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.     

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.     

Zur Kenntnis komplexer Fluoride mit Cu2+ und Pd2+: MPtF6 (M  Pd,Cu) und RbCuPdF5

On Complex Fluorides with Cu²⁺ and Pd²⁺: MPtF₆ (M ? Pd, Cu) and RbCuPdF₅ For the first time single crystals of PdPtF₆ (green), trigonal-rhomboedric, a = 503.8, c = 1431.6 pm, spcgr. R3 ? C (No. 148), Z = 3, CuPtF₆ (orange), triclinic, a = 495.2, b = 498.5, c = 962.4 pm, α = 89.98, β = 104.23, γ = 120.35°, spcgr. P1 ? C (No. 2), Z = 2 and RbCuPdF₅ (orange brown, in connection with investigations on M^IPd₂F₅ [1]), orthorhombic, a = 626.9, b = 719.9, c = 1076.3 pm, spcgr. Pnma? D (No. 62), Z = 4, four circle diffractometer data, have been obtained.     

Zur Kristallstruktur von MnF3 und MnPtF6

On the Crystal Structure of MnF₃ and MnPtF₆ Single crystal investigations of MnF₃ (rubyred) confirmed the crystal structure based on powder data [2]: monoclinic, space group C 2/c?C (No. 15) with a = 892.02 pm, b = 504.72 pm, c = 1 347.48 pm, β = 92.64° with Z = 12. The corresponding determination of the crystal structure of MnPtF₆, yellow, confirmed the unit cell [3] with a = 510.47 pm, c = 1 421.0 pm and γ = 120°, Z = 3 space group R 3 -C (No. 148). For both compounds detailed parameters respectively interatomic distances have been obtained.     

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)°).     

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.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [OsCl(acac)(EPh3)], E = P,As, Sb

Synthesis, Crystal Structures, and Vibrational Spectra of [OsCl(acac)(EPh₃)], E = P, As, Sb By reaction of tetrachloroacetylacetonatoosmate(IV) with PPh₃, AsPh₃ or SbPh₃ in ethanol the complexes [OsCl(acac)(EPh₃)], E = P, As, Sb are formed, which are purified by chromatography on silica gel. X-ray crystal structure determinations of the isotypic single crystals of [OsCl(acac)(EPh₃)] (monoclinic, space group P 2₁/c, Z = 4; E = P ( 1 ): a = 12.972(2), b = 18.255(2), c = 16.517(2) Å, β = 112.61(2)°; E = As ( 2 ): a = 13.173(5), b = 18.299(5), c = 16.429(5) Å, β = 112.346(5)°; E = Sb ( 3 ): a = 13.573(3), b = 18.520(3), c = 16.440(9) Å, β = 111.78(2)°) result in mean bond distances Os–P = 2.412, Os–As = 2.485, Os–Sb = 2.619, Os–Cl = 2.354 and Os–O = 2.032 Å. The IR spectra (10 K) exhibit the inner ligand vibrations of the acac and EPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 500–524, of OsAs at 330–339, of OsSb at 271–278, of OsCl at 317–322 and of Os–O in the range 460–694 cm^–1.     

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.     

Synthese,Struktur und magnetische Eigenschaften der Verbindungen NaMIIZr2F11 (MII = Ti,V und Cu) und einem Anhang über NaPdZr2F11

Synthesis, Structure, and Magnetic Properties of Compounds NaM^IIZr₂F₁₁ (M^II = Ti, V, Cu) and a Notice on NaPdZr₂F₁₁ By synthesizing NaTiZr₂F₁₁ in form of red single crystals, it was possible to obtain a complex fluoride with Ti²⁺ for the first time. It crystallizes like the analogous greenish blue vanadium compound isotypic to AgPdZr₂F₁₁ [1] monoclinic, spacegroup C2/m–C (No. 12) with a = 918.0/911.5 pm, b = 682.6/675.7 pm, c = 780.8/776.6 pm, β = 116.2/116.2º and Z = 2. Colourless NaCuZr₂F₁₁ however crystallizes as a result of the Jahn-Teller distortion of Cu²⁺ triclinic (space group P1 –C (No. 2), a = 552.7 pm, b = 568.2 pm, c = 768.0 pm, α = 111.0º, β = 97.4º, γ = 106.4º) and is – as expected – isotypic to NaAgZr₂F₁₁ [1].     

Zur Chemie und Strukturchemie der Phosphide und Polyphosphide. 26. Dibariumheptaphosphidchlorid Ba2P7Cl,eine Verbindung mit dem polycyclischen Anion P

Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 26. Dibariumheptaphosphidechloride Ba₂P₇Cl, a Compound with the Polycyclic Anion P Ba₂P₇Cl is formed by the synthesis of Ba₃P₁₄ from the elements in a melt of BaCl₂ (dehydrated) at 1170 K. The compound forms light rubyred platelets which decompose in protic systems immediately to phosphanes. Ba₂P₇Cl crystallizes in the space group P2₁/m with Z = 2 formular units (a = 1172.6(2) pm; b = 682.9(1) pm; c = 633.7(1) pm; β = 95.27(2)°). The structure (964 reflexions hkl, R = 0.035) is related to the NaCl type, in which the half of the anionic positions is occupied by the gravi-centers of the polycyclic anions P. The bond lengths d(P? P) show the typical topological dependence for the anionic heptaphosphanortricyclene system: (d : 226.4 pm in the three-membered ring; 214.5 pm ring to bridge; 217.2 pm bridge to bridge head). The Ba atoms are surrounded by 9 and 10 non metallic atoms, respectively. Cl^? is coordinated tetrahedrally by Ba.     

Zur Kristallchemie der Kupfer-Lanthanoid-Oxowolframate: (I) triklin-α-CuTbW2O8, (II) monoklin-CuInW2O8 und (III) monoklin-CuYW2O8

The Crystal Chemistry of Copper Rare-Earth Oxotungstates: (I): triclinic-α-CuTbW₂O₈, (II): monoclinic-CuInW₂O₈ and (III): monoclinic-CuYW₂O₈ Single crystals of (I), (II) and (III) were prepared by recrystallisation in closed systems and examined by X-ray technique. (I): space group C? P1 , a = 7.3080, b = 7.8945, c = 7.1476 Å, α = 115.23, β = 116.21, γ = 56.98°, Z = 2; (II): space group C? C2/c, a = 9.6576, b = 11.6496, c = 4.9863 Å, β = 91.17°, Z = 4; (III): space group C? P2/n, a = 10.0504, b = 5.8214, c = 5.0224 Å, β = 94.23°, Z = 2. The crystal structures are discussed with respect to calculations of the coulombterms of lattice energy and possible valence states of Cu²⁺ and Mo⁵⁺.     

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.     

Ag2+ in trigonal-bipyramidaler Umgebung: Neue Fluoride mit zweiwertigem Silber: AgMMF20 (MII = Cd,Ca, Hg; MIV = Zr,Hf)

Ag²⁺ in Trigonal-Bipyramidal Surrounding New Fluorides with Divalent Silver AgM M F₂₀ (M^II = Cd, Ca, Hg; M^IV = Zr, Hf) The intensively green compounds AgMMMF₂₀ (M^II = Cd, Ca, Hg; M^IV = Zr, Hf) have been obtained for the first time as single crystals and investigated by X-ray methods. They crystallize in space group P6₃/m-C_6h² (Nr. 176) with

• a = 1052.0(2) pm, c = 828.6(2) pm (AgCd₃Zr₃F₂₀),
• a = 1048.0(2) pm, c = 832.6(3) pm (AgCd₃Hf₃F₂₀),
• a = 1059.4(2) pm, c = 841.0(3) pm (AgCa₃Zr₃F₂₀),
• a = 1053.7(2) pm, c = 830.6(3) pm (AgCa₃Hf₃F₂₀),
• a = 1058.9(3) pm, c = 832.6(4) pm (AgHg₃Zr₃F₂₀),
• a = 1056.9(2) pm, c = 833.0(3) pm (AgHg₃Hf₃F₂₀), Z = 2.

     

Zur Kenntnis von NiPtF6 und CdPtF6

Anotation to Compounds MPtF₆ (M = Ni, Cd) Yellow single crystals of M¹¹PtF₆ (M¹¹ = Ni, Cd) have been obtained for the first time and investigated by X-ray methods. The powder data of the compounds are confirmed. Both samples are isostructural to LiSbF₆, space group R3 -C (Nr. 148) with a = 500.5(3) pm, c = 1375.6(7) pm for NiPtF₆ and a = 511.56(9) pm, c = 1460.3(4) pm for CdPtF₆, Z = 3.     

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.     

Sulfoximid und Sulfoximidium-Salze – Strukturen und H?Brückenbindungen

Sulfoximide and Sulfoximidium Salts – Structures and Hydrogen Bonding In the solid state dimethylsulfoximide ( 1 ) (orthorhombic; space group Pbca; a = 577.8, b = 931.2 and c = 1645.6 pm) makes intermolecular N? H ? N hydrogen bonds. The hydrogen halide salts (CH₃)₂S(O)NH₂⁺Hal^? (( 2 ), Hal^??Cl^?; ( 4 ), Hal^??Br^?) reacts with metal halides to yield (CH₃)₂S(O)NH₂⁺MHal with the complex anions (( 5 ), MHal?SbCl₄^?; ( 6 ), MHal?SbCl₅^2?; ( 7 ), MHal?SbCl₆^?; ( 8 ), MHal?SbBr₅^2?; ( 9 ), MHal?AlCl₄^?). 2 crystallizes from ethanol (96%) as [(CH₃)₂S(O)NH₂⁺Cl^?]₂ · H₂O ( 3 ). The structures of 3 (monoclinic; space group P2₁/c; a = 917.0, b = 1344.7, c = 1080.8 pm and β = 103.8°; Z = 10), 4 (orthorhombic; space group Pbcn; a = 1028.9, b = 1132.6, c = 1074.1 pm; Z = 8) and 6 (monoclinic; space group C2/c; a = 2041.1, b = 1101.4, c = 3365.6 pm and β = 153.8°; Z = 8) are determined by X-ray analysis. In 6 Sb is coordinated in a distorted octahedra by 6 Cl in three short (mean 245,5 pm; SbCl₃) and three long distances (291 to 299 pm; Cl^?). Two of the chloride ions connect the Sb atoms to infinite Sb …? Cl …? Sb chains. Except for 7 and 9 there are bridges between the NH₂ groups and the halide ions. The NH valence vibrations are discussed in view of hydrogen bonding.     

Bi13Pt3I7: Ein Subiodid mit einer pseudosymmetrischen Schichtstruktur

Bi₁₃Pt₃I₇: A Subiodide with a Pseudo-Symmetric Layer Structure The reaction of PtI₂ with Bi and BiI at 630 K yields black, lustrous, air insensitive crystals of the subiodide Bi₁₃Pt₃I₇. The layered crystal structure (triclinic, C1 , a = 1581.0(2) pm, b = 912.6(1) pm, c = 2149.6(6) pm, α = 90.03(2)°, β = 96.96(2)°, γ = 90.11(1)°, V = 3078.6 · 10⁶ pm³) contains edge-sharing [PtBi_8/2] cubes, which form nets of Kagomé type. Iodine atoms fill the hexagonal-prismatic voids therein. These [(PtBi_8/2)₃I] layers are alternately separated by layers of iodine atoms or [BiI] zigzag-chains. The marked pseudo-symmetry of the structure favours stacking faults, which cause streaks of diffuse scattering in the diffraction pattern.     

Zur Polymorphie von In5Br7

On the Polymorphism of In₅Br₇ The existence of two polymorphs of In₅Br₇ has been proved by single crystal structure determinations. In₅Br₇ (tP192) crystallizes with the tetragonal space group P4₁2₁2 and lattice parameters a_t = 1318.9(5) pm and c_t = 3723.8(9) pm (293 K). Concerning monoclinic In₅Br₇ (mC192), the centrosymmetric space group C2/c with lattice parameters a_m = 1867.3(4) pm, b_m=1867.0(5) pm, c_m = 1918.0(7) pm, and β_m = 103.96(2)° (293 K) has been confirmed. Both modifications of In₅Br₇ are built up from layers of the same type. These layers with a thickness of about 930 pm consist of structure fragments [InBr₂]⁴⁺ and [InBr₁₂]^4–. The anion is composed of two ethan‐like [InBr₆]^2– units, which contain In–In bonds. The stacking sequence of the layers with symmetry C 1 2 (1) differs for the two modifications of In₅Br₇. The tetragonal form is generated by applying a 4₁ screw axis; the monoclinic polymorph is formed by introducing inversion centers between the layers. The adequate name of In₅Br₇ = In[InBr₆]Br is triindium(I)‐hexabromodiindate(II)(In–In)‐bromide.     

Zur Frage nach der Existenz eines kubischen Pyrochlors Pb2Sb2O7

On the Problem of the Existence of a Cubic Pyrochlore Pb₂Sb₂O₇ The reaction of PbO, PbO₂, PbCO₃ or Pb(CH₃CO₂)₂ · 3 H₂O with Sb₂O₃ (ratio 2:1 Mol.) gives up to 700°C a cubic pyrochlore together with PbSb₂O₆. The pyrochlore contains Pb(IV) and has the approximate composition Pb[PbSb]O_6,75 with a = 1066–1069 pm. After heating up to 900°C rhombohedral Pb₂Sb₂O₇ is formed. There is no evidence for the existence of a cubic Pb₂Sb₂O₇ with Pyrochlore structure.     

Einkristalluntersuchungen an Fluoroperowskiten MPdF3 (M = Rb,K) und PdF2

Single Crystal Investigations on Fluoroperovskites MPdF₃ (M = Rb, K) and PdF₂ Single crystal investigations on PdF₂ (violet) confirm the tetragonale rutile structure [1, 2] with a = 495.44(3) pm, c = 338.48(3) pm, Z = 2, space group P4₂/mnm-D (No. 136) (x_F = 0.3058(8)). RbPdF₃ and KPdF₃ have been obtained. RbPdF₃ and KPdF₃ both ruby-red single crystals crystallize cubic (perovskite-structure), space group Pm3m-O (No. 221) with a = 429.41(8) pm (RbPdF₃) respectively a = 424.30(4) pm (KPdF₃).