Kristallstruktur von Tl4Fe(CN)6

Crystal Structure of Tl₄Fe(CN)₆ Single crystals of Tl₄Fe(CN)₆ have been prepared for the first time and its crystal structure was determined. The pale yellow compound crystallizes in the triclinic space group P1 (No. 2) with the lattice parameters a = 726.6(1) pm, b = 797.4(8) pm, c = 1 336.0(1) pm, α = 104.7(9)°, β = 90.0(8)°, γ = 97.6(7)°, Z = 2 in a new structure type.     

Zur Bildung und Struktur der Phosphinophosphiniden-phosphorane tBu2P?PP(Me)tBu2 1, tBu(Me3Si)P?PP(Me)tBu2 2 und tBu2P?PP(Br)tBu2 3

Synthesis and Structure of Phosphinophosphinidene-phosphoranes tBu₂P? P?P(Me)tBu₂ 1, tBu(Me₃Si)P? P?P(Me)tBu₂ 2, and tBu₂P? P?P(Br)tBu₂ 3 A new method for the synthesis of 1 and 2 (Formulae see ?Inhaltsübersicht”?) is reported based on the reaction of 5 with substitution reagents (Me₂SO₄ or CH₃Cl). The results of the X-ray structure determination of 1 and 2 are given and compared with those of 3 . While in 3 one P? P distance corresponds to a double bond and the other P? P distance to a single bond (difference 12.5 pm) the differences of the P? P distances in 1 and 2 are much smaller: 5.28 pm in 1 , 4.68 pm in 2 . Both 1 and 2 crystallize monoclinic in the space group P2₁/n (Z = 4). 2 additionally contains two disordered molecules of the solvent pentane in the unit cell. Parameters of 1 : a = 884.32(8) pm, b = 1 924.67(25) pm, c = 1 277.07(13) pm, β = 100.816(8)°, and of 2 : a = 1 101.93(12) pm, b = 1 712.46(18) pm, c = 1 395.81(12) pm, β = 111.159(7)°, all data collected at 143 K. The skeleton of the three P atoms is bent (PPP angle 100.95° for 1 , 100.29° for 2 and 105.77° for 3 ). Ab initio SCF calculations are used to discuss the bonding situation in the molecular skeleton of the three P atoms of 1 and 3 . The results show a significant contribution of the ionic structure R₂P? P(^?)? P(⁺)(X)R₂. The structure with (partially) charged P atoms is stabilized by bulky polarizable groups R (as tBu) as compared to the fully covalent structure R₂P? P(X)? PR₂.     

Tetrafluoroaurate(III) der Lanthaniden M2F[AuF4]5 (M = Tb,Dy, Ho,Er)

Tetrafluoroaurates(III) of Lanthanoides M₂F[AuF₄]₅ (M = Tb, Dy, Ho, Er) Tetrafluoroaurates(III) M₂F[AuF₄]₅ with M = Tb, Dy, Ho, Er, all yellow, have been obtained. From single crystal data they crystallize triclinic, space group P1 -C¹_i (No. 2) with Tb: a = 1 194,34(7) pm, b = 798,46(6) pm, c = 902,02(7) pm, α = 89,033(7)°, β = 88,990(6)°, γ = 89,006(7)°; Dy: a = 1 191,66(9) pm, b = 796,33(8) pm, c = 899,65(9) pm, α = 88,956(8)°, β = 89,056(8)°, γ = 88,972(8)°; Ho: a = 1 189,06(10) pm, b = 795,46(6) pm, c = 896,81(7) pm, α = 88,912(8)°, β = 89,101(7)°, γ = 88,873(8)°; Er: a = 1 185,20(40), b = 793,98(14), c = 893,83(20), α = 88,751(23)°, β = 89,187(26)°, γ = 88,884(9)°     

Synthese und Kristallstruktur von Bis(1,2-dimethyl-5-nitro-imidazol)dichlorocobalt(II)

Synthesis and Crystal Structure of Bis(1,2-dimetyl-5-nitro-imidazole)dichlorocobalt(II) Bis(1,2-dimethyl-5-nitro-imidazol)dichlorocobalt(II) was obtained by reaction of CoCl₂ · 6 H₂O with 1,2-dimethyl-5-nitro-imidazole in methanol. The compound forms blue crystals which were characterized by IR and UV-vis spectroscopy and by an X-ray crystal structure determination. Co(C₅H₇N₃O₂)₂Cl₂: tetragonal, space group I4 2d, Z = 8, a = 1142.1(1) pm, c = 2577.3(2) pm. R = 0.036 for 670 independent reflexions. The Co atom is tetrahedrally surrounded by two chlorine and two N atoms at distances of 222.8(2) and 203.5(4) pm.     

Ein neuer Zugang zu Alkalivanadaten(IV,V) Die Kristallstruktur von Rb2V3O8

A New Access to Alkali Vanadates(IV,V) Crystal Structure of Rb₂V₃O₈ By heating vanadium(V) oxide with rubidium iodide to 500°C, the vanadium experiences partial reduction and Rb₂V₃O₈ is obtained. It has the fresnoite structure. Crystal data: a = 892.29(7), c = 554.49(9) pm at 20°C, tetragonal, space group P4bm, Z = 2. X-ray crystal structure determination with 620 observed reflexions, R = 0.027. V₂O₇ units share vertices with VO₅ square pyramids, forming layers; a layer can be regarded as association product of VO²⁺ and V₂O₇^4? ions. The Rb⁺ ions between the layers have pentagonal-antiprismatic coordination.     

Zinkselenid- und Zinktelluridcluster mit Phenylselenolat- und Phenyltellurolatliganden. Die Kristallstrukturen von [NEt4]2[Zn4Cl4(SePh)6], [NEt4]2[Zn8Cl4Se(SePh)12], [Zn8Se(SePh)14(PnPr3)2], [HPnPr2R]2[Zn8Cl4Te(TePh)12] (R = nPr,Ph) und [Zn10Te4(TePh)12(PR3)2] (R = nPr,Ph)

Zincselenide- and Zinctellurideclusters with Phenylselenolate- and Phenyltellurolateligands. The Crystal Structures of [NEt₄]₂[Zn₄Cl₄(SePh)₆], [NEt₄]₂[Zn₈Cl₄Se(SePh)₁₂], [Zn₈Se(SePh)₁₄(PⁿPr₃)₂], [HPⁿPr₂R]₂[Zn₈Cl₄Te(TePh)₁₂] (R = ⁿPr, Ph), and [Zn₁₀Te₄(TePh)₁₂(PR₃)₂] (R = ⁿPr, Ph) In the prescence of NEt₄Cl ZnCl₂ reacts with PhSeSiMe₃ or a mixture of PhSeSiMe₃/Se(SiMe₃)₂ to form the ionic complexes [NEt₄]₂[Zn₄Cl₄(SePh)₆] 1 or [NEt₄]₂[Zn₈Cl₄Se(SePh)₁₂] 2 respectively. The use of PⁿPr₃ instead of the quarternary ammonia salt leads in toluene to the formation of crystalline [Zn₈Se(SePh)₁₄(PⁿPr₃)₂] 3 . Reactions of ZnCl₂ with PhTeSiMe₃ and tertiary phosphines result in acetone in crystallisation of the ionic clusters [HPⁿPr₂R]₂[Zn₈Cl₄Te(TePh)₁₂] (R = ⁿPr 4 , Ph 5 ) and in THF of the uncharged [Zn₁₀Te₄(TePh)₁₂(PR₃)₂] (R = ⁿPr 6 , Ph 7 ). The structures of 1–7 were obtained by X-ray single crystal structure. ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1212,4(2) pm, b = 3726,1(8) pm, c = 1379,4(3) pm β = 99,83(3)°; 2 space group P2₁/c (Nr. 14), Z = 4, a = 3848,6(8) pm, b = 1784,9(4) pm, c = 3432,0(7) pm, β = 97,78(3)°; 3 : space group Pnn2 (No. 34), Z = 2, a = 2027,8(4) pm, b = 2162,3(4) pm, c = 1668,5(3) pm; 4 : space group P2₁/c (No. 14), Z = 4, a = 1899,8(4) pm, b = 2227,0(5) pm, c = 2939,0(6) pm, β = 101,35(3)°; 5 : space group space group P2₁/n (No. 14), Z = 4, a = 2231,0(5) pm, b = 1919,9(4) pm, c = 3139,5(6) pm, β = 109,97(4)°; 6 : space group I4₁/a (No. 88), Z = 4, a = b = 2566,0(4) pm, c = 2130,1(4) pm; 7 : space group P1¯ (No. 2), Z = 2, a = 2068,4(4) pm, b = 2187,8(4) pm, c = 2351,5(5) pm, α = 70,36°, β = 84,62°, γ( = 63,63°)     

Reaktionen von Lanthanoidhalogeniden mit Alkalibenzylverbindungen. Darstellung und Kristallstrukturen von [(tmeda)(C6H5CH2)2Y(μ-Br)2Li(tmeda)], [(tmeda)2SmBr(μ-Br)2Li(tmeda)] und [(dme)2SmBr(μ-Br)]2

Reactions of Lanthanide Halides with Alkalibenzyl Compounds. Synthesis and Crystal Structures of [(tmeda)(C₆H₅CH₂)₂Y(μ-Br)₂Li(tmeda)], [(tmeda)₂SmBr(μ-Br)₂Li(tmeda)] and [(dme)₂SmBr(μ-Br)]₂ Alkali-benzyl compounds react via a metathesis reaction with lanthanide halides to benzyl complexes of the rare earths. Reaction of [(C₆H₅CH₂)Li(tmeda)] with YBr₃ leads to the complex [(tmeda)Y(C₆H₅CH₂)₂ (μ-Br)₂Li(tmeda)] 1 , in which Yttrium and lithium are linked via two bromide bridges. However, the reaction of [(C₆H₅CH₂)Li(tmeda)] with SmBr₃ in toluene/tmeda leads under reduction of the Sm ion to the compound [(tmeda)₂SmBr(μ-Br)₂Li(tmeda)] 2 . 2 reacts with DME to yield the dimeric compound [(dme)₂SmBr(μ-Br)]₂ 3 . The structures of 1 – 3 were determined by X-ray single crystal structure analysis:

• 1: Space group P2₁/c, Z = 4, a = 829.5(6) pm, b = 1477.9(11) pm, c = 2575.0(10) pm, β = 92.03(6)°,
• 2: Space group P2₁, Z = 2, a = 954,7(3) pm, b = 1338.5(6) pm, c = 1244.9(5) pm, β = 107.51(3)°,
• 3: Space group P1 , Z = 1, a = 797.2(7) pm, b = 818.3(7) pm, c = 1169.7(8) pm, α = 100.96(6)°, β = 92.03(6)°, γ = 91.75(7)°.

     

Die Kristallstruktur von Bis(N,N-diethyl-N′ -benzoylselenoureato)nickel(II)

The Crystal Structure of Bis(N,N-diethyl-N′ -benzoylselenoureato)nickel(II) Ni(C₁₂H₁₅N₂OSe)₂ crystallizes in the monoclinic space group P2₁/c. The cell parameters are a = 11.399(3), b = 16.016(4), c = 14.910(6) Å, β = 104.64(3)° and Z = 4. The structure was solved with Patterson and direct methods and was refined to a final R-value of 5.43%. Nickel is coordinated to two N,N-diethyl-N′ -benzoylselenourea molecules to form a bidentally coordinated chelate complex with cis arrangement of the donor atoms. Coordinaton around the nickel atom is planar while the chelate rings diverge from planarity. The ethyl groups of one diethylamino group are disordered. The Ni? Se bond lengths are 2.244(1) and 2.264(1) Å, the Ni? O bond lengths are 1.871(4) and 1.883(4) Å, respectively.     

Darstellung von Organylquecksilber(II)‐di(methansulfonyl)amiden und Kristallstruktur von Ph–Hg–N(SO2Me)2

Polysulfonylamines. CXXIV. Preparation of Organylmercury(II) Di(methanesulfonyl)amides and Crystal Structure of Ph–Hg–N(SO₂Me)₂ Four N,N‐disulfonylated organylmercury(II) amides R–Hg–N(SO₂Me)₂, where R is Me, ⁱPr, Me₃SiCH₂ or Ph, were obtained on treating the appropriate chlorides RHgCl with AgN(SO₂Me)₂, and characterized by ¹H and ¹³C NMR spectra. In the crystal structure of the phenyl compound (orthorhombic, space group Pbca, Z = 8, X‐ray diffraction at –95 °C), the molecule exhibits a covalent and significantly bent C–Hg–N grouping [bond angle 172.7(3)°; Hg–C 204.0(8), Hg–N 209.1(7) pm]. One sulfonyl oxygen atom forms a short intramolecular Hg…O contact [296.1(5) pm] and simultaneously catenates glide‐plane related molecules via a second Hg…O interaction 297.6(5) pm], thus conferring upon Hg^II the effective coordination number 4 and a geometrically irregular coordination polyhedron (bond angles from 173 to 54°).     

Neue Phosphor-verbrückte Übergangsmetall-Komplexe Die Kristallstrukturen von [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)(PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2] und [Ni8(PtBu)6(PPh3)2]

New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co₄(CO)₁₀(PⁱPr)₂], [Fe₃(CO)₉(P^tBu)(PPh)], [Cp₃Fe₃(CO)₂(PP^tBu)· (P^tBu)], [(NiPPh₃)₂(PⁱPr)₆], [(NiPPh₃)Ni{(P^tBu)₃}₂], and [Ni₈(P^tBu)₆(PPh₃)₂] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co₄(CO)₁₀ · (PⁱPr)₂] ( 2 ), [Fe₃(CO)₉(P^tBu)(PPh)] ( 3 ), [Cp₃Fe₃(CO)₂(PP^tBu) · (P^tBu)] ( 4 ), [(NiPPh₃)₂(PⁱPr)₆] ( 5 ), [(NiPPh₃)Ni{(P^tBu)₃}₂] ( 6 ) and [Ni₈(P^tBu)₆(PPh₃)₂] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P2₁ (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).     

Pentacalciumhexaphosphahypodiphosphat,Ca5P8: Eine Verbindung mit isolierten Anionen P810− mit der gestaffelten Konformation von Ethan

Pentacalcium Hexaphosphahypodiphosphate, Ca₅P₈, a Compound with Isolated Anions P₈^10? in the Staggered Ethane Conformation Ca₅P₈ is prepared from calcium and red phosphorus in a molar ratio 5:8 in argon atmosphere in corundum crucibles inserted in quartz ampullae (3.5 d 1 000°C). It is a red-brown powder which is hydrolyzed by moisture. Single crystals are formed from powder at 1 100°C within 60 d. Ca₅P₈ crystallizes in a new structure type (mC26) with isolated anions P₈^10? in staggered conformation: C2/m (no. 12); a = 689.9(4) pm, b = 1 188,3(4) pm, c = 748.4(3) pm, β = 108.25(2)°, Z = 2; d = 2.56(1). Ca₅P₈ is the first compound containing polyphosphide anions with fourfold and single bonded phosphorus atoms (formally P⁺ and P^2?, resp.). The cations Ca²⁺ are arranged in a distorted cubic close-packing. The centers of the polyphosphide anions replace in an ordered way one third of Ca²⁺ in every second layer. The terminal P atoms occupy all octahedral interstices, so that P₈^10? is coordinated by 18 Ca²⁺ in form of a cuboctahedron with capped squaric faces.     

Darstellung und Kristallstruktur von Ptl3, einem valenzgemischten Platin (II,IV)-iodid

Preparation and Crystal Structure of PtI₃, a Mixed-valence Platinum (II, IV) Iodide PtI₃ was obtained by thermal decomposition of PtI₄ in a closed system at 300°C and 8 atm iodine pressure. Single crystals were formed by the reaction of PtI₄ with aqueous solutions of KI and I₂ at 270°C. The crystal structure of the monoclinic compound (a = 673.5(2) pm; b = 1206.1(4) pm; c = 1331.3(5) pm; β = 101.25(6)°; Z = 8; space group C2/c-C_2h⁶) contains square planar PtI₄ and octahedral PtI₆ groups which are connected by common edges to chains.     

Chloroantimonate(III): Die Kristallstruktur des 4,4′-Dipyridylium-pentachloroantimonats, (C10H8N2H2)SbCl5

Chloroantimonates(III): Crystal Structure of 4,4′-Dipyridylium Pentachloroantimonate, (C₁₀H₈N₂H₂)SbCl₅ (C₁₀H₈N₂H₂)SbCl₅ crystallizes in the triclinic space group P1 with a= 843.1(5), b = 958.6(8), c = 1098.0(10) pm, α = 112.45(6), β = 101.95(6), γ = 97.78(6)° and Z = 2. The structure is built up of 4,4 °-dipyridylium cations and pentachloroantimonate anions. The Sb atoms are distorted octahedrally coordinated. Mean distances are Sb? Cl = 242 pm (1×), Sb? Cl = 255 pm (2×), Sb ? Cl = 275 pm (2×) and Sb…?Cl.= 319 pm (1× ). The anions build up dimers.     

Phosphaniminato-Komplexe von Mangan(II) und Nickel(II) mit Heterocubanstruktur. Die Kristallstrukturen von [MCl(NPEt3)]4 mit M = Mn und Ni

Phosphoraneiminato Complexes of Manganese(II) and Nickel(II) with Heterocubane Structure. Crystal Structures of [MCl(NPEt₃)]₄ with M = Mn and Ni The phosphoraneiminato complexes [MCl(NPEt₃)]₄ with M = manganese and nickel as well as [MnBr(NPEt₃)]₄ are formed from the anhydrous halides MX₂ and excess phosphoraneimine Me₃SiNPEt₃ by fusion reaction. They form paramagnetic, moisture-sensitive, orange (M = Mn) and turquoisegreen (M = Ni) crystals, respectively, which are characterized by i.r. spectroscopy and by crystal structure determinations. [MnCl(NPEt₃)]₄ ( 1 ): Space group C2/c, Z = 4, structure solution with 3 591 unique reflections, (2 811 > 2σ(I)) R = 0.036. Lattice dimensions at -50°C: a = 2104.3, b = 1100.6, c = 1966.5 pm, β = 115.87°. [NiCl(NPEt₃)]₄ ( 2 ): Space group C2/c, Z = 4, structure solution with 2 711 unique reflections, (1611 > 2σ(I)) R = 0.056. Lattice dimensions at ?50°C: a = 2051.6, b = 1099.2, c = 1954.6 pm, β = 115.80°. 1 and 2 are isostructural with one another. They form heterocubane structures in which the metal atoms are linked via μ₃-N-bridges of the phosphoraneiminato groups with M₄N₄ bridge-type bond angles close to 90°.     

Synthese,Eigenschaften und Struktur von oktamerem Titanimidchlorid [Ti(NSiMe3)Cl2]8

Synthesis, Properties, and Structure of Octameric Titanium Imide Chloride [Ti(NSiMe₃)Cl₂]₈ The reaction of TiCl₄ with N(SiMe₃)₃ in sealed glas-tubes yields the titanium imide chloride [Ti(NSiMe₃)Cl₂]₈ ( 1 ). It crystallizes in the space group C2/c with a = 2 704.5(4), b = 1 303.9(1), c = 2 205.4(2) pm, β = 112.78(1)°, Z = 4. In 1 six Ti atoms are linked together by chloro and trimethylsilylimido bridges to form a ring structure. Two TiCl₂-groups are bound in addition to the ring by two imido bridges. Upon annealing at 250°C 1 transformes to the isomeric polymer [Ti(NSiMe₃)Cl₂]_n. Above 250°C 1 decomposes under separation of Me₃SiCl affording TiNCl.     

Struktur und elektrochemische Untersuchung von Nb3Cl8

Structure and Electrochemical Study of Nb₃Cl₈ The compound Nb₃Cl₈ was synthesized from NbCl₅ and niobium metal in a sealed quartz ampoule at 700 °C. Single crystals, obtained from LiCl melt were used for X‐ray structure determination (space group P 3 m1, Z = 2, lattice parameters a = b = 672.95(7) pm, c = 1223.2(2) pm (at 100 K), R1 = 0.029, wR2 = 0.064 for all independent reflections). Electrical resistivity measurements are reported. Electrochemical intercalation of lithium into the structure of Nb₃Cl₈ was studied.     

Neue Phosphor-verbrückte Übergangsmetallcarbonyl-Komplexe Die Kristallstrukturen von [Re2(CO)7(PtBu)3], [Co4(CO)10(PtBu)2], [Ir4(CO)6(PtBu)6] und [Ni4(CO)10(PiPr)6]

New Phosphorus-bridged Transition Metal Carbonyl Complexes. The Crystal Structures of [Re₂(CO)₇(P^tBu)₃], [Co₄(CO)₁₀(P^tBu)₂], [Ir₄(CO)₆(P^tBu)₆], and [Ni₄(CO)₁₀(PⁱPr)₆], (P^tBu)₃ reacts with [Mn₂(CO)₁₀], [Re₂(CO)₁₀], [Co₂(CO)₈] and [Ir₄(CO)₁₂] to form the multinuclear complexes [M₂(CO)₇(P^tBu)₃] (M = Re ( 1 ), Mn ( 5 )), [Co₄(CO)₁₀(P^tBu)₂] ( 2 ) and [Ir₄(CO)₆(P^tBu)₆] ( 3 ). The reaction of (PⁱPr)₃ with [Ni(CO)₄] leads to the tetranuclear cluster [Ni₄(CO)₁₀(PⁱPr)₆] ( 4 ). The complex structures were obtained by X-ray single crystal structure analysis: ( 1 : space group P1 (Nr. 2), Z = 2, a = 917.8(3) pm, b = 926.4(3) pm, c = 1 705.6(7) pm, α = 79.75(3)°, β = 85.21(3)°, γ = 66.33(2)°; 2 : space group C2/c (Nr. 15), Z = 4, a = 1 347.7(6) pm, b = 1 032.0(3) pm, c = 1 935.6(8) pm, β = 105.67(2)°; 3 : space group P1 (Nr. 2), Z = 4, a = 1 096.7(4)pm, b = 1 889.8(10)pm, c = 2 485.1(12) pm, α = 75.79(3)°, β = 84.29(3)°, γ = 74.96(3)°; 4 : space group P2₁/c (Nr. 14), Z = 4, a = 2 002.8(5) pm, b = 1 137.2(8) pm, c = 1 872.5(5) pm, β = 95.52(2)°).     

Synthese und Struktur von Mo2NCl7

Synthesis and Structure of Mo₂NCl₇ The reaction of VN with MoCl₅ at 175 °C in a sealed glass ampoule yields the molybdenum(V) nitride chloride Mo₂NCl₇ in form of air sensitive black crystals with the triclinic space group P1¯ and a = 905.7(8); b = 975.4((6); c = 1283.4(8) pm, α = 103.13(4)°; β = 109.83(5)° und γ = 98.58(5)°. The crystal structure is built up from dinuclear units [Mo₂N₂Cl₇]^3— and [Mo₂Cl₇]³⁺, which are connected by asymmetric nitrido bridges to form endless chains. Within both dinuclear units the Mo atoms are bridged by three Cl atoms resulting in a Mo‐Mo distance of 349.2(3) pm in the unit [Mo₂N₂Cl₇]^3—. In case of [Mo₂Cl₇]³⁺, however, a shorter Mo‐Mo distance of 289.4(3) pm is observed, which can be interpreted by a single bond. Correspondingly a reduced magnetic moment of 0.95 B.M. per Mo atom is observed.     

Polysulfonylamine. LVII. Zwei Silber(I)-di(organosulfonyl)-amide mit einer Silber-η2-Aryl- beziehungsweise einer Silber-Silber-Wechselwirkung: Kristallstrukturen von Silberdi(benzolsulfonyl)-amid-Wasser (1/0,5) und von wasserfreiem Silberdi(4-toluolsulfonyl)-amid

Polysulfonyl Amines. LVII. Two Silver(I) Di(organosulfonyl)-amides with Silver-η²-Aryl or Silver-Silver Interactions: Crystal Structures of Silver Di(benzenesulfonyl)amide-Water (1/0.5) and of Anhydrous Silver Di(4-toluenesulfonyl)-amide Crystals of [(PhSO₂)₂NAg(μ-H₂O)AgN(SO₂Ph)₂]_n ( 5 ) and [(4-Me? C₆H₄SO₂)₂NAgAgN(SO₂C₆H₄-4-Me)₂]_n ( 6 ) were obtained from aqueous solutions. The crystallographic data are for 5 (at ?95°C): monoclinic, space group C2/c, a = 2 743.8(5), b = 600.49(12), c = 1 664.5(3) pm, β = 101.143(15)°, V = 2.6908 nm³, Z = 8, D_x = 2.040 Mg m^?3; for 6 (at ?130°C): monoclinic, space group P2₁/n, a = 1 099.8(5), b = 563.7(3), c = 2 487.7(13) pm, β = 99.68(4)°, V = 1.5203 nm³, Z = 4, D_x = 1.888 Mg m^?3. In both crystals, the silver atom has a fivefold coordination. The structure of 5 displays [(RSO₂)₂N? Ag(μ-H₂O)Ag′? N(SO₂R)₂] units with Ag? N 226.9 pm, Ag? O 236.7 pm and Ag? O? Ag′ 95.3°; the water oxygen lies on a crystallographic twofold axis. These units are extended to two fused six-membered rings by intramolecular dative bonds (S)O → Ag′ and S(O)′ → Ag (249.3 pm). One phenyl group from each (PhSO₂)₂N moiety is η²-coordinated with its p-C and one m-C atom to a silver atom of a neighbouring bicyclic unit related by a glide plane to form infinite parallel strands (p-C? Ag 252.2, m-C? Ag 263.9 pm). The strands are interconnected into parallel layers through hydrogen bonds between H₂O and sulfonyl oxygens [O …? O(S) 276.1 pm]. These layers consist of a hydrophilic inner region containing metal ions, N(SO₂)₂ fragments and water molecules, and hydrophobic surfaces formed by phenyl groups. The structure of 6 features centrosymmetric [(RSO₂)₂N? Ag? Ag′? N(SO₂R)₂] units with two intramolecular dative bonds (S)O → Ag′ and (S)O′ → Ag (Ag? Ag′ 295.4, Ag? N 226.0, Ag? O 229.4 pm). These bi-pentacyclic units are associated by translation parallel to y into infinite strands by two dative (S)O → Ag bonds per silver atom (Ag? O 243.2 and 253.3 pm).     

Komplexchemie P-reicher Phosphane und Silylphosphane. VII [1]. Bildung und Struktur von [Li(DME)3]2{(SiMe3)[Cr(CO)5]2 P?PP?P[Cr(CO)5]2(SiMe3)}

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VII. Formation and Structure of [Li(DME)₃]₂{(SiMe₃)[Cr(CO)₅]₂ P-P ? P-P[Cr(CO)₅]₂(SiMe₃)} Deep red crystals of the title compound 1 are produced in the reaction of LiP(Me₃Si)₂[Cr(CO)₅] with 1, 2-dibromoethane in DME. The structure of 1 was derived from the investigation of the ³¹P-NMR spectra and confirmed by a single crystal structure determination. 1 crystallizes in the space group P1 (no. 2); a = 1307.8(5)pm, b = 1373.1(5)pm, c = 1236.1(4)pm, α = 106.22(4)°, β = 88.00(3)°, γ = 115.52(4)° and Z = 1. 1 forms a salt composed of a dianion R₂R₄′P₄^2? (R ? SiMe₃, R′ ? Cr(CO)₅) and solvated Li⁺ cations. The zigzag shaped dianion possesses the symmetry 1 -C_i. The distances d(P? P) = 202.5(1)pm and d(P? P) = 221.9(1)pm correspond to a double bond and single bonds, respectively. The distances d(Cr? P) = 251.1(1) pm and 255.3(1) pm are larger than those observed so far which might be caused by the charge distribution in the dianion.