Über Neue Hexafluororhodate(IV): AIIRhIVF6 (AII = Ba,Sr, Ca,Mg, Zn,Cd, Hg,Ni sowie Cu)

On Novel Hexafluoro Rhodates(IV): A^IIRh^IVF₆. (A^II = Ba, Sr, Ca, Mg, Zn, Cd, Hg, Ni, Cu) We obtained hithertoo unknown BaRhF₆ and SrRhF₆ (both lemon yellow) of (hexag.) BaSiF₆?Type [a = 7.37₉, c = 7.21₁Å bzw. a = 7.15₇, c = 6.94₈ Å] as well as CaRhF₆ (light yellow) [a = 5.26₇, c = 14.61₂ Å], MgRhF₆ (light yellow) [a = 5.02₇, c 13.51₁Å], ZnRhF₅ (light yellow) [a = 4.99₆, c = 13.68₃ Å], CdRhF₆ (light yellow) [a = 5.,12₈ c = 14.44₇ Å], HgRhF₆ (orange) [a = 5.13₃, c = 14.67₆ Å], NiRhF₆ (light brown) [a = 4.96₀, c = 13.51₄ Å] all of (hexag.) LiSbF₆?type. The strukture of CuRhF₆ (light brown) is yet unknown.     

Ternäre Fluoride mit vierwertigem Chrom: M″CrF6mit M″ = Ba,Sr, Ca,Mg, Zn,Cd, Hg,Ni

Ternary fluorides with tetravalent chromium: M^IICrF₆ with M^II = Ba, Sr, Ca, Mg, Zn, Cd, Hg, Ni. We obtained hithertoo unknown BaCrF₆ (light yellow) and SrCrF₆ (yellow), both of (hexag.) BaSiF_B-type [a = 7.32₈, c = 7.13₇ Å; and a = 7.10₉ c = 6.86₃ Å, respectively] as well as CaCrF₆ (pink) [a = 5.33₆, c = 14.15₃ Å], MgCrF₆ (pink) [a = 5.09₁ c = 13.14₃ Å], CdCrF₆ (pink) [a = 5.14₆, c = 14.07₅ Å] and HgCrF₆ (orange-yellow) [a = 5.12₈, c = 14.26₅ A], all of (hexag.) LiSbF₆-type. NiCrF₆ (brown) [a = 4.97₅, c = 13.26₂ Å] and ZnCrF₆ (orange-yellow) [a = 5.02₆, c = 13.33₇ Å] crystallize in the hexag. VF₃-type.     

Zur Kenntnis Neuer Hexafluoroplatinate(IV)

On New Hexafluoroplatinates(IV) New prepared are PbPtF₆ (light yellow), hex. BaGeF₆-Type, [a = 7.22₇, c = 7.07₁ Å]; CaPtF₆ (light yellow) [a = 5.24₅, c = 14.78₄ Å]; ZnPtF₆ (light yellow) [a = 4.98₀, c = 13.82₈ Å]; CdPtF₆ (light yellow) [a = 5.11₈, c = 14.62₃ Å]; HgPtF₆ (light yellow) [5.13₂, c = 14.81₄ Å]; MnPtF₆ (ocker) [a = 5.09₄, c = 14.23₁ Å], CoPtF₆ (light brown) [a = 5.00₂, c = 13.81₅ Å]; NiPtF₆ (egg yellow) [a = 4,93₇, c = 13.68₇Å], all these of hex. LiSbF₆-structure. The structure of CuPtF₆ (light yellow) is yet unknown.     

Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.     

Synthesis of trans‐disubstituted cyclam ligands appended with two 6‐hydroxymethylpyridin‐2‐ylmethyl sidearms: Crystal structures of the 1,8‐dimethyl‐4,ll‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)cylam ligand and its Co(II) and Ni(II) complexes

Two new trans‐disubstituted cyclam ligands; 1,8‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)‐1,4,8,11‐tetra‐azacyclotetradecane ( 5 ) and 1,8‐dimethyl‐4, 11‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)‐1,4,8,11 ‐tetraaza‐cyclotetradecane ( 6 ); have been synthesized and characterized. The crystal structures of ligand 6 and its Ni(II) and Co(II) complexes have been determined. Crystal data are given for 6 , space group, P2₁/c, a = 11.095 (6) Å, b = 9.467 (5) Å, c = 13.283 (8) Å; β = 106.95 (5)°, Z = 2, R = 0.0715; for [Ni 6 ](C10₄)₂, space group P2₁/c, a = 9.4848 (14) Å, b = 33.941(6) Å, c = 9.793(2) A, β = 95.264(14)°, Z = 4, R = 0.0567; for [Co 6 ](C10₄)₂, space group, P2₁/c, a = 9.440 (6) Å, b = 33.848 (13) Å, c = 9.820 (3) Å, β = 95.16(3)°, Z = 4, R = 0.0718. In both complexes, the metal atoms are six‐coordinate with only one of the pendants interacting with the central metal atom and the other pendant remaining uncoordinated.     

Chalkogenohalogenogallate(III) und -indate(III): Eine neue Verbindungsklasse in der dritten Hauptgruppe. Synthese und Struktur von [Ph4P]2[In2SX6], [Et4N]3[In3E3Cl6] · MeCN und [Et4N]3[Ga3S3Cl6] · THF (X = Cl,Br; E = S,Se)

Chalcogenohalogenogallates(III) and -indates(III): A New Class of Compounds for Elements of the Third Main Group. Preparation and Structure of [Ph₄P]₂[In₂SX₆], [Et₄N]₃[In₃E₃Cl₆] · MeCN and [Et₄N]₃[Ga₃S₃Cl₆] · THF (X = Cl, Br; E = S, Se) [In₂SCl₆]^2?, [In₂SBr₆]^2?, [In₃S₃Cl₆]^3?, [In₃Se₃Cl₆]^3?, and [Ga₃S₃Cl₆]^3? were synthesised as the first known chalcogenohalogeno anions of main group 3 elements. [Ph₄P]₂[In₂SCl₆] ( 1 ) (P1 ; a = 10.876(4) Å, b = 12.711(6) Å, c = 19.634(7) Å, α = 107.21(3)°, β = 96.80(3)°, γ = 109.78(3)°; Z = 2) and [Ph₄P]₂[In₂SBr₆] ( 2 ) (C2/c; a = 48.290(9) Å, b = 11.974(4) Å, c = 17.188(5) Å, β = 93.57(3)°, Z = 8) were prepared by reaction of InX₃, (CH₃)₃SiSSi(CH₃)₃ and Ph₄PX (X = Cl, Br) in acetonitrile. The reaction of MCl₃ (M = Ga, In) with Et₄NSH/Et₄NSeH in acetonitrile gave [Et₄N]₃[In₃S₃Cl₆] · MeCN ( 3 ) (P2₁/c; a = 17.328(4) Å, b = 12.694(3) Å, c = 21.409(4) Å, β = 112.18(1)°, Z = 4), [Et₄N]₃[In₃Se₃Cl₆] · MeCN ( 4 ) (P2₁/c; a = 17.460(4) Å, b = 12.816(2) Å, c = 21.513(4) Å, β = 112.16(2)°, Z = 4), and [Et₄N]₃[Ga₃S₃Cl₆] · THF ( 5 ) (P2₁/n; a = 11.967(3) Å, b = 23.404(9) Å, c = 16.260(3) Å, β = 90.75(2)°, Z = 4). The [In₂SX₆]^2? anions (X = Cl, Br) in 1 and 2 consist of two InSX₃ tetrahedra sharing a common sulfur atom. The frameworks of 3, 4 and 5 each contain a six-membered ring of alternating metal and chalcogen atoms. Two terminal chlorine atoms complete a distorted tetrahedral coordination sphere around each metal atom.     

New Heptafluorozirconates and ‐hafnates AIBIIZr(Hf)F7 (AI = Rb,Tl; BII = Ca,Cd) – Synthesis,Structures, and Structural Relationships

Four new ABZrF₇ heptafluorozirconates (A = Rb, Tl; B = Ca, Cd) and their homologous heptafluorohafnates, all colorless, orthorhombic Cmcm (n^o63), Z = 4, have been synthesized by heating stoichiometric mixtures of RbF or TlF, CaF₂ or CdF₂ and ZrF₄ (HfF₄) in sealed platinum tubes at temperature ranging from 550 °C (Tl) to 600 °C (Rb). The crystal structures of both RbCdZrF₇ and TlCdZrF₇ have been solved from single‐crystal X‐rays diffraction data. Rietveld refinements were performed from X‐rays powder patterns for RbCaZrF₇ and TlCaZrF₇. In this series of heptafluorides, both B²⁺ and Zr⁴⁺ cations exhibit a pentagonal bipyramidal 7‐coordination. Their structural relationships with other heptafluorozirconates A^IB^IIZrF₇ as well as β‐KYb₂F₇ are discussed. RbCaZrF₇: a = 6.863(1) Å, b = 11.130(1) Å, c = 8.485(1) Å; TlCaZrF₇: a = 6.868(1) Å, b = 11.165(1) Å, c = 8.486(1) Å; RbCdZrF₇: a = 6.780(1) Å, b = 11.054(4) Å, c = 8.420(4) Å; TlCdZrF₇: a = 6.784(3) Å, b = 11.099(2) Å, c = 8.424(9) Å.     

Penta‐Ammoniates of Aluminium Halides: The Crystal Structures of AlX3·5NH3 with X = Cl,Br, I

Colourless crystals grow in the colder part of a glass ampoule when AlX₃·5NH₃ with X = Cl, Br, I is heated for 3—6 d to 330 °C (Cl), 350 °C (Br) and 400 °C (I), respectively. The chloride forms hexagonal prisms while the bromide and iodide were obtained as a bunch of lancet‐like crystals. The chloride and bromide crystallize isotypic whereas the iodide has an own structure type. All three are related to the motif of the K₂PtCl₆ type. So the formula of the ammoniates may be written as X₂[Al(NH₃)₅X] ≙ [Al(NH₃)₅X]X₂. The compounds are characterized by the following crystallographic data AlCl₃·5NH₃: Pnma, Z = 4, a = 13.405 (1)Å, b = 10.458 (1)Å, c = 6.740 (2)Å AlBr₃·5NH₃: Pnma, Z = 4, a = 13.808 (2)Å, b = 10.827 (1)Å, c = 6.938 (1)Å AlI₃·5NH₃: Cmcm, Z = 4, a = 9.106 (2)Å, b = 11.370 (2)Å, c = 11.470 (2)Å For the chloride and the bromide the structure determinations were successful including hydrogen positions. All three compounds contain octahedral molecular cations [Al(NH₃)₅X]²⁺ located in distorted cubes formed by the remaining 2X^— ions. The orientation of the octahedra to each other is clearly different for those with X = Cl, Br in comparison to the one with X = I.     

Syntheses,Characterizations, and Crystal Structures of Two New Organically Templated Borates

Two new organically templated borates, [H₂DAB][B₇O₉(OH)₅]·2H₂O ( 1 ) and [H₂DAB][B₇O₁₀(OH)₃] ( 2 ), have been synthesized under mild conditions in the presence of DAB acting as structure‐directing agent (DAB = 1,4‐diaminobutane). The structures were determined by single crystal X‐ray diffraction and further characterized by FTIR, elemental analysis, and thermogravimetric analysis. Both 1 and 2 crystallize in the same triclinic system, space group (No. 2); 1: a = 8.238(4) Å, b = 8.348 (5) Å, c = 14.574(8) Å, a = 101.050(3)°, β = 92.313(7)°, γ = 112.694(5)°, V = 900.3(8) ų, Z = 2; 2: a = 8.8769(3) Å, b = 9.3204(2) Å, c = 10.2204(5) Å, α = 74.474(2)°, β = 85.292(5)°, γ = 72.730(2)°, V = 778.01(5) ų, Z = 2. The structure of 1 consists of [B₇O₉(OH)₅]^2? groups, which represents the first example of organically templated heptaborate. The structure exhibits interesting hydrogen‐bonded network formed by borate polyanion [B₁₄O₂₀(OH)₆]^4?, which can be regarded as being constructed from the dehydration of the FBBs in 1 . The diprotonated organic amines are filled in the free space of the hydrogen‐bonded network and interact with the inorganic framework by extensive hydrogen bonds.     

Neue Oxocuprate (I). Über Cs3Cu5O4, Rb2KCu5O4, RbK2Cu5O4 und K3Cu5O4

New Oxocuprates(I). On Cs₃Cu₅O₄, Rb₂KCu₅O₄, RbK₂Cu₅O₄ and K₃Cu₅O₄ Cs₃Cu₅O₄ light yellow, powder as well as single crystals [a = 10.313(9), b = 7.630(1), c = 14.750(4) Å, β = 106.48(6)°], Rb₂KCu₅O₄ [a = 9.724(2), b = 7.443(0), c = 14.246(2) Å, β = 106.78(8)°], RbK₂Cu₅O₄ [a = 9.561(1), b = 7.411(0), c = 14.111(1) Å, β = 106.76(7)°] and K₃Cu₅O₄ [a = 9.422(1), b = 7.364(1), c = 13.995(2) Å, β = 107.00(2)°] are new prepared. The colour of the powders becomes lighter according to the sequence showed above. K₃Cu₅O₄ shows pale yellow. The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Vierkernige Clusterkomplexe vom Typ [MM′(AuPR3)2(μ‐H)(μ‐PCy2)(μ4‐PCy)(CO)6] (M,M′ = Mn,Re; R = Ph,Cy, Et): Synthese,Struktur und Topomerisierung

Tetranuclear Cluster Complexes of the Type [MM′(AuR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (M,M′ = Mn, Re; R = Ph, Cy, Et): Synthesis, Structure, and Topomerisation The dirhenium complex [Re₂(μ‐H)(μ‐PCy₂)(CO)₇(ax‐H₂PCy)] ( 1 ) reacts at room temperature in thf solution with each two equivalents of the base DBU and of ClAuPR₃ (R = Ph, Cy, Et) in a photochemical reaction process to afford the tetranuclear clusters [Re₂(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 2 ), Cy ( 3 ), Et ( 4 )) in yields of 35–48%. The homologue [Mn₂(μ‐H)(μ‐PCy₂)(CO)₇(ax‐H₂PCy)] ( 5 ) leads under the same reaction conditions to the corresponding products [Mn₂(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 6 ), Et ( 8 )). Also [MnRe(μ‐H)(μ‐PCy₂)(CO)₇(ax/eq‐H₂PCy)] ( 9 ) reacts under formation of [MnRe(AuPR₃)₂(μ‐H)(μ‐PCy₂)(μ₄‐PCy)(CO)₆] (R = Ph ( 10 ), Et ( 11 )). All new cluster complexes were identified by means of ¹H‐NMR, ³¹P‐NMR and ν(CO)‐IR spectroscopic measurements. 2 , 4 and 10 have also been characterized by single crystal X‐ray structure analyses with crystal parameters: 2 triclinic, space group P 1, a = 12.256(4) Å, b = 12.326(4) Å, c = 24.200(6) Å, α = 83.77(2)°, β = 78.43(2)°, γ = 68.76(2)°, Z = 2; 4 monoclinic, space group C2/c, a = 12.851(3) Å, b = 18.369(3) Å, c = 40.966(8) Å, β = 94.22(1)°, Z = 8; 10 triclinic, space group P 1, a = 12.083(1) Å, b = 12.185(2) Å, c = 24.017(6) Å, α = 83.49(29)°, β = 78.54(2)°, γ = 69.15(2)°, Z = 2. The trapezoid arrangement of the metal atoms in 2 and 4 show in the solid structure trans‐positioned an open and a closed Re…Au edge. In solution these edges are equivalent and, on the ³¹P NMR time scale, represent two fluxional Re–Au bonds in the course of a topomerization process. Corresponding dynamic properties were observed for the dimanganese compounds 6 and 8 but not for the related MnRe clusters 10 and 11 . 2 and 4 are the first examples of cluster compounds with a permanent Re–Au bond valence isomerization.     

Crystal Structures of Mono-, Di-, and Triaminoguanidinium Sulfate,as Well as Azidoformamidinium Sulfate: Important Precursors for Syntheses of Nitrogen Rich Ionic Compounds

Bis(1-aminoguanidinium) sulfate monohydrate (AG₂SO₄ … H₂O, 1), bis(1,3-diamino-guanidinium sulfate (DAG₂SO₄, 2), bis(1,3,5-triaminoguanidinium) sulfate dihydrate (TAG₂SO₄ … 2 H₂O, 3) and bis(azidoformamidinium) sulfate (AF₂SO₄, 5) were synthesized and characterized by multinuclear NMR, IR, and Raman spectroscopy and elemental analysis. In the synthesis of 3, double protonated triaminoguanidinium sulfate (HTAGSO₄, 4) was obtained as a byproduct. The molecular structures of 1–5 in the crystalline state were determined by low-temperature single crystal X-ray diffraction. 1: orthorhombic, Pnma, a = 6.7222 (8) Å, b = 14.153 (2) Å, c = 11.637 (1) Å, V = 1107.1(2) ų, Z = 4, ρ_calc.= 1.586 g cm^?3 R₁ = 0.0442, wR₂ = 0.1007 (all data). 2: hexagonal, P6₁22, a,b = 6.6907 (1) Å, c = 43.4600 (8) Å, γ= 120°, V = 1684.86 (5) ų, Z = 6, ρ_calc.= 1.634 g cm^?3, R₁ = 0.0321, wR² = 0.0714 (all data). 3: monoclinic, C2/c, a = 9.6174 (8) Å, b = 22.858 (1) Å, c = 6.7746 (5) Å, β= 109.49 (1), V = 1404.0 (4) ų, Z = 4, ρ_calc.= 1.620 g cm_?3, R₁ = 0.0292, wR₂ = 0.0781 (all data). 4: monoclini c, P2₁/c, a = 8.9998 (9), b = 6.3953 (6), c = 13.3148(12) Å, β= 99.679 (8), V = 755.44 (13) ų, Z = 4, ρ_calc.= 1.778 g cm^?3, R₁ = 0.0305, wR₂ = 0.0809 (all data); 5: orthorhombic, Pbca, a = 11.3855 (9), b = 7.1032 (6), c = 12.807 (1) Å, V = 1035.74 (14) ų, Z = 4, ρ_calc.= 1.720 g cm^?3, R₁ = 0.0389, wR₂ = 0.0862 (all data).     

Zur Koordinationschemie von cis-Trioxowolfram(VI)-Komplexen. Die Kristallstrukturen von LWO3 · 3 H2O, [L′WO2(OH)]Br, [LWO2Br]Br, [L2W2O5](S2O6) · 4 H2O und [LWO2(μ-O)WO(O2)2(OH2)] (L = 1,4,7-Triazacyclononan; L′ = 1,4,7-Trimethyl-1,4,7-triazacyclononan)

Coordination-chemistry of cis-Trioxotungsten(VI) Complexes. Crystal Structures of LWO₃ · 3 H₂O, [L′WO₂(OH)]Br, [LWO₂Br]Br, [L₂W₂O₅](S₂O₆) · 4 H₂O and [LWO₂(μ-O)WO(O₂)₂(OH₂)] (L = 1,4,7-Triazacyclonane; L′ = 1,4,7-Trimethyl-1,4,7-triazacyclononane) The cyclic triamines 1,4,7-triazacyclononane (L; C₆H₁₅N₃) and 1,4,7-trimethyl-1,4,7-triazacyclononane (L′; C₉H₂₁N₃) react in aqueous solution with WO₃ affording LWO₃ · 3 H₂O, 1 , and L′WO₃ · 3 H₂O, respectively, which yield [L′WO₂(OH)]Br, 2 , and [LWO₂Br]Br, 3 , in concentrated HBr solutions. In aqueous CH₃SO₃H solution 1 dimerizes. The iodide and dithionate 4 salts of [L₂W₂O₅]²⁺ have been isolated. In 35% H₂O₂ complex 1 yields the neutral species [LWO₂(μ-O)WO(O₂)₂(H₂O)] 5 . The crystal structures of 1 – 5 have been determined by X-ray analysis. Crystal data: 1 : P2₁/c; a = 7.729(2), b = 14.887(3), c = 10.774(2) Å, β = 90.77(2)°, Z = 4; 2 : Cc; 8.910(3), b = 12.220(6), c = 13.279(6) Å, β = 101.31(3)°, Z = 4; 3 : Cmc2₁, a = 8.857(5), b = 12.062(7), c = 11.218(7) Å, Z = 4; 4 : Cc, a = 17.601(7), b = 12.906(7), c = 14.107(8) Å, β = 124.08(4)°, Z = 4; 5 : P2₁2₁2₁; a = 8.452(4), b = 11.301(6), c = 13.750(6) Å, Z = 4.     

Preparation,Crystal Structure,Physical Properties and Electronic Band Structure of TlScQ2 (Q = S,Se and Te)

The title compounds were prepared by reaction of Tl₂Q (Q = S, Se and Te) Sc and Q in the temperature range of 200 to 500 °C. The structures of the selenide and the telluride adopt the α‐NaFeO₂ type, while TlScS₂ crystallizes in the β‐RbScO₂ type structure. The space group is for TlScSe₂ and TlScTe₂ with a = 3.9370(4) Å, c = 23.194(5) Å, and a = 4.2129(4) Å, c = 24.099(3) Å, respectively. The sulphide crystallizes in P6₃/mmc with a = 3.761(3) Å and c = 14.942(4) Å. The crystal chemical relations between the three chalcogenides are discussed. According to the electrical measurements and the band structure calculations, the compounds are semiconductors or poor metals.     

Pb2PdX6 (X = Cl,Br) – Verbindungen mit gestreckten [PdX6]-Oktaedern

Pb₂PdX₆ (X = Cl, Br) – Compounds with Elongated [PdX₆] Octahedra In contradiction to published data new compounds in the systems PbX₂—PdX₂ (X = Cl, Br) with the formula Pb₂PdCl₆ (I) and Pb₂PdBr₆ (II) were found. These were synthesized by thermal treatment of the corresponding mixtures of PbX₂ and PdX₂ (X = Cl, Br). X-ray single crystal structure analysis shows isotypism of I and II, monoclinic, P2₁/c (No. 14), Z = 2, I: a = 9.037(2) Å, b = 6.224(1) Å, c = 8.162(1) Å, β = 90.31(7)β, II: a = 9.512(7) Å, b = 6.584(8) Å, c = 8.383(3) Å, β = 90.07(5)º. Strongly elongated PdX₆ octahedra are found in the crystal structure. Additional characterisation of the compounds was done by DTA, IR/RAMAN spectra and ²⁰⁷Pb MAS NMR investigations. Remarcable low field shifts were found for ²⁰⁷Pb.     

Complexation of Alkali Triflates by Crown Ethers: Synthesis and Crystal Structure of [Na(12‐crown‐4)2][SO3CF3], [Na(15‐crown‐5)][SO3CF3], [Rb(18‐crown‐6)][SO3CF3], and [Cs(18‐crown‐6)][SO3CF3]

Complexes of trifluoromethanesulfonates (triflates) with alkali metals Na, Rb, Cs have been prepared in the presence of various macrocyclic polyether crowns [(12‐crown‐4), (15‐crown‐5) and (18‐crown‐6)]. Depending on the combination of alkali ion with crown, the complexes include separated ion pairs [Na(12‐crown‐4)₂] [SO₃CF₃] ( 1 ) and contact ion pairs [Na(15‐crown‐5)] [SO₃CF₃] ( 2 ), [Rb(18‐crown‐6)] [SO₃CF₃] ( 3 ), and [Cs(18‐crown‐6)] [SO₃CF₃] ( 4 ), in which the triflate acts as a bidentate ligand. It is shown that the choice of crown ether is of paramount importance in determining the solid‐state structural outcome. The complex resulting from the pairing of crown ether ( 1 ) develops, when the crown ether is too small in relation to the alkali ion radius. When the cavity size of the crown ether is matched with the alkali ion radius, simple monomeric structures are identified in 2 , 3 and 4 . The title compounds crystallize in the monoclinic crystal system: 1 : space group P2/c with a = 9.942(3), b = 11.014(2), c = 10.801(3) Å, β = 97.30(2)°, V = 1173.1(4) ų, Z = 2, R1 = 0.0812, wR2 = 0.1133: 2 : space group P2₁/m with a = 7.949(2), b = 12.063(3), c = 9.094(2) Å, β = 105.98(2)°, V = 838.3(4) ų, Z = 2, R1 = 0.0869, wR2 = 0.1035: 3 : space group P2₁/c with a = 12.847(5), b = 8.448(2), c = 22.272(6) Å, β = 122.90(3)°, V = 2029.5(1) ų, Z = 4, R1 = 0.0684, wR2 = 0.1044: 4 : space group P2₁/n with a = 12.871(3), b = 8.359(1), c = 19.019(4) Å, β = 92.61(2)°, V = 2044.2(6) ų, Z = 4, R1 = 0.0621, wR2 = 0.0979.     

Synthese,Kristallstruktur und thermischer Abbau von Fluoroaluminaten der Zusammensetzung (NH4)[M(H2O)6][AlF6] (M = Zn,Ni), [Zn(H2O)6][AlF5(H2O)] und (PyH)4[Al2F10] · 4 H2O

Synthesis, Crystal Structure and Thermal Behaviour of Fluoroaluminates of the Composition (NH₄)[M(H₂O)₆](AlF₆) (M = Zn, Ni), [Zn(H₂O)₆][AlF₅(H₂O)], and (PyH)₄[Al₂F₁₀] · 4 H₂O Four new fluoroaluminates were obtained from fluoroacidic solutions of respective metal salts. The compounds of zinc ( I a : P2₁/c, a = 12.688(3), b = 6.554(1), c = 12.697(3) Å, β = 95.21(3)°, V = 1051.5(4) ų, Z = 4) and nickel ( I b : P2₁/c, a = 12.685(3), b = 6.517(1), c = 12.664(2)Å, β = 94.55(2)°, V = 1043.6(4) ų, Z = 4) are isotypic and represent a new structure type consisting of two different cations, NH₄⁺ and [M(H₂O)₆]²⁺ and [AlF₆]^3–‐anions. [Zn(H₂O)₆][AlF₅(H₂O)] ( II : C2/m, a = 10.769(2), b = 13.747(3), c = 6.487(1)Å, β = 100.02(3)°, V = 945.7(3) ų, Z = 4) is characterized by a H₂O/F‐disorder in the [AlF₅(H₂O)]‐octahedra in two trans positions. In (PyH)₄[Al₂F₁₀] · 4 H₂O ( III : Cmc2₁, a = 15.035(3), b = 20.098(4), c = 12.750(4) Å, V = 5364(2) ų, Z = 8), bioctahedral [Al₂F₁₀]^4– anions have been found for the first time. The structures are described and discussed in comparison. The new compounds were used as precursors in order to obtain new AlF₃‐phases. However, the thermal decomposition did not result in the formation of any new metastable AlF₃‐phase. Instead, phase mixtures of either α‐AlF₃ and β‐AlF₃ or AlF₃ and MF₂ were obtained.     

1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe₃N)₄[(dto)₂In(dto)In(dto)₂] ( 1 ), (BzlPh₃P)₄[(dto)₂In(dto)In(dto)₂] ( 2 ), (BzlMe₃N)₃[In(dtsq)₃] ( 3 ), (Bu₄N)₃[In(dtsq)₃] ( 4 ) and (Ph₄P)[In(dtsq)₂(DMF)₂] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P2₁/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P2₁/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.     

Four New Thioantimonates(III) with the General Formula [TM(tren)]Sb4S7 (TM = Mn,Fe, Co,Zn) with the Transition Metal as Part of a Thioantimonate(III) Network Synthesized under Solvothermal Conditions and Tuning of the Optical Band Gap by the Transition Metal Cation

Four new thioantimonate(III) compounds with the general formula [TM(tren)]Sb₄S₇, TM = Mn 1 , Fe 2 , Co 3 and Zn 4 , were synthesized under solvothermal conditions by reacting elemental TM, Sb and S in an aqueous solution of tren (tren = tris(2‐aminoethyl)amine). All compounds crystallize in the monoclinic space group P2₁/n with four formula units in the unit cell. Single crystal X‐ray analyses of 1 [a = 8.008(2), b = 10.626(2), c = 25.991(5) Å, β = 90.71(3)°, V = 2211.4(8) ų], 2 [a = 8.0030(2), b = 10.5619(2), c = 25.955(5) Å, β = 90.809(3)°, V = 2193.69(8) ų], 3 [a = 7.962(2), b = 10.541(2), c = 25.897(5) Å, β = 90.90(3)°, V = 2173.0(8) ų] and 4 [a = 7.978(2), b = 10.625(2), c = 25.901(5) Å, β = 90.75(3)°, V = 2195.2(8) ų] reveal that the compounds are isostructural. The [Sb₄S₇]^2‐ anions are composed of three SbS₃ trigonal pyramids and one SbS₄ unit as primary building units (PBU). The PBUs share common edges and corners to form semicubes (Sb₃S₄) which may be regarded as secondary building units (SBU). The SBUs and SbS₃ pyramids are joined in an alternating fashion yielding the equation/tex2gif-stack-1.gif[Sb₄S₇^‐] anionic chain which is directed along [100]. Weaker Sb‐S bonding interactions between neighbored chains lead to the formation of layers within the (001) plane which contain pockets that are occupied by the cations. The TM²⁺ ions are in a trigonal bipyramidal environment of four N atoms of the tren ligand and one S atom of the thioantimonate(III) anion. The optical band gaps depend on the TM²⁺ ion and amount to 3.11 eV for 1 , 2.04 eV for 2 , 2.45 eV for 3 , and 2.60 eV for 4 .     

Neue ein- und mehrkernige Komplexe der Lanthanoiden. Zur Reaktion von Ph2Se2 mit Ytterbium

New Mono- and Polynuclear Complexes of the Lanthanides. On the Reaction of Ph₂Se₂ with Ytterbium Surprising formation of different complexes during the reaction of Ytterbium with Dichalcogenides. With THF is the mononuclear complex [Yb(SePh)₃(thf)₃] 1 (space group P31c (No. 159), Z = 2, a = 15.353(3) Å, c = 7.8920(10) Å) built up. In this compound is the Lanthanidion octahedrally souronded by the ligands. Reaction in Toluol/THF leads in contrast to the tetranuclear complex [Yb₄(SePh)₈O₂(thf)₆] 2 (space group C2/c (No. 14), Z = 4, a = 27.084(9) Å, b = 13.021(4) Å, c = 24.002(8) Å, β = 106.13(3)°). In DME it is possible to isolate the ionic species [Yb₃(SePh)₆(dme)₄][Yb(SePh)₄(dme)] 3 (space group P1 (No. 2), Z = 2, a = 11.109(3) Å, b = 11.664(2) Å, c = 36.303(10) Å, α = 84.60(4)°, β = 89.52(3)°, γ = 73.69(2)°). In this reactions are neutral and also ionic complexes accesible.