similar bite angles of the bidentate ligands, but unsymmetric Sn–N bond lengths, each of the longer bonds being trans to a methyl group [ring 1: N–Sn–N 71.24(7)°, Sn–N 226.81(19) and 237.5(2) pm; ring 2: 71.63(7)°, 228.0(2) and 232.20(19) pm]. In both structures, the bicyclic and effectively C_S symmetric A^⊖ ions have their five‐membered rings distorted into an envelope conformation, with N atoms displaced by 28–43 pm from the corresponding C₆S₂ mean plane.