Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Struktur‐ und magnetochemische Untersuchungen an Ba5Mn3F19 und verwandten Verbindungen AII5MIII3F19

Structural and Magnetochemical Studies of Ba₅Mn₃F₁₉ and Related Compounds A^II₅M^III₃F₁₉ Single crystal structure determinations by X‐ray methods were performed at the following compounds, crystallizing tetragonally body‐centred (Z = 4): Sr₅V₃F₁₉ (a = 1423.4(2), c = 728.9(1) pm), Sr₅Cr₃F₁₉ (a = 1423.5(2), c = 728.1(1) pm), Ba₅Mn₃F₁₉ (a = 1468.9(1), c = 770.3(1) pm, Ba₅Fe₃F₁₉ (a = 1483.5(1), c = 766.7(1) pm), and Ba₅Ga₃F₁₉ (a = 1466.0(2), c = 760.1(2) pm). Only Ba₅Mn₃F₁₉ was refined in space group I4cm (mean distances for elongated octahedra Mn1–F: 185/207 pm equatorial/axial; for compressed octahedra Mn2–F: 199/182 pm), the remaining compounds in space group I4/m. In all cases the octahedral ligand spheres of the M1 atoms showed disorder, the [M1F₆] octahedra being connected into chains in one part of the compounds and into dimers in the other. The magnetic properties of the V, Cr and Mn compounds named above and of Pb₅Mn₃F₁₉ and Sr₅Fe₃F₁₉ as well were studied; the results are discussed in context with the in part problematic structures.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

Einkristalluntersuchungen an LiMF6 (M = Rh,Ir), Li2RhF6 und K2IrF6

Single Crystal Investigations on LiMF₆ (M = Rh, Ir), Li₂RhF₆, and K₂IrF₆ LiRhF₆, LiIrF₆, Li₂RhF₆, and K₂IrF₆ were obtained again, but for the first time investigated by single crystal X‐ray methods. Rubyred LiRhF₆ and yellow LiIrF₆ crystallize isostructural in the trigonal space group R3 – C²_3i (Nr. 148) with the lattice parameters LiRhF₆: a = 502.018(7) pm, c = 1355.88(3) pm, Z = 3 and d(Rh–F) = 185.5(1) pm; LiIrF₆: a = 506.148(4) pm, c = 1362.60(2) pm, Z = 3, d(Ir–F) = 187.5(3) pm (LiSbF₆‐Typ). Yellow Li₂RhF₆ crystallizes tetragonal in the space group P4₂/mnm – D¹⁴_4h (Nr. 136) with a = 463.880(8) pm, c = 905.57(2) pm, Z = 2 and d(Rh–F) = 190.3(4)–191.4(3) pm (Trirutil‐Typ). Yellow K₂IrF₆ crystallizes trigonal in the space group P3m1 – D³_3d (Nr. 164) with a = 578.88(7) pm, c = 465.06(5) pm, Z = 1 and d(Ir–F) = 194.0(6) pm, isotypic with K₂GeF₆.     

Kristallstrukturen von Octacyanomolybdaten(IV). III [1] (NMe4)3Li[Mo(CN)8] · 3,5 H2O und Cs7Na[Mo(CN)8]2 · 4,17 H2O: Beispiele für dodekaedrische und quadratisch-antiprismatische Achterkoordination

Crystal Structures of Octacyanomolybdates(IV). III (NMe₄)₃Li[Mo(CN)₈] · 3.5 H₂O and Cs₇Na[Mo(CN)₈]₂ · 4.17 H₂O: Examples of Dodecahedral and Square Antiprismatic Eight-Coordination At single crystals of the hydrated tetragonal cyano complexes (NMe₄)₃Li[Mo(CN)₈] · 3.5 H₂O (a = 1707.5(3), c = 1054.9(2) pm, space group P42₁m, Z = 4) and Cs₇Na[Mo(CN)₈]₂ · 4.17 H₂O (a = 1547.9(1), c = 3254.6(6) pm, I4₁/a, Z = 8) X-ray structure determinations were performed. The [Mo(CN)₈]^4– polyhedra agree with respect to their mean distances Mo–C and C–N (216,7/114,3 pm resp. 216,1/114,7 pm) within their standard deviations, however, there is a distorted dodecahedron in the first case ((NMe₄)₃Li-complex), and a distorted square antiprism in the second (Cs₇Na-complex). The coordination of the counter cations, partly hydrated, the formation of hydrogen bridges and the packing of the complex anions is discussed.     

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).     

Alkalimetall‐Oxoantimonate: Synthesen,Kristallstrukturen und Schwingungsspektren von ASbO2 (A = K,Rb), A4Sb2O5 (A = K,Rb, Cs) und Cs3SbO4

Alkaline Metal Oxoantimonates: Synthesis, Crystal Structures, and Vibrational Spectroscopy of ASbO₂ (A = K, Rb), A₄Sb₂O₅ (A = K, Rb, Cs), and Cs₃SbO₄ The compounds ASbO₂ (A = K/Rb; monoclinic, C2/c, a = 785.4(3)/799.6(1) pm, b = 822.1(4)/886.32(7) pm, c = 558.7(3)/559.32(5) pm, β = 124.9(1)/123.37(6)°, Z = 4) are isotypic with CsSbO₂ and the corresponding bismutates. The structures of the antimonates A₄Sb₂O₅ (A = K/Rb: orthorhombic, Cmcm, a = 394.9(1)/407.34(7) pm, b = 1807.4(1)/1893.5(1) pm, c = 636.34(9)/655.60(8) pm, Z = 2) and Cs₄Sb₂O₅ (monoclinic, Cm, a = 1059.81(7) pm, b = 692.68(8) pm, c = 811.5(1) pm, β = 98.7(1)°, Z = 2) both contain the anion [O₂SbOSbO₂]^4–. Cs₃SbO₄ (orthorhombic, Pnma, a = 1296.1(1) pm, b = 919.24(8) pm, c = 679.95(6) pm, Z = 4) crystallizes with the K₃NO₄ structure type.     

Chromhexacyano‐Komplexe: Die Kristallstrukturen der Cyanoelpasolithe (NMe4)2ACr(CN)6 (A = K,Cs) und der kubischen Bariumverbindung Ba3[Cr(CN)6]2 · 20 H2O

Chromium Hexacyano Complexes: The Crystal Structures of the Cyano Elpasolites (NMe₄)₂ACr(CN)₆ (A = K, Cs) and of the Cubic Barium Compound Ba₃[Cr(CN)₆]₂ · 20 H₂O The crystal structures of the cyano elpasolites (NMe₄)₂KCr(CN)₆ (a = 1527.3(1), b = 888.1(1), c = 1539.0(1) pm, β = 109.92(1)°; C2/c, Z = 4) and (NMe₄)₂CsCr(CN)₆ (a = 1278.9(1) pm; Fm3m, Z = 4), as well as of the cubic compound Ba₃[Cr(CN)₆]₂ · 20 H₂O (a = 1631.0(1) pm; Im3m, Z = 4) were determined by X‐ray methods with single crystals. Reasons for the enlarged distances within the [Cr(CN)₆]^3–‐octahedron of the K compound (Cr–C: 209.3 pm) compared to the observations within both cubic complexes (206.1 resp. 206.9 pm) are discussed in context with the tolerance factors of cyano elpasolites. As is the case there concerning the cyano bridges Cr–CN–A towards the alkali ions the novel structure type of the barium compound, too, exhibits nearly linear bridging towards Ba. It contributes, however, only four N ligands to the ninefold [BaN₄O₅] coordination; part of the aqua ligands show disorder (Ba–N: 287.5, Ba–O: 281/293 pm).     

Struktur und Magnetismus von Fluoriden Cs2MCu3F10 (M = Mg,Mn, Co,Ni), Varianten des CsCu2F5‐Typs

Structure and Magnetism of Fluorides Cs₂MCu₃F₁₀ (M = Mg, Mn, Co, Ni), Variants of the CsCu₂F₅ Type X‐ray structure determinations of single crystals showed that compounds Cs₂MCu₃F₁₀ crystallize with Z = 2 in space group P2₁/n (No.14) (M = Mn) of the CsCu₂F₅ type resp. in its supergroup I2/m (No.12) (M = Mg, Co, Ni). Cs₂MgCu₃F₁₀: a = 714.9(1), b = 736.8(1), c = 940.4(1) pm, b = 96.29(1)°, (Mg‐F: 199.2 pm); Cs₂MnCu₃F₁₀: a = 725.1(1), b = 742.7(1), c = 951.0(2) pm, b = 97.28(3)°, (Mn‐F: 209.1 pm); Cs₂CoCu₃F₁₀: a = 717.8(3), b = 739.1(2), c = 939.4(4) pm, b = 97.49(2)°, (Co‐F: 203.1 pm); Cs₂NiCu₃F₁₀: a = 716.3(1), b = 737.7(1), c = 938.2(2) pm, b = 97.09(1)°, (Ni‐F: 201.0 pm). As determined directly for the Mg compound and generally concluded from the average distances M‐F noted, M substitution concerns mainly the octahedrally coordinated position of the CsCu₂F₅ structure, the distortion of which is very much reduced thereby. Within the remaining [CuF₄] and [CuF₅] coordinations, in contrast to CsCu₂F₅, one F ligand is disordered, in case of the Mn compound the pyramidally coordinated Cu atom, too. The magnetic properties are complex and point to frustration and spin glass effects. Only at the diamagnetically substituted variants with M = Mg, Zn no Néel point appears, which is reached at 27, 23, 36 and 55 K for M = Mn, Co, Ni and Cu, resp. At lower temperatures ferri‐ resp. weak ferromagnetism and hysteresis is observed.     

Synthese und Kristallstruktur von Mangan(II)‐ und Zinkamid,Mn(NH2)2 und Zn(NH2)2

Synthesis and Crystal Structure of Manganese(II) and Zinc Amides, Mn(NH₂)₂ and Zn(NH₂)₂ Metal powders of manganese resp. zinc react with supercritical ammonia in autoclaves in the presence of a mineralizer Na₂Mn(NH₂)₄ resp. Na₂Zn(NH₂)₄_.0.5NH₃ to well crystallized ruby‐red Mn(NH₂)₂ (p(NH₃) = 100 bar, T = 130°C, 10 d) resp. colourless Zn(NH₂)₂ (p(NH₃) = 3.8 kbar, T = 250°C, 60 d). The structures including all H‐positions were solved by x‐ray single crystal data: Mn(NH₂)₂: I4₁/acd, Z = 32, a = 10.185(6) Å, c = 20.349(7) Å, N(F_o) with F > 3σ (F) = 313, N(parameter) = 45, R/R_w = 0.038/0.043. Zn(NH₂)₂: I4₁/acd, Z = 32, a = 9.973(3) Å, c = 19.644(5) Å, N(F_o) with F > 3σ (F) = 489, N(parameter) = 45, R/R_w = 0.038/0.043. Both compounds crystallize isotypic with Mg(NH₂)₂ [1] resp. Be(NH₂)₂ [2]. Nitrogen of the amide ions is distorted cubic close packed. One quarter of tetrahedral voids is occupied by Mn²⁺‐ resp. Zn²⁺‐ions in such an ordered way that units M₄(NH₂)₆(NH₂)_4/2 occur. The H‐atoms of the anions have such an orientation that the distance to neighboured cations is optimum.     

Tetragonale Fluorperowskite AM0,75 ▭ 0,25F3 mit Kationendefizit: K4MnIIMn2IIIF12 und Ba2Cs2Cu3F12

Tetragonal Fluoroperovskites AM_0,75 □ _0,25F₃ Deficient in Cations: K₄Mn^IIM₂^IIIF₁₂ and Ba₂Cs₂Cu₃F₁₂ By heating 2KMnF₃ + K₂MnF₆ and BaF₂, CsF + CuF₂ respectively, the isostructural tetragonal compounds K₄Mn₃F₁₂ (a = 832.2, c = 1643.0 pm) and Ba₂Cs₂Cu₃F₁₂ (a = 854.1, c = 1704.1 pm) were prepared. They crystallize in a cation-deficient perovskite structure exhibiting ordering of octahedral vacancies. Single crystal structures determinations in the space group I4₁/amd, Z = 4, yielded the following average distances within the octahedra, which are Jahn-Teller distorted for Mn^III and Cu^II:Mn^II? F = 208.3 pm, Mn^III? F = 4 × 183.0/2 × 209.7 pm; Cu? F = 190.7/227.1 and 190.6/236.4 pm, respectively. The results are discussed in comparison with related compounds.     

Carbonat‐Hydrate der schweren Alkalimetalle: Darstellung und Struktur von Rb2CO3 · 1,5 H2O und Cs2CO3 · 3 H2O

Carbonate Hydrates of the Heavy Alkali Metals: Preparation and Structure of Rb₂CO₃ · 1.5 H₂O und Cs₂CO₃ · 3 H₂O Rb₂CO₃ · 1.5 H₂O and Cs₂CO₃ · 3 H₂O were prepared from aqueous solution and by means of the reaction of dialkylcarbonates with RbOH and CsOH resp. in hydrous alcoholes. Based on four‐circle diffractometer data, the crystal structures were determined (Rb₂CO₃ · 1.5 H₂O: C2/c (no. 15), Z = 8, a = 1237.7(2) pm, b = 1385.94(7) pm, c = 747.7(4) pm, β = 120.133(8)°, V_EZ = 1109.3(6) · 10⁶ pm³; Cs₂CO₃ · 3 H₂O: P2/c (no. 13), Z = 2, a = 654.5(2) pm, b = 679.06(6) pm, c = 886.4(2) pm, β = 90.708(14)°, V_EZ = 393.9(2) · 10⁶ pm³). Rb₂CO₃ · 1.5 H₂O is isostructural with K₂CO₃ · 1.5 H₂O. In case of Cs₂CO₃ · 3 H₂O no comparable structure is known. Both structures show [(CO₃^2–)(H₂O)]‐chains, being connected via additional H₂O forming columns (Rb₂CO₃ · 1.5 H₂O) and layers (Cs₂CO₃ · 3 H₂O), respectively.     

Einkristallstrukturuntersuchungen an hexagonalen Fluorperowskiten AMIIF3 (MII = Mg,Mn, Fe,Co, Ni)

Single Crystal Structural Studies at Hexagonal Fluoride Perovskites AM^IIF₃ (M^II = Mg, Mn, Fe, Co, Ni) At single crystals of nine fluoride phases AMF₃ the hexagonal perovskite structures were refined by X‐ray methods, of RbNiF₃ below T_C £ 145 K, too. The hexagonal 6 L type (P6₃/mmc, Z = 6) is found at: RbMgF₃ (a = 585.7(1); c = 1426.0(1) pm), CsMnF₃ (624.4(1); 1515.4(4) pm), CsFeF₃ (616.8(1); 1488.4(6) pm), Rb_0.63Cs_0.37CoF₃ (599.1(1); 1460.3(4) pm), RbNiF₃ (128 K: 582.6(1); 1426.4(6) pm), Cs₂BaLiNi₂F₉ (593.1(1); 1447.1(4) pm). Of the hexagonal‐rhombohedral 9 L type (R 3 m, Z = 9) are CsCoF₃ (620.1(1); 2264.0(7) pm) and yellow CsNiF₃ (614.7(1); 2235.3(6) pm), prepared at lower temperatures resp. under high pressure, whereas light green CsNiF₃ (625.5(1); 524.2(1) pm) belongs to the 2 L type (P6₃/mmc, Z = 2). The occurence of these structures and the interatomic distances observed, comparing also normal and high pressure phases, are discussed in connection with the tolerance factor.     

Yb3F4S2: Ein gemischtvalentes Ytterbiumfluoridsulfid gemäß YbF2 · 2 YbFS

Yb₃F₄S₂: A mixed‐valent Ytterbium Fluoride Sulfide according to YbF₂ · 2 YbFS Attempts to synthesize ytterbium(III) fluoride sulfide (YbFS) from 2 : 3 : 1‐molar mixtures of ytterbium metal (Yb), elemental sulfur (S) and ytterbium trifluoride (YbF₃) after seven days at 850 °C in silica‐jacketed gastight‐sealed arc‐welded tantalum capsules result in the formation of the mixed‐valent ytterbium(II,III) fluoride sulfide Yb₃F₄S₂ (tetragonal, I4/mmm; a = 384,61(3), c = 1884,2(4) pm; Z = 2) instead. The almost single‐phase product becomes even single‐crystalline and emerges as black shiny platelets with square cross‐section when equimolar amounts of NaCl are present as fluxing agent. Its crystal structure can be described as a sheethed intergrowth arrangement of one layer of CaF₂‐type YbF₂ followed by two layers of PbFCl‐type YbFS parallel (001). Accordingly there are two chemically and crystallographically different ytterbium cations present. One of them (Yb²⁺) is surrounded by eight fluoride anions in a cubic fashion, the other one (Yb³⁺) exhibits a capped square‐antiprismatic coordination sphere consisting of four F^– and five S^2– anions. In spite of being structurally very plausible, the obvious ordering of the differently charged ytterbium in terms of a localized mixed valency can only be fictive because of the black colour of Yb₃F₄S₂ which rather suggests charge delocalization coupled with polaron activity.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂ReCl₄, [(Me₂PhP)₃Cl₂ReN]₂ReCl₄ · 2 SbCl₃ and [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] The reaction of ReNCl₂(PMePh)₃ with SbCl₅ in toluene yields the trinuclear complex [(Me₂PhP)₃Cl₂Re≡N]₂ReCl₄ · 2 SbCl₃ ( 1 · 2 SbCl₃). It forms triclinic crystals with the composition 1 · 2 SbCl₃, as well as monoclinic crystals 1 · 2 SbCl₃ · 4 C₇H₈. The monoclinic crystals with the space group P2₁/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, β = 95.51(1)°, Z = 2, have been used for a crystal structure determination. In the centrosymmetric complex 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit ReCl₄. The SbCl₃ molecules are coordinated by chlorine bridges to Cl atoms of 1 , and, in addition, connect the complexes 1 with each other. The SbCl₃ free compound 1 is obtained in good yield by the reaction of ReNCl₂(PMePh)₃ with ReCl₄(NCEt)₂. It crystallizes in the triclinic space group P1 with a = 1037.7(3), b = 1153.0(2), c = 1393.8(3) pm, α = 72.31(2)°, β = 74.06(2)°, γ = 67.94(2)°, and Z = 1. The bond lengths of the Re–N triple bonds are 172 pm in 1 and 170 pm in 1 · 2 SbCl₃. By the reaction of ReNCl₂(PMePh)₃ with SbCl₅ in CH₂Cl₂ the solvent is decomposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] ( 2 ) crystallizing in the monoclinic space group P2₁/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, β = 92,72(1)° and Z = 4. The Re–N distance in the almost linear unit Re≡N–H is 169,1 pm.     

Syntheses and Crystal Structures of [(AMTTO)Pd(PPh3)Cl]Cl · MeOH and [(AMTTO)Pd(SCN)2] · MeCN

The reaction of [(AMTTO)PdCl₂] ( 1 ) (AMTTO = 4-Amino-6-methyl-1,2,4-triazine-3(2H)-thione-5-one) with triphenylphosphane and sodium thiocyanate led to the air-stable crystalline complexes [(AMTTO)Pd(PPh₃)Cl]Cl · MeOH ( 2 ) and [(AMTTO)Pd(SCN)₂] · MeCN ( 3 ) in excellent yields. 2 and 3 have been characterized by IR and ³¹P NMR spectroscopy, elemental analyses as well as X-ray diffraction studies. Crystal data for 2 at –83 °C: monoclinic, space group P2₁/n, with a = 974.4(1), b = 988.6(1), c = 2750.7(2) pm, β = 98.16(1)°, Z = 4, R₁ = 0.0241 and for 3 at –80 °C: orthorhombic, space group P2₁2₁2₁, with a = 972.0(3), b = 1168.1(4), c = 1316.6(1) pm, Z = 4, R₁ = 0.0817.     

[(C2H5)3NH]2Sn3Se7 · 0,25 H2O und [(C3H7)2NH2]4Sn4Se10 · 4 H2O

Synthesis, Structure, and Properties of Some Selenidostannates. II. [(C₂H₅)₃NH]₂Sn₃Se₇ · 0,25 H₂O and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O The new selenidostannate hydrates [(C₂H₅)₃NH]₂Sn₃Se₇ · 0.25 H₂O ( I ) and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O ( II ) were synthesized from an aqueous suspension of triethylammonium (tripropylammonium), tin, selenium I and in addition sulfur II at 130 °C. I crystallizes at ambient temperature in the monoclinic space group P2₁/n (a = 2069,3(4) pm, b = 1396,6(3) pm, c = 2342,8(5) pm, β = 114,68(3)°, Z = 8) and is characterized by two different anions, chains from edge‐sharing [Se₃Se₇]^2– units and nets from trigonal SnSe₅ bipyramids. II crystallizes at ambient temperature in the tetragonal space group I4₁/amd (a = 2150,0(3) pm, c = 1174,4(2) pm, Z = 4) and contains adamantane like [Sn₄Se₁₀]^4–‐cages. The UV‐VIS spectra of the selenidostannates demonstrate that the absorption edges red shift as the dimensionality of the compounds is increased.     

Tris[3‐hydroxy‐2(1 H)‐pyridinonato]‐Komplexe von Al3+, Cr3+ und Fe3+ – Kristall‐ und Molekülstrukturen von 3‐Hydroxy‐2(1 H)‐pyridinon und Tris[3‐hydroxy‐2(1 H)‐pyridinonato]chrom(III)

Tris[3‐hydroxy‐2(1 H)‐pyridinonato] Complexes of Al³⁺, Cr³⁺, and Fe³⁺ – Crystal and Molecular Structures of 3‐Hydroxy‐2(1 H)‐pyridinone and Tris[3‐hydroxy‐2(1 H)‐pyridinonato]chromium(III) Tris[3‐hydroxy‐2(1 H)‐pyridinonato] complexes of Al³⁺, Cr³⁺ and Fe³⁺ are obtained by reactions of 3‐hydroxy‐2(1 H)pyridinone with the hydrates of AlCl₃, CrCl₃ or Fe(NO₃) in aqueous alkaline solutions as polycrystalline precipitates. The compounds are isotypic. X‐ray structure determinations were performed on single crystals of the uncoordinated 3‐hydroxy‐2(1 H)‐pyridinone ( 1 ) (orthorhombic, space group P2₁2₁2₁, a = 405.4(1), b = 683.0(1), c = 1770.3(3) pm, Z = 4) and of the chromium compound 3 (rhombohedral with hexagonal setting, space group R3c, a = 978.1(1), c = 2954.0(1) pm, Z = 6).     

(CH3)2SBr2 – einige Reaktionen und Strukturen

(CH₃)₂SBr₂ – Reactions and Structures (CH₃)₂SBr₂ ( 1 ) is a donor acceptor complex (8-S-3 + 10-Br-2) which reacts with (CH₃)₂S(?O)NSi(CH₃)₃ to yield [(CH₃)₂S(O)?N? S(CH₃)₂]⁺Br^? ( 2 ). With SbBr₃ (CH₃)₂SBr⁺SbBr₄^? ( 3 ) can be isolated. 1 crystallizes monoclinic in the space group P2₁/c with a = 733.8, b = 734.2, c = 1132.7 pm, β = 92.8° and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 967.2, b = 793.3, c = 1168.3 pm and Z = 4. The SBr and BrBr force constants of 1 are compared with those of S₂Br₂, 3 and Br₂ resp. The nmr and mass spectra of 1 and 2 are communicated.     

Synthese und spektroskopische Charakterisierung von Fluorocarbonylosmaten sowie Normalkoordinatenanalyse und Kristallstruktur von fac-[OsF3Br2(CO)]2–

Synthesis and Spectroscopic Characterization of Fluorocarbonylosmates, Normal Coordinate Analysis and Crystal Structure of fac -[OsF₃Br₂(CO)]^2– By treatment of (n-Bu₄N)₂[OsBr₅(CO)] with TlF in C₆H₅CF₃ fac-(n-Bu₄N)₂[OsF₃Br₂(CO)] is formed, from which salts with the cations (Et₄N)⁺, (py₂CH₂)²⁺, Tl⁺ and Cs⁺ are obtainable. Oxidation of the by-product [OsF₅(CO)]^2– with Cl₂ yields [OsF₅(CO)]^– which ¹⁹F NMR spectrum reveals a quintet (δ_F = 89.9) and a dublet (43.5 ppm) in the ratio 1 : 4 with coupling constants ²J_FF = 94.9 Hz. Simultaneously produced mer-[OsF₃Cl₂(CO)]^– exhibits in the high field region a triplet (δ_F = –70.4) and a dublet (–66.2 ppm) in the ratio 1 : 2 and ²J_FF = 9.5 Hz. The X-ray structure determinations of fac-Tl₂[OsF₃Br₂(CO)] ( 1 ) (monoclinic P2₁/n, a = 11.143(12), b = 11.654(4), c = 13.751(10) Å, β = 91.50(6)°, Z = 8) and fac-(py₂CH₂)[OsF₃Br₂(CO)] · 1/2(CH₃)₂CO ( 2 ) (triclinic, P 1, a = 8.432(1), b = 9.009(1), c = 12.402(2) Å, α = 80.30(1), β = 79.68(2), γ = 68.14(1)°, Z = 2) result in nearly C_s symmetry of the complex anion with bond lengths in the ranges Os–F = 1.98–2.08, Os–Br = 2.45–2.46, Os–C = 1.83–1.84, C–O = 1.10 – 1.17 Å. Using the molecular parameters of the X-ray determinations the IR spectra have been assigned by normal coordinate analysis. The valence force constants are f_d(CO) = 15.4–15.7, f_d(OsC) = 4.4–4.7, f_d(OsF) = 2.4–2.7, f_d(OsF˙) = 1.6–2.0, f_d(OsBr) = 1.7–2.1 mdyn/Å.