Zur Kristallstruktur von La[AuF4]3, dem Anfangsglied der Reihe M[AuF4]3−xFx (x = 0, 0,5 und 1)

On the Crystal Structure of La[AuF₄]₃, the Final Link in the Series M[AuF₄]_3?xF_x (x = 0, 0.5 and 1) Yellow La(AuF₄)₃ was prepared for the first time in form of single crystals and investigated by X-ray methods. It crystallizes in space group R3 c-D (Nr. 167) with a = 1056.2(2) pm, c = 1633.7(8) pm, Z = 6.     

Darstellung und Struktur der Tetrafluoroaurate(III) MI[AuF4] mit MI = Li,Rb

Synthesis and Structure of Tetrafluoroaurates(III) M^I[AuF₄] with M^I = Li, Rb Single crystal investigations on Rb[AuF₄], light yellow, confirm the tetragonal unit cell (K[BrF₄]-type) with a = 618.2(1) and c = 1191(1) pm, Z = 4, space group I 4/mcm-D (No. 140). Li[AuF₄], light yellow too, crystallizes monoclinic with a = 485.32(7), b = 634.29(8), c = 1004.43(13) pm, β = 92.759(12), Z = 4; space group P 2/c-C (No. 13). The structure of Li[AuF₄] is related to the Rb[AuF₄]-type of structure.     

Synthese und Struktur von MII[AuF4]2 (MII  Cd,Hg)

Synthesis and Structure of M^II[AuF₄]₂ (M^II ? Cd, Hg) Cd[AuF₄]₂ and the isotypic compound Hg[AuF₄]₂, both are yellow, crystallize tetragonal in the space-group P4/mcc-D (No. 124) with a = 575.0/575.6 pm, c = 1034.8/1042.3 pm and Z = 2. The single-crystals were obtained by solid-state reactions in goldtubes.     

Synthese und Struktur von Silber(II)-tetrafluoroaurat(III) Ag[AuF4]2

Synthesis and Structure of Silver(II) Tetrafluoroaurate(III) Ag[AuF₄]₂ Intensive green single crystals of Ag[AuF₄]₂ can be obtained by heating up micro crystalline Ag[AuF₄]₂ in autoclaves (p(F₂) ～ 200 bar, T ～ 400°C, t ～ 14 d). It crystallizes monoclinic, space group P2₁/n ? C; (No. 14) with a = 522.3(1), b = 1101.3(3), c = 550.5(2) pm, β = 94.98(3), Z = 2 and is isotypic with Pd[AuF₄]₂.     

Tetrafluoroaurate(III) der Lanthaniden MF[AuF4]2 (M = Tm,Yb, Lu)

Tetrafluoroaurates(III) of Lanthanides MF[AuF₄]₂ (M = Tm, Yb, Lu) . Tetrafluoroaurates(III) MF[AuF₄]₂ with M = Tm, Yb, Lu, all yellow, have been prepared for the first time. From single crystal data they crystallize orthorhombic, space group Pbcn-D (No. 60) with M = Tm: a = 1 102.92(8) pm, b = 904.38(8) pm, c = 2 164.46(23) pm; M = Yb: a = 1 100.98(12) pm, b = 902.23(8) pm, c = 2 157.36(23) pm; M = Lu: a = 1 099.28(18) pm, b = 900.70(15) pm, c = 2 151.50(46) pm.     

KCuMIVF7 (MIV = Zr4+, Hf 4+), ein neuer Strukturtyp

KCuM^IVF₇ (M^IV = Zr⁴⁺, Hf ⁴⁺) a New Type of Structure KCuZrF₆ (colourless, orthorhombic, Cmcm – D (No. 63); a = 829,6 pm, b = 1276,5 pm, c = 1011,6 pm, Z = 8) and KCuHfF₇ (colourless, orthorhombic, Cmcm – D (Nr. 63); a = 829,6 pm, b = 1276,5 pm, c = 1011,6 pm, Z = 8) could be prepared by heating up in a goldtube at 700 °C for 3 weeks a mixture of KF, CuF₂, and ZrF₄ or HfF₄, respectively. Both compounds crystallize isotypic in a previous unknown structure.     

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.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [(Mo6X)Y]2–; Xi = Cl,Br; Ya = NO3, NO2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Mo₆X)Y]^2–; Xⁱ = Cl, Br; Y^a = NO₃, NO₂ By treatment of [(Mo₆X)Y]^2–; Xⁱ = Y^a = Cl, Br with AgNO₃ or AgNO₂ by strictly exclusion of oxygene in acetone the hexanitrato and hexanitrito cluster anions [(Mo₆X)Y]^2–, Y^a = NO₂, NO₃ are formed. X-ray structure determinations of (Ph₄As)₂[(Mo₆Cl)(NO₃)] · 2 Me₂CO ( 1 ) (monoclinic, space group P2₁/n, a = 12.696(3), b = 21.526(1), c = 14.275(5) Å, β = 115.02(2)°, Z = 2), (n-Bu₄N)₂[(Mo₆Br)(NO₃)] · 2 CH₂Cl₂ ( 2 ) (monoclinic, space group P2₁/n, a = 14.390(5), b = 11.216(5), c = 21.179(5)Å, β = 96.475(5)°, Z = 2) and (Ph₄P)₂[(Mo₆Cl)(NO₂)] (3) (monoclinic, space group P2₁/n, a = 11.823(5), b = 13.415(5), c = 19.286(5) Å, β = 105.090(5)°, Z = 2) reveal the coordination of the ligands via O atoms with (Mo–O) bond lengths of 2.11–2.13 Å, and (MoON) angles of 122–131°. The vibrational spectra of the nitrato compounds show the typical innerligand vibrations ν_as(NO₂) (∼ 1500), ν_s(NO₂) (∼ 1270) and ν(NO) (∼ 980 cm^–1). The stretching vibrations ν(N=O) at 1460–1490 cm^–1 and ν(N–O) in the range of 950–1000 cm^–1 are characteristic for nitrito ligands coordinated via O atoms.     

Dibrommethylsulfoniumsalze – Darstellung und Kristallstruktur [1]

Dibromomethylsulfoniumsalts — Preparation and Crystal Structure The salts CH₃SBrA^? (A^? = SbCl, AsF) were prepared by various routes and characterized by their Ramanspectra. CH₃SBrAsF crystallized in the monoclinic space group P2₁/c with a = 770,5(4) pm, b = 942,4(12) pm, c = 1329,3(14) pm, β = 100,28(6)°, Z = 4. Distances and bond angles in the cation are as expected.     

Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

Darstellung,Schwingungsspektren und Kristallstrukturen von [(Ph3P)2N]2[(W6Cl)I] · 2 Et2O · 2 CH2Cl2 und [(Ph3P)2N]2[(W6Cl)(NCS)] · 2 CH2Cl2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Ph₃P)₂N]₂[(W₆Cl )I ] · 2 Et₂O · 2 CH₂Cl₂ and [(Ph₃P)₂N]₂[(W₆Cl )(NCS) ] · 2 CH₂Cl₂ By treatment of [(W₆Cl)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(W₆Cl)(NCS)]^2– is formed. X‐ray structure determinations have been performed on single crystals of [(Ph₃P)₂N]₂[(W₆Cl)I] · 2 CH₂Cl₂ · 2 Et₂O ( 1 ) (triclinic, space group P1, a = 10.324(5), b = 14.908(3), c = 17.734(8) Å, α = 112.78(2)°, β = 99.13(3)°, γ = 92.02(3)°, Z = 1) and [(Ph₃P)₂N]₂[(W₆Cl)(NCS)] · 2 CH₂Cl₂ ( 2 ) (triclinic, space group P1, a = 11.115(2), b = 14.839(2), c = 17.036(3) Å, α = 104.46(1)°, β = 105.75(2)°, γ = 110.59(1)°, Z = 1). The thiocyanate ligands of 2 are bound exclusively via N atoms with W–N bond lengths of 2.091–2.107 Å, W–N–C angles of 173.1–176.9° and N–C–S angles of 178.1–179.3°. The vibrational spectra exhibit characteristic innerligand vibrations at 2067–2045 (ν_CN), 879–867 (ν_CS) and 490–482 (δ_NCS). Based on the molekular parameters of the X‐ray determination of 1 the vibrational spectra of the corresponding (n‐Bu₄N) salt of 1 are assigned by normal coordinate analysis. The valence force constants are f_d(WW) = 1.61, f_d(WI) = 1.23 and f_d(WCl) = 1.10 mdyn/Å.     

Zur Insertion in die Lanthanoid–Kohlenstoffbindung Synthese und Struktur von [CpSm(C6H5CH2NNO)]2 und [K(18-Krone-6)CpYb(NCS)2]∞

On the Insertion into the Lanthanide–Carbon Bond. Synthesis and Structure of [Cp Sm(C₆H₅CH₂NNO)]₂ and [K(18-crown-6)Cp Yb(NCS)₂]_∞ The compound [CpSm(CH₂C₆H₅)(thf)] was investigated, regarding its reactions with small molecules. The main subject was to detect an insertion into the Ln–C bond. With N₂O an insertion reaction is observed, yielding the dimer [CpSm(C₆H₅CH₂NNO)]₂ ( 1 ). The structural data of 1 was collected by a single crystal X-Ray diffraction analysis. (Space group P 1, Z = 1, a = 982.8(2) pm, b = 1052.2(2) pm, c = 1383.8(3) pm, α = 89.29(3)°, β = 73.64(3)°, γ = 66.41(3)°). In the dimer, the two Samarium ions are linked via an (η¹ : η²) bridge by two benzyl diazotato ligands. A nearly planar six-membered central Sm₂N₂O₂-ring is formend. Two pentamethylcyclopentadienyl ligands complete the coordination sphere of each Samarium ion, which are thus surrounded by four ligands each and have a distorted tetrahedral coordination geometry. An insertion of a SCN^– fragment in the Ln–C bond could not be observed. The substitution of the benzyl ligand leads to a polymeric chain structure. The new compound [K(18-crown-6)CpYb(NCS)₂]_∞ 2 contains a tetrahedrally coordinated Yb(III)-ion. (Space group P2₁/n}, Z = 4, a = 1640.6(3) pm, b = 1482.2(3) pm, c = 1674.5(3) pm, β = 102.82(1)°).     

Zur Kristallstruktur von OMF (M = Sb,Ru, Pt,Au)

On the Crystal Structure of O MF (M = Sb, Ru, Pt, Au) OMF (M = Sb, Ru, Pt, Au) were obtained again, but for the first time investigated by X-ray methods. Colourless OSbF and the rubyred compounds ORuF and OPtF crystallize isostructural in space group Ia3 -T_h⁷ (Nr. 206) with a = 1016(1) pm (Sb), a = 1002.6(9) pm (Ru) and a = 1003.6(9) pm (Pt), Z = 8. Yellow OAuF crystallizes trigonal-rhombohedric in space group R3 -D₃₂⁶ (Nr. 148) with a = 775.9(3) pm, c = 711.7(4) pm, Z = 3.     

NaAuIn2, ein ternäres Aurid mit ethananalogen In2Au6-Baueinheiten und [In2/2]-Ketten

NaAuIn₂, a Ternary Auride with Ethane Analogous In₂Au₆ Building Units and [In_2/2] Chains Silver coloured, brittle single crystals of NaAuIn₂ were synthesized by the reaction of NaN₃, gold-sponge and indium at 500°C. The structure was determined from X-ray single-crystal diffractometry data: space group Cmcm, Z = 4, a = 4.482(1) Å, b = 10.366(2) Å, c = 7.869(2) Å, R/R_w(w = 1) = 0.017/0.020, Z(F) ≥ 3σ(F) = 547 and N(var.) = 16. NaAuIn₂ crystallizes in the MgCuAl₂-structure type. Gold and indium form a framework structure. [AuIn_6/3] layers with trigonal prismatically coordinated gold are connected via In—In contacts along [010] which consist of ethane analogous In₂Au₆-building units. The In-partial structure consists of saw tooth like [In_2/2] chains along [001]. The sodium atoms occupy channel-like cavities within the Au—In framework structure.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [OsBr(acac)(PPh3)] und [OsBr(acac)(AsPh3)]

Synthesis, Crystal Structures, and Vibrational Spectra of [OsBr(acac)(PPh₃)] and [OsBr(acac)(AsPh₃)] By reaction of tetrabromoacetylacetonatoosmate(IV) with PPh₃ or AsPh₃ in ethanol the complexes [OsBr(acac)(PPh₃)] ( 1 ) and [OsBr(acac)(AsPh₃)] ( 2 ) are formed, which are purified by chromatography on silica gel. X-ray structure determinations of single crystals of ( 1 ) (monoclinic, space group P 2₁/n, a = 13.035(2), b = 18.2640(14), c = 16.636(3) Å, β = 112.776(14)°, Z = 4) and ( 2 ) (monoclinic, space group P 2₁/c, a = 13.23(5), b = 18.35(2), c = 16.65(2) Å, β = 112.9(5)°, Z = 4) result in mean bond distances Os–P = 2.413, Os–As = 2.483, Os–Br = 2.488 and Os–O = 2.037 Å. The vibrational spectra (10 K) exhibit the inner ligand vibrations of the acac, PPh₃ and AsPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 499–522, of OsAs at 330–339, of OsBr at 213–214 and of OsO in the range 460–694 cm^–1.     

Synthese und Struktur eines Caesium-tetraimidophosphat-diamids,Cs5[P(NH)4](NH2)2 = Cs3[P(NH)4] · 2 CsNH2

Synthesis and Crystal Structure of a Cesium-tetraimidophosphate-diamide, Cs₅[P(NH)₄](NH₂)₂ = Cs₃[P(NH)₄] · 2 CsNH₂ Well crystallized Cesium-tetraimidophosphate-diamide is obtained by the reaction of CsNH₂ with P₃N₅ in autoclaves at 673 K within three days. X-ray single crystal investigations led to the following data

• Ccca, Z = 4, a = 8.192(5) Å, b = 20.472(5) Å,
• c = 8.252(3) Å
• Z(F) ≥3σ(F) = 916, Z(Var.) = 32, R/R_w=1 = 0.017/0.021

The compound contains the hitherto unknown anion [P(NH)₄]^3?.     

Cs4[Sc6C]Cl13 und Cs4[Pr6(C2)]I13 — zwei Beispiele für das fehlende Bindeglied bei der Verknüpfung der Baueinheiten [M6Z]XX

Cs₄[Sc₆C]Cl₁₃ and Cs₄[Pr₆(C₂)]I₁₃ — Two Examples for the Missing Link in the Connectivity of [M₆Z]X X Building Units Cs₄[Sc₆C]Cl₁₃ (tetragonal, I4₁/amd, a = 1 540.5(4), c = 1 017.9(7) pm, c/a = 0.661, Z = 4, R = 0.038, R_w = 0.026) and Cs₄[Pr₆(C₂)]I₁₃ (a = 1 804.9(3), c = 1 259.5(3) pm, c/a = 0.698, R = 0.106, R_w = 0.068) are obtained as green-black and blue-black single crystals with brass-like metallic lustre through metallothermic reduction of ScCl₃ and PrI₃, respectively, with cesium in the presence of carbon in sealed tantalum containers. The, overall, isotypic compounds contain isolated [Sc₆C] and [Pr₆(C₂)] clusters, respectively, that are surrounded by 18 halide (X) ligands (12 Xⁱ and 6 X^a; X = Cl or I). The connection is carried out via the motif [M₆Z]XXXX (M = Sc and Pr; Z = C and C₂, respectively) and is thereby the missing link of the motifs of connection for the composition A_x[M₆Z]X₁₃. Analogous interconnection of [TiO₆] octahedra is found in the anatase-type of structure of TiO₂.     

Eine Chlorosäure des dreiwertigen Rheniums: Hydroxonium-decachloro-diaqua-trirhenat(III)-pentahydrat,H3O[Re3Cl10(H2O)2] · 5H2O

A Chloroacid of Trivalent Rhenium: Hydroxonium Decachloro Diaqua Trirhenate(III) Pentahydrate, H₃O[Re₃Cl₁₀(H₂O)₂] · 5H₂O . A chloroacid of rhenium(III), H₃O[Re₃Cl₁₀(H₂O)₂] · 5H₂O, was obtained at room temperature from a saturated solution of “ReCl₃ · 2H₂O” with an excess of NaCl in concentrated hydrochloric acid. The crystal structure (tetragonal, P4₁2₁2 (Nr. 92); a = 1 150.9(2) pm; c = 1 592.2(6) pm; Z = 4; R = 0.086; R_w = 0.066) has been determined from four-circle diffractometer data. The structure contains isolated cluster anions, [Re₃ClClCl^i,t (H₂O)]^?, which are enclosed by a cage of water molecules. These building units are connected with each other through a “strong” hydrogen-bonding system.     

Darstellung,Schwingungsspektrum und Kristallstruktur von (n‐Bu4N)2[(W6Cl)F] · 2 CH2Cl2 und 19F‐NMR‐spektroskopischer Nachweis der gemischten Clusteranionen [(W6Cl)FCl]2–, n = 1–6

Synthesis, Vibrational Spectra, and Crystal Structure of ( n ‐Bu₄N)₂[(W₆Cl )F ] · 2 CH₂Cl₂ and ¹⁹F NMR Spectroscopic Evidence of the Mixed Cluster Anions [(W₆Cl )F Cl ]^2–, n = 1–6 The reaction of (n‐Bu₄N)₂[(W₆Cl)Cl] with CF₃COOH in dichloromethane gives intermediately a mixture of the cluster anions [(W₆Cl)(CF₃COO)Cl]^2–, n = 1–6. By treatment with NH₄F the outer sphere coordinated trifluoracetato ligands are easily substituted and the components of the series [(W₆Cl)FCl], n = 1–6 are formed and characterized by their distinct ¹⁹F NMR chemical shifts. An X‐ray structure determination has been performed on a single crystal of (n‐Bu₄N)₂[(W₆Cl)F] · 2 CH₂Cl₂ (orthorhombic, space group Pbca, a = 15.628(4), b = 17.656(3), c = 20.687(4) Å, Z = 4). The low temperatur IR (60 K) and Raman (20 K) spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(WW) = 1.89, f_d(WF) = 2.43 and f_d(WCl) = 0.93 mdyn/Å.     

Disupersilylsilanide M(SiHR*2)2 der Zinkgruppenmetalle (M = Zn,Cd, Hg; R* = SitBu3): Synthesen,Charakterisierung und Strukturen

Disupersilylsilanides M(SiHR^*₂)₂ of Metals of the Zinc Group (M = Zn, Cd, Hg; R* = Si t Bu₃): Syntheses, Characterization, and Structures Bis(disupersilyl)silylmetals M(SiHR )₂ (R* = Supersilyl = SitBu₃) with M = Zn, Cd, Hg are obtained in tetrahydrofuran/benzene/pentane by the reaction of NaSiHR with ZnCl₂, CdI₂, HgCl₂ in the molar ratio 2 : 1. The compounds form colorless, in organic media soluble, not hydrolysis‐ and air‐sensitive crystals, the stabilities of which for thermolysis or photolysis decrease in the row Zn > Hg > Cd compound. According to X‐ray structure analyses, the compounds M(SiHR )₂ are monomeric with a – to date not observed – non‐linear framework –M– (angle SiMSi for M(SiHR )₂ with M = Zn/Cd/Hg 170.7/174.2/174.4°).