Synthese und Kristallstruktur von Silber(II)‐Fluoriden AgMIVF6 (MIV = Sn,Ti, Pb,Pd, Pt,Rh)

Synthesis and Crystal Structure of Silver(II) Fluorides AgM^IVF₆ (M^IV = Sn, Ti, Pb, Pd, Pt, Rh) For the first time single crystals of AgSnF₆ (light blue, triclinic with a = 519.93(7) pm, b = 524.96(10) pm, c = 563.13(9) pm, α = 115.66(2)°, β = 89.28(2)°, γ = 118.77(2)°, spcgr. P1–C ; (No. 2), Z = 1) and AgPdF₆ (brown green, triclinic with a = 501.5(2) pm, b = 508.7(2) pm, c = 996.4(2) pm, α = 89.58(2)°, β = 103.10(2)°, γ = 120.88(2)°, spcgr. P1–C , (No. 2), Z = 2) have been synthesized and investigated. Other compounds of this type, like AgTiF₆ and AgPbF₆ (isotypic to AgSnF₆) or AgPtF₆ and AgRhF₆ (isotypic to AgPdF₆) have been synthesized in form of microcrystalline powders, their lattice parameters have been determined by Guinier data. All compounds are structure variants oft the LiSbF₆‐type and isotypic with CuMF₆ (M = Ti, Sn, Pb and Pd, Pt, respectively).     

Ag6B10S18: Ein neues Thioborat mit tetraedrischer Koordination des Bors

Ag₆B₁₀S₁₈: A Novel Thioborate with Tetrahedral Coordination of Boron Ag₆B₁₀S₁₈ was prepared as a novel thioborate from the reaction of stoichiometric amounts of Ag₂S, B, and S at 700°C with successive annealing at 580–460°C. The orange-yellow compound crystallizes in the monoclinic space group C2/c with a = 21.663(8), b = 21.639(8), c = 16.572(5) Å, ß = 129.40(4)°, Z = 8, d_x = 2.948 g · cm^?3. According to the complete X-ray crystal structure analysis the anionic part of the Ag₆B₁₀S₁₈ structure contains B₁₀S₂₀ “supertetrahedra” consisting of ten parallel corner-sharing BS₄ tetrahedra; the B₁₀S₂₀ groups are linked through corners to form a layer-like arrangement of (B₁₀S₁₆S_4/2^6?)_n = (B₁₀S₁₈^6?)_n polyantions. The mean B? S bond length is 1.915 Å. The electron densities in the regions of the Ag⁺ ions show a dynamically disordered arrangement which can be described by a distribution of the 6 Ag⁺ ions of the asymmetric unit over 18 partially occupied sites, these structural characteristics making Ag₆B₁₀S₁₈ an Ag⁺ ionic conductor. The i.r. spectrum of the compound shows B? S stretching vibrations at 610, 640, 685, 735, and 760 cm^?1.     

Doping Sumanene with Both Chalcogens and Phosphorus(V): One‐Step Synthesis,Coordination, and Selective Response Toward AgI

Heterasumanenes 4 – 6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in a one‐pot reaction from trichalcogenasumanenes 1 – 3 by replacing one chalcogen atom with a P=S unit. The P=S unit makes 4 – 6 almost planar and shrinks the HOMO–LUMO gap as compared to 1 – 3 . The bonding between Ag⁺ and S atom on P=S brings about a distinct change to the optical properties of 4 – 6 ; 4 in particular shows a selective fluorescence response toward Ag⁺ with LOD of 0.21 μm . Compounds 4 – 6 form complexes with AgNO₃ to be ( 4 )₂?AgNO₃, ( 5 )₂?AgNO₃, and ( 6 )₂?(AgNO₃)₃. In complexes, the coordination between Ag⁺ and P=S is observed, which leads to shrinkage of C?P and C?X (X=S, Se, Te) bond lengths. As a result, 4 , 5 , and 6 are all bowl‐shaped in complexes with bowl‐depths reaching to 0.66 Å, 0.42 Å, and 0.40 Å, respectively. There are Ag?Te dative bonds between Ag⁺ and Te atom on telluorophene in ( 6 )₂?(AgNO₃)₃.     

Doping Sumanene with Both Chalcogens and Phosphorus(V): One‐Step Synthesis,Coordination, and Selective Response Toward AgI

Heterasumanenes 4 – 6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in a one‐pot reaction from trichalcogenasumanenes 1 – 3 by replacing one chalcogen atom with a P=S unit. The P=S unit makes 4 – 6 almost planar and shrinks the HOMO–LUMO gap as compared to 1 – 3 . The bonding between Ag⁺ and S atom on P=S brings about a distinct change to the optical properties of 4 – 6 ; 4 in particular shows a selective fluorescence response toward Ag⁺ with LOD of 0.21 μm . Compounds 4 – 6 form complexes with AgNO₃ to be ( 4 )₂?AgNO₃, ( 5 )₂?AgNO₃, and ( 6 )₂?(AgNO₃)₃. In complexes, the coordination between Ag⁺ and P=S is observed, which leads to shrinkage of C?P and C?X (X=S, Se, Te) bond lengths. As a result, 4 , 5 , and 6 are all bowl‐shaped in complexes with bowl‐depths reaching to 0.66 Å, 0.42 Å, and 0.40 Å, respectively. There are Ag?Te dative bonds between Ag⁺ and Te atom on telluorophene in ( 6 )₂?(AgNO₃)₃.     

Synthesis,Crystal Structure Determination,and Physical Properties of Ag5IO6

The silver iodate(VII), Ag₅IO₆, was obtained by reacting a stoichiometric mixture of Ag₂O and KIO₃, at elevated oxygen pressure, adding a small portion of distilled water. The synthesis was done at 673 K and 270 MPa of oxygen pressure. The crystal structure was solved by direct methods based on single crystal diffraction data ( , Z = 6, a = 5.9366(1), c = 32.1471(6) Å, 323 independent reflections, R₁ = 2.31 %). According to conductivity measurements, Ag₅IO₆ is semiconducting with a specific resistance of 0.08 Ωcm at 300 K. The activation energy was determined as 7.4(1) meV in the temperature range of 220 – 300 K, and 4.3(1) meV in the temperature range of 90 – 180 K. The optical band gap for Ag₅IO₆ is 1.4 eV. Ag₅IO₆ is diamagnetic with a magnetic susceptibility of ?4.4×10^?4 emu/mol.     

Die Tieftemperaturmodifikationen von Ag6Si2O7 und Ag6Ge2O7 – Darstellung,Kristallstruktur und Vergleich der Ag?Ag-Abstände

On the Low Temperature Modifications of Ag₆Si₂O₇ and Ag₆Ge₂O₇ – Synthesis, Crystal Structure, and Comparison of Ag? Ag Distances For the first time, single crystals of Ag₆Si₂O₇ and Ag₆Ge₂O₇ have been obtained by solid state reactions of the binary oxides at temperatures of 350°C while applying oxygen pressures of 700 bar. According to the results of X-ray crystal structure determinations both compounds crystallize isostructural in P2₁ (Ag₆Si₂O₇: a = 5.3043(5) Å, b = 9.7533(7) Å, c = 15.9283(13) Å, β = 91.165(8)°, 3881 independent reflections, R1 = 3.3%, wR2 = 7.2%; Ag₆Ge₂O₇: a = 5.3713(4) Å, b = 9.9835(8) Å, c = 16.2249(14) Å, β = 90.904(8)°, 2111 independent reflections, R1 = 4.3%, wR2 = 6.0%, Z = 4). The crystal structures contain two independent M₂O₇^6? anions, one in a staggered, and the other in an ecliptic conformation. The cationic partial structure may be described as a distorted bcc arrangement of Ag⁺ and M⁴⁺. Comparison of the structures with respect to the Ag? Ag separations reveals the latter to be probably due to intrinsic d¹⁰–d¹⁰ bonding interactions as far as the range of 2.89 Å to 3.25 Å is considered.     

Ternäre Halogenide vom Typ A3MX6. II. Das System Ag3−xNaxYCl6: Synthese,Strukturen, Ionenleitfähigkeit

Ternary Halides of the A₃MX₆ Type. II. The System Ag_3?xNa_xYCl₆: Synthesis, Structures, Ionic Conductivity . The influence of the substitution of Ag⁺ by Na⁺ ions on the crystal structure and the ionic conductivity of Ag₃YCl₆ (stuffed LiSbF₆-type structure) has been investigated. The system Ag_3?xNa_xYCl₆ forms a complete solid solution. The stuffed LiSbF₆-type structure is stable for all compositions. For compounds with Na⁺ contents of x > 1.67, the cryolite-type structure is observed as the high-temperature form. The transition temperature decreases steadily with increasing Na⁺ content. The “end member” phase Na₃YCl₆ transforms at 243 K from the monoclinic cryolite-type structure to the stuffed LiSbF₆-type structure (trigonal, R3 ; a = 697.3(1), c = 1 868.4(14) pm, Z = 3; R = 0.094; R_w = 0.069). The crystal structures of Ag_1.3Na_1.7YCl₆ (trigonal, R3 ; a = 691.5(2), c = 1 853.7(6) pm, Z = 3; R = 0.099, R_w = 0.081) and AgNa₂YCl₆ (trigonal, R3 ; a = 691.7(1), c = 1 853.9(5) pm, Z = 3; R = 0.099, R_w = 0.064) have also been determined. Both chlorides crystallize like Ag₃YCl₆ and Na₃YCl₆-I in the stuffed LiSbF₆-type structure. The monovalent cations, Ag⁺ and Na⁺, are distributed over the five octahedral voids that are occupied by the Ag⁺ ions alone in Ag₃YCl₆. The ionic conductivity for compounds within the solid solution Ag_3?xNa_xYCl₆ decreases with increasing Na⁺ content. The values for Na₃YCl₆ (σ = 1 · 10^?6 Ω^?1 cm^?1 at T = 500 K) are by 2.5 to 3.5 orders of magnitude smaller than those for Ag₃YCl₆ (σ = 6 · 10^?4 Ω^?1 cm^?1 at T = 500 K).     

NaAg3S2, ein Thioargentat mit dem Clusteranion [Ag6S4]2−

NaAg₃S₂, a Thioargentate Containing the Anionic Cluster [Ag₆S₄]^2? . Dark-red octahedrally shaped crystals of NaAg₃S₂ could be obtained by the reaction of NaAg(CN)₂ and NaCN in a stream of hydrogen sulfide at 630 K. NaAg₃S₂ crystallizes cubic, a=12.358(1) Å, space group Fd3 m, Z=16. The structure was determined from four-circle diffractometer data. NaAg₃S₂ contains the anionic cluster [Ag₆S₄]^2?. The structure can be traced back to the spinel structure typ. An extended Hückel calculation for the cluster anion, which is considered to be isolated, shows weak bonding silver-silver interactions. NaAg₃S₂ is diamagnetic at room temperature.     

Homologous Silver Bismuth Chalcogenide Halides (N,x)P. III. The (4, x)P, (5, x)P,and (7, x)P Structure Families of Modular Compounds with Tunable Composition and Structure

The crystal structures of six members of the homologous series with general formula [BiQX]₂[Ag_xBi_1?xQ_2?2xX_2x?1]_N+1 (Q = S, Se; X = Cl, Br; 1/2 ≤ x ≤ 1) and N = 4, 5, or 7 were determined by single‐crystal X‐ray diffraction. The series are characterized by the parameters N and x and are denoted ^{(N, x)}P. Ag₃Bi₄S₆Cl₃ (x = 0.60) (I) , Ag_3.5Bi_3.5S₅Br₄ (x = 0.70) (II) and Ag_3.65Bi_3.35Se_4.70Br_4.30 (x = 0.73) (III) belong to ^{(4, x})P series Ag_5xBi_7?5xQ_12?10xX_10x?3 and adopt the AgBi₆S₉ structure type. The ^{(5, x)}P compound Ag_3.66Bi_4.34S_6.68Br_3.32 (IV) , which corresponds to x = 0.61 in Ag_6xBi_8?6xS_14?12xBr_12x?4, crystallizes isostructurally to AgBi₃S₅. The compounds Ag_4.56Bi_5.44Se_8.88Br_3.12 (x = 0.57) (V) and Ag_5.14Bi_4.86S_7.76Br_4.24 (x = 0.64) (VI) , which are members of ^{(7, x)}P series Ag_8xBi_10?8xQ_18?16xBr_16x?6, adopt the Ag₃Bi₇S₁₂ structure type. In the monoclinic crystal structures (space group C2/m) two kinds of layered modules alternate along [001]. Modules of type A uniformly consist of paired rods of face‐sharing monocapped trigonal prisms around Bi atoms with octahedra around mixed occupied metal positions (M = Ag/Bi) between them. Modules of type B are composed of [MZ₆] octahedra, which are arranged in NaCl‐type fragments of thickness N. All structures exhibit Ag/Bi disorder in octahedrally coordinated metal positions as well as Q/X mixed occupation of some anion positions. Corresponding to their black color, all compounds are narrow‐gap semiconductors (E_g = 0.35 eV for (II) ). General characteristics of the entire class of ^{(N, x)}P compounds are gathered in a catalogue.     

Beiträge zur Chemie der Silicium-Schwefel-Verbindungen. XXXIV. Das tetramere Silber(I)-Tri-tert-Butoxysilanthiolat

Contributions to the Chemistry of Silicon Sulfur Compounds. XXXIV. Tetrameric Silver(I)-tri-tert-butoxysilanethiolate Silver(I)-tri-tert-butoxysilanethiolate is formed as a tetramere by reaction of tritert-butoxysilanethiol with AgNO₃. The compound crystallizes as colourless triclinic plates and sublimes in vacuum at 170°C without decomposition. F.I. mass spectra shows only the mass of the tetrameric unit (m/e = 1 548), whereas this unit is observed in E.I. mass spectra with lower intensity. The ²⁹Si n.m.r. spectrum shows a remarkable splitting of the signal around ?68.54 ppm, which is explained by Si? Ag couplings. The central unit of the molecule is a nearly plane alternating Ag₄S₄ eight-membered ring with threefold bonded sulfur and twofold bonded silver atoms. Most important are the significant deviations from colinear S? Ag? S bonds (172.3°) resulting from shifts of the silver atoms toward the center of the eight-membered Ag₄S₄ ring (Ag? Ag = 313.5 pm). This effect is taken as a strong indication for high order direct Ag(I)-to-Ag(I) interactions. Related details of the structure are discussed. (Molecule symmetry is 2-C₂; space group P1 ; a = 1 769.7, b = 2012.8, c = 1 266.8 pm, α = 119.63°, β = 82.22°, γ = 95.08°; Z = 2; R = 0.067; 7 656 reflections h kl.)     

Neue Komplexe Fluoride mit Ag2+ und Pd2+: NaMIIZr2F11 (MII = Ag,Pd) und AgPdZr2F11

New Complex Fluorides with Ag²⁺ and Pd²⁺: NaM^IIZr₂F₁₁ (M^II = Ag, Pd) and AgPdZr₂F₁₁ For the first time single crystals of NaAgZr₂F₁₁, NaPdZr₂F₁₁ and AgPdZr₂F₁₁ have been obtained and investigated by X-ray methods. The isotypic compounds NaM^IIZr₂F₁₁ (M^II = Ag, Pd) crystallize triclinic, spcgr. P1 ? C (No. 2) with a = 780.9, b = 570.0, c = 583.2 pm, α = 106.1°, β = 112.2°, γ = 97.9° (NaPdZr₂F₁₁), AgPdZr₂F₁₁ is monoclinic, spcgr. C2/m? C_2h (No. 12) with a = 935.1, b = 699.1, c = 780.1 pm, β = 115.7°, Z = 2 (Four circle diffractometer data, Siemens AED 2). Their structure is closeley related to the Ag₃Hf₂F₁₄-type of structure.     

N,N-Dialkylcarbamato Complexes of the d10 cations of copper,silver, and gold

The reaction of CuO'Bu with CO₂, and ⁱPr₂NH in the presence of PPh₃, gives the dialkylcarbamato complex [Cu(O₂CNⁱPr₂)(PPh₃)₂] ( 1 ). The CO₂/R₂NH system (R = Me, Et) in an appropriate organic medium reacts with Ag₂O giving the corresponding N,N-dialkylcarbamato complexes of analytical formula [Ag(C₂CNR₂)] (R = Me, 2 ; R = Et, 3 ). The methyl derivative 2 was characterized by X-ray diffraction methods. Crystal data of 2 : for [Ag₂(O₂CNMe₂)₂], C₆H₁₂Ag₂N₂O₄, mol. wt. 391.9; monoclinic, space group P2₁/c, a = 12.08(1), b = 3.797(2), c = 11.316(7) Å, β = 113.37(6)°, V = 476.3 ų, Z = 2, D_c = 2.732 g cm^?3; μ(MoK_α) = 40.64 cm^?1, F(000) = 376.0; R = 0.059, R_w = 0.067; g.o.f. 1.27. The structure consists of dinuclear [(Ag₂OCNMe₂)₂] units with slightly distorted linearly two-coordinated Ag-atoms containing bridging carbamato groups to form a substantially planar eight-membered ring with an intra-annular Ag? Ag distance of 2.837(2) Å; the dinuclear units are further joined by Ag? O bonds to form an infinite array. Compound 3 , which is presumably dinuclear, as suggested by cryoscopic measurements in benzene, undergoes a structural fission with PPh₃, giving the mononuclear triphenylphosphine derivative [Ag(O₂CNEt₂)(PPh₃)₂] ( 4 ). The amine-catalyzed conversion of Ag₂O into Ag₂CO₃, in the presence of the ⁱPr₂NH/CO₂ system, is also reported. Cl-Exchange from [AuCl(PPh₃)] with [Ag(O₂CNEt₂)] ( 3 ) gives the first N,N-dialkylcarbamato complex of gold, namely [Au(O₂CNEt₂)(PPh₃)] ( 5 ), which crystallizes in the monoclinic system: C₂₃H₂₅AuNO₂P · 0.5 C₇H₁₆, mol. wt. 625.5, space group P2₁/c; a = 13.212(5), b = 12.25(1), c = 16.795(6) Å, β = 109.09(2)°, V = 2568(2) Å₃, Z = 4, D_c, = 1.618 g cm^?3; μ(AgK_α) = 31.40 cm^?1, F(000) = 1236.0; R = 0.058; R_w = 0.064; g.o.f. 2.121. The compound contains two-coordinated Au-atom, namely to the P-atom and to the O-atom of the monodentate carbamato group, the P? Au? O bond angle being 174.7(3)°. The reaction with MeI showed these compounds to react predominantly at the carbamato O-atom giving the corresponding urethanes R₂NCO₂Me. Evidence was gathered for the transient coordination of CO to Ag in 3 .     

Metalla- und Phosphaheterocyclen mit Diamino-Supermesitylboryl-Einheiten

Metalla- and Phosphaheterocycles with Diaminosupermesitylboryl Units RB(NMeLi)₂ is reacted with dimethylmetaldichlorides to give four membered (n = 1) metallacycles of the type (? RB? NMe? MMe₂? NMe? )_n (M = Si, IIa ; M = Ge, IIb ) and the eight membered ring (n = 2) with M = Sn, III . The four membered ring (? RB? NMe? PCMe₃? NMe? ), IV , is formed with Me₃CPCl₂. RBF₂ and lithiated N,N′-dimethylethylenediamine give the five membered ring RB(? NMe? CH₂—)₂, Va . The reaction of RB(NHMe)₂ with trimethylaluminum upon elimination of methane yields the symmetrical eight membered ring system (? RB? NMe? AlMe? NMe? )₂, VI . The compounds are characterized by their m.s. and n.m.r. (¹H, ¹¹B, ¹³C, ²⁹Si, ³¹P, ¹¹⁹Sn and in part ¹⁵N) spectra, and with the exception of III and VI also by elemental analyses. An X-ray structure analysis is provided for III .     

New Examples for the Unexpected Stability of the 10π‐Electron Hückel Arene [Si6]10–

The compounds Ba₄Ag₂Si₆, Eu₄Ag₂Si₆, and Ca₄Ag₂Si₆, prepared from the elements at 1273 K (the components in inner corundum crucibles are enclosed in sealed quartz ampoules), are brittle semiconductors with silvery luster. They react slowly with acids liberating hydrogen. Ba₄Ag₂[Si₆] and Eu₄Ag₂[Si₆] crystallize like Ba₄Li₂[Si₆] (space group Fddd (No. 70); a = 8.613 Å, b = 14.927 Å, c = 19.639 Å, and a = 8.420 Å, b = 14.585 Å, c = 17.864 Å, respectively), whereas Ca₄Ag₂[Si₆] represents a new structure type (space group Fmmm (No. 69); a = 8.315 Å, b = 14.391 Å, c = 8.646 Å). The three compounds are Zintl phases with the formal charges M²⁺, Ag⁺ and [Si₆]^10–. The mean bond lengths d(Si–Si) = 2.335–2.381 Å in the 10π‐Hückel arene [Si₆]^10– as well as d(Ag–Si) = 2.464–2.595 Å vary with the size of the M²⁺ cations. The chemical bonding was analyzed in terms of the Electron Localization Function (ELF) and compared with the bonding in related systems (Ce₄Co₂Si₆).     

Halogenometallate von Übergangselementen mit Kationen stickstoffhaltiger heterocyclischer Basen. I. Die Kristallstrukturen von 1,4-Dimethylpiperazinium-tetrachlorocobaltat(II) und -zinkat(II), (dmpipzH2)[MIICl4] (M = Co,Zn)

Halogenometalates of Transition Elements with N-heterocyclic Base Cations. I. The Crystal Structures of 1,4-Dimethylpiperazinium Tetrachlorocobaltate(II) and -zincate(II), (dmpipzH₂)[M^IICl₄] (M = Co, Zn) The compounds (dmpipzH₂)[M^IICl₄] crystallize in the monoclinic space group P2₁/m with a = 6.133(1), b = 14.306(1), c = 6.902(1) Å, β = 90.54(2)°, Z = 2 for M = Co and with a = 6.141(1), b = 14.282(1), c = 6.907(1) Å, β = 90.60(2)°, Z = 2 for M = Zn. The structures consist of tetrahedra [MCl₄]^2? and centrosymmetric cations (dmpipzH₂)²⁺ in the chair form. Bifurcated hydrogen bridging bonds of the N? H …? Cl type connect the nitrogen atom to two chloride ions. Two short distances C …? Cl are interpreted in terms of C? H …?Cl hydrogen bridges.     

Polysulfonylamine. XLII. Ein Aquasilber(I)-Komplex mit einem Ag(m̈-H2O)2Ag-Strukturmotiv: Röntgenstrukturanalytische und thermoanalytische Charakterisierung von Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silber(I)

Polysulfonyl Amines. XLII. An Aquasilver(I) Complex with an Ag(m?-H₂O)₂Ag Structural Unit: Characterization of Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silver(I) by X-Ray Diffractometry and Thermal Analysis The title compound C₆H₄(SO₂)₂NAg · H₂O, where C₆H₄(SO₂)₂N^º is the anion of 1,2-benzenedisulfonimide, crystallizes in the monoclinic space group C2/m with (at ?95°C) a = 1 129,7(3), b = 1 196.1(3), c = 810.7(2) pm, β = 124.25(2)°, V = 0.9055 nm³, Z = 4, D_x = 2.524 Mg m^?3. The crystal packing consists of [Ag(m?-H₂O)₂Ag{m?-C₆H₄(SO₂)₂N}₂]_n bands with crystallographic mirror symmetry, associated into layers by H-bonds with O(W)—O(S) 289.7 pm. The Ag(m?-H₂O)₂Ag moiety forms a planar four-membered ring with Ag? O(W)? Ag 97.3°, O(W)? Ag? O(W) 82.7° and Ag°Ag 372.1 pm. In the Ag{C₆H₄(SO₂)₂N}₂Ag′ unit, the anions act as tridentate (N, 1-O, 3-O)-ligands: One is N-bonded to Ag and O,O-chelated to Ag′, the other N-bonded to Ag′ and O,O-chelated to Ag. The silver atoms are (O₄N)-pentacoordinate, with nitrogen in the apical position of a distorted square pyramid [Ag? N 223.6, Ag? O(W) 247.8, Ag? O(S) 259.4 pm]. The thermochemical behaviour of the hydrate was investigated by thermal analysis and calorimetry. Water is only released at temperatures above 220°C. The dehydration enthalpy at 298 K is + 13.9 kJ mol^?1.     

Neue Fluorozirconate und ‐hafnate mit V2+ und Ti2+

New Fluorozirconates and ‐hafnates with V²⁺ and Ti²⁺ During investigations of the systems MF₂/KF/MF₄ e. g. MF₂/NaF/MF₄ (M²⁺ = Ti²⁺, V²⁺, M⁴⁺ = Zr⁴⁺, Hf⁴⁺) we obtained blue crystals of VZrF₆, VHfF₆, KVZrF₇, blue‐green crystals of NaVHf₂F₁₁, yellow crystals of TiHfF₆ and NaTiHf₂F₁₁, and yellow to rubyred crystals of TiZrF₆, respectively. According to single crystal data, VZrF₆ VHfF₆ and TiZrF₆ crystalizes in the ordered ReO₃‐type (cubic, Fm3m, a = 812,1(5), 804,2(8), and 821,0(2) pm, Z = 4). TiHfF₆ crystalizes in a high‐temperature‐modification (cubic, ReO₃‐type, Pm3m, a = 392,3(2) pm, Z = 2). KVZrF₇ is isotyic to KPdZrF₇ (orthorhombic, Pnna, a = 1109,8(6), b = 788,0(7), c = 648,0(15) pm, Z = 4). NaTiHf₂F₁₁ and NaVHf₂F₁₁ crystalizes monoclinic (C2/m, a = 910,5(7), b = 675,9(7), c = 773,6(5) pm, β = 116,10(6)° and a = 917,7(5), b = 685,7(5), c = 752,4 pm, β = 118,28(1)°, Z = 2, respectively) and are also isotypic to already known AgPdZr₂F₁₁.     

Die Reaktion von SeCl4 mit Übergangsmetalltetrachloriden. Synthese und Kristallstrukturen von (SeCl3)2MCl6 mit M = Zr,Hf, Mo,Re

The Reaction of SeCl₄ with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl₃)₂MCl₆ with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl₄, HfCl₄ and MoCl₄ react with SeCl₄ in closed ampoules at temperatures of 140°C to (SeCl₃)₂MCl₆ (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl₃)₂ReCl₆ structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl^? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se⁴⁺ and M⁴⁺ in an ordered way. The MCl₆ octahedra are regular, the SeCl₆ octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl₃⁺ and MCl₆^2? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly.     

Pseudochalkogenverbindungen. XXVI. Reaktionen von Organocyanamiden,RNHCN (R = iProp) und Ag[RNCN] (R = Ph), mit Hexachloro-cyclotriphosphazen

Pseudochalcogen Compounds. XXVI. Reactions of Organocyanamides, RNHCN (R = ⁱProp) and Ag[RNCN] (R = Ph), with Hexachloro-cyclotriphosphazene Reactions of organocyanamides, RNHCN (R = ⁱProp) and Ag[RNCN] (R = Ph), yield compounds of the type P₃N₃Cl_6?n[N(CN)R]_n. For these organocyanamides is observed in dependence on the radical R a nongeminal (R = ⁱProp, n = 3) respectively a geminal (R = Ph, n = 2,6) mode of chlorine replacement. The new compounds have been characterized on the basis of their ³¹P n.m.r. and i.r. spectra. The bonding type of the cyanamide substituents, P? N(CN)R, is confirmed by i.r. data as well as well by a modified synthetic route.