CuClS0.94Te1.06 und CuBrS0.92Te1.08, zwei neue Kupfer(I)-chalkogenhalogenide mit neutralen [STe]-Schrauben

CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08, Two New Copper(I) Chalcogen Halides Containing Neutral [STe] Screws CuClS_0.94Te_1.06 and CuBrS_0.92Te_1.08 are two new, isotypic compounds of general composition CuXYY′ (X = halide, Y, Y′ = chalcogen) with a mixed chalcogen substructure. They crystallize in the monoclinic system, space group P2₁/n (No. 14), a = 7.878(2), b = 4.727(1), c = 10.759(2) Å, β = 103.97(2)°, V = 388.8(2) ų (CuClS_0.94Te_1.06) and a = 8.043(3), b = 4.746(2), c = 11.240(4) Å, β = 103.46(3)°, V = 417.3(3) ų (CuBrS_0.92Te_1.08), both with Z = 4. The crystal structures are dominated by ordered [STe^±0]-screws. From a crystal chemical point of view the sulfur and tellurium atoms are significantly different. The melting points are 341 °C (CuClS_0.94Te_1.06) and 336 °C (CuBrS_0.92Te_1.08). The compounds CuXYY′ (X = Cl, Br, I; Y, Y′ = S, Se, Te) are compared and discussed.     

The Crystal Structure of Tl2Te3 – a Reinvestigation

Crystals of the title compound were obtained by annealing a powder of Tl₂Te₃ in a vertical temperature gradient (230 °C–240 °C, 4 weeks). Tl₂Te₃ crystallizes in space group C2/c with lattice parameters of a = 13.275(1) Å, b = 6.562(1) Å, c = 7.918(1) Å, and β = 107.14°(2). The tellurium atoms form chains [Te₃^2–], consisting of interconnected linear triatomic · Te–^Te–Te · groups which are isosteric with XeF₂. The Te–Te distances of the XeF₂-like units are 3.02 Å, the connecting ones 2.83 Å.     

Ein Beitrag zur Kristallstruktur von CuYW2O8, CuHoW2O8 und CuYbW2O8

A Contribution on the Crystal Structure of CuYW₂O₈, CuHoW₂O₈, and CuYW₂O₈ Single crystals of (I) CuY₂O₈, (II), CuHoW₂O₈, and (III) CuYbW₂O₈ were prepared and investigated by X-ray technique. (I) crystallizes with triclinic symmetry, space group C? P1 (a = 5.939 Å, b = 6.042 Å, c = 5.025 Å; α = 112.30°, β = 111.77°; Z = 1). (II) and (III) belong to monoclinic symmetry, space group C? P2/n (II) (a = 10.045 Å, b = 5.808 Å, c = 5.021 Å; β = 94.38°; z = 2 (III) a = 9.948 Å, b = 5.824 Å, c = 5.008 Å; β = 93.36°; Z = 2). The crystal structures will be discussed with respect to other to copper rare earth tungstates.     

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⁺.     

The Crystal Structure of Pb8FeIIFeF24: an ordered Fluorite-like Compound

Pb₈Fe^IIFeF₂₄ is triclinic: a = 20.118(3) Å, b = 5.597(1) Å, c = 9.440(2) Å, α = 89.75(2)°, β = 105.79(2)°, α = 89.38(2)°, Z = 2. The structure is solved in the unconventional space group C1 , from X-ray single crystal data using 1 641 independent reflections (R = 0.048, R_w = 0.051). It is built up from the stacking of two subnetworks along the a axis: fluorite-like [Pb₈F₁₀]_n⁶ⁿ⁺ layers and infinite dimetallic [Fe^IIFeF₁₄]_n^6n? double-chains of corner-sharing octahedra running along the b axis.     

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.     

CuClSe1.53Te0.47 and CuClSe0.56Te1.44: Structural and Vibrational Spectroscopic Investigations on Copper(I) Chalcogen Chlorides

CuClSe_1.53Te_0.47 and CuClSe_0.56Te_1.44 are obtained from the reaction of CuCl, Se, and Te in stoichiometric amounts. Both copper(I) selenium tellurium chlorides are monoclinic, space group P2₁/n (no. 14) with lattice constants of a = 7.837(1) Å, b = 4.699(1) Å, c = 10.762(2) Å, β = 104.37(2)°, V = 383.9(1) ų (CuClSe_1.53Te_0.47), and a = 8.074(1) Å, b = 4.830(1) Å, c = 10.973(1) Å, β = 103.87(2)°, V = 415.5(1) ų (CuClSe_0.56Te_1.44), and Z = 4. A common feature of these isostructural compounds are heteroatomic strands [YY'] (Y, Y' = chalcogen). These strands are running along [010] and are connected to layers by chains [CuCl]. Vibrational spectra of CuClSe_1.53Te_0.47, CuClSe_0.56Te_1.44, CuXTe₂ and CuX'Se₂ (X = Cl, Br, I; X' = Cl, Br) are analysed with respect to the bonding relations of the chalcogen chains. Modes derived from IR and Raman spectra are assigned by correlation with tri gonal Se and related copper(I) chalcogen halides. Both, X‐ray structural data and an analysis of the chalcogen vibrational modes in IR and Raman spectra, lead to a detailed insight into the ordering phenomena of the chalcogen chains in this type of copper(I) chalcogen halides.     

Rapid and Simple Isolation of the Crystalline Molybdenum-Blue Compounds with Discrete and Linked Nanosized Ring-Shaped Anions: Na15[MoMoO462H14(H2O)70]0.5 [MoMoO457H14(H2O)68]0.5 · ca. 400 H2O and Na22[MoMoO442H14(H2O)58] · ca. 250 H2O

The blue mixed-crystal title compound Na₁₅[MoMoO₄₆₂H₁₄ (H₂O)₇₀]_0.5[MoMoO₄₅₇H₁₄ · (H₂O)₆₈]_0.5 · ca. 400 H₂O ≡ Na₁₅[ 1 a ]_0.5[ 1 b ]_0.5 · ca. 400 H₂O 1 , which crystallizes in the triclinic space group P 1 (a = 30.785(2), b = 32.958(2), c = 47.318(3) Å, α = 90.53(1), β = 89.86(1), γ = 96.85(1)°, V = 47665(6) ų, Z = 2, D_calc = 2.149 g cm^–3), precipitates within one day when an acidic (pH ≈ 1) aqueous solution of sodium molybdate (because of the extremely high solubility of the reaction product used in relatively high concentration) is reduced by sodium dithionite. 1 contains hitherto unknown pure molybdenum-oxide based, nanosized, ring-shaped, crystallographically independent cluster anions of the type {Mo₁₅₄} 1 a and {Mo₁₅₂} 1 b , the lacunary-type analogue of 1 a . Using the same reducing agent but in the presence of a reagent with a high affinity to the specific {Mo₂}-type building unit (also a leaving group) of 1 a , such as formic acid, the compound Na₂₂[MoMoO₄₄₂H₁₄(H₂O)₅₈] · ca. 250 H₂O 2 (space group P 1, a = 24.724(1), b = 35.726(2), c = 44.608(3) Å, α = 93.25(1), β = 93.51(1), γ = 106.72(1)°, V = 37552(4) ų, Z = 2, D_calc = 2.401 g cm^–3) is obtained in which the giant rings, having four missing {Mo₂} units compared to 1 a , are linked to chains. Until now, similar chain-type compounds could only be obtained using a non-well-defined synthetic method.     

EPR-Einkristalluntersuchungen System Fe(NO)(Et2dsc)2/In(Et2dsc)3 (Et2dsc = Diethyldiselenocarbamat). Kristall- und Molekülstruktur von Tris(diethyldiselenocarbamato)indium(III), In(Et2dsc)3

Single Crystal Electron Paramagnetic Resonance Study on the System Fe(NO)(Et₂dsc)₂/In(Et₂dsc)₃ (Et₂dsc = diethyldiselenocarbamate). Crystal and Molecular Structure of Tris(diethyldiselenocarbamato)indium(III), In^III(Et₂dsc)₃ A single-crystal EPR study (T = 295 K) of Bis(diethyldiselenocarbamato)nitrosyliron(I) incorporated in Tris(diethyldiselenocarbamato)indium(III) is reported. The tensors g an A^N have rhombic symmetry with g₁ = 2.048, g₂ = 2.058, g₃ = 2.062 and A = 9.2 · 10^?4 cm^?1, A = 10.0 · 10^?4 cm^?1, A = 11.3 · 10^?4 cm^?1. The A values are discussed in terms of spin density distribution. The x-ray crystallographic data of In^III(Et₂dsc)₃ (space group P2₁/c, a = 6.731(3) Å, b = 18.05(9) Å, c = 20.914(10) Å, α = 90.02(2)°, β = 93.74(2)° and γ = 90.01(2)°) are given.     

Reaktion von cyclopentadienyl-substituierten Molybdän(V)-tetrachloriden mit LiPH(2,4,6-BuC6H2) und KPPh2(Dioxan)2. Molekülstrukturen von [Cp0Mo(μ-Cl)2]2 und [CpMo2(μ-Cl)3(μ-PPh2)] (Cp0 = C5Me4Et)

Reaction of Cyclopentadienyl Substituted Molybdenum(V) Tetrachlorides with LiPH(2,4,6-Bu C₆H₂) and KPPh₂(Dioxane)₂. Crystal Structures of [Cp⁰Mo(μ? Cl)₂]₂ and [Cp Mo₂(μ? Cl)₃(μ? PPh₂)] (Cp⁰ = C₅Me₄Et) The reaction of [Cp⁰Mo(CO)₃]₂ (Cp⁰ = C₅Me₄Et) and [Cp′Mo(CO)₃]₂ (Cp′ = C₅H₄Me) with PCl₅ in CH₃CN furnishes the Mo(V) complexes Cp⁰MoCl₄(CH₃CN) 1 and Cp′MoCl₄(CH₃CN) 2 in good yields. While 1 and 2 are reduced by LiPH(2,4,6-BuC₆H₂) to the Mo(III) complexes [Cp⁰Mo(μ? Cl)₂]₂ 3 and [Cp′Mo(μ? Cl)₂]₂ 4 , the reaction of 1 with KPPh₂(dioxane)₂ yields the reduction/substitution product [CpMo₂(μ? Cl)₃(μ? PPh)] 5 in low yield. 1 – 4 were characterized spectroscopically (i.r., mass, 3 and 4 also n.m.r.). An X-ray crystal structure determination was carried out on 3 and 5. 3 crystallizes in the triclinic space group P1 (No. 2) with a = 8.278(4), b = 12.508(7), c = 12.826(7) Å, α = 86.78(5), β = 81.55(2), γ = 75.65(4)°, V = 1 272.4 ų and two formula units in the unit cell (data collection at ? 67°C, 4 255 independent observed reflections, R = 2.9%); 5 crystallizes in the triclinic space group P1 (No. 2) with a = 11.536(8), b = 12.307(9), c = 13.157(9) Å, α = 91.41(6), β = 100.42(5), γ = 112.26(6)°, V = 1 688.7 ų and two formula units in the unit cell (data collection at ? 60°C, 6 147 independent observed reflections, R = 4.9%). The crystal structure of 3 shows the presence of centrosymmetric dimeric molecules with four bridging chloro ligands. In 5, two Mo atoms are bridged by three chloro ligands and one PPh₂ ligand. The Mo? Mo bond length in 3 and 5 (2.600(2), 2.596(2) Å and 2.6388(8) Å) is in agreement with a Mo? Mo bond.     

The crystal structure of Pb7FeIIFe6IIIF34: A new jarlite-type compound

Pb₇Fe^IIFeF₃₄ is monoclinic: a = 16.375(2) Å, b = 11.233(2) Å, c = 7.615(1) Å, β = 102.67(1)º, Z = 2. The crystal structure was solved in the space group C2/m (nº 12), from X-ray single crystal data using 957 independent reflections (705 with F/σ(F) > 4, leading to R = 0.038). It consists in infinite helicoidal [Fe^IIFeF₃₄]_n^14n? double-chains of cornersharing octahedra running along the b-axis and separated from each other by lead ions.     

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.     

Die Kristallstruktur von Ammonium-dioxodifluorovanadat

The Crystal Structure of NH₄VO₂F₂ Crystals of NH₄VO₂F₂ are monoclinic, space group Pc, a = 4.814(2), b = 11.434(3), c = 7.214(2) Å, β = 108.84(4)°. Z = 4. The VO₂F-ion is polymeric. The structure consists of endless chains of strongly distorted octahedra with common edges. Two adjacent polyhedra are linked by an asymmetrical oxygen bridge (bond lengths 1.74 and 2.21 Å) and an asymmetrical fluorine bridge (bond lengths 1.97 und 2.21 Å). The terminal V? O- and V? F-distances are 1.55 and 1.86 Å, respectively.     

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].     

Zur Kenntnis der NaCl-Strukturfamilie Die Kristallstruktur von NaMnO2

To the Knowledge of the NaCl Family of Structure: The Crystal Structure of NaMnO₂ Ochre coloured single crystals of NaMnO₂ show a monoclinic [a = 5.662 Å, b = 2.860 Å, c = 5.799 Å, β = 113.1°] variant [C–C2/m; Na in 2(d), Mn in 2(a), O in 4(i), R = 11.2% (MoK_α)] of the α-NaFeO₂-type of structure. The Jahn-Teller-distortion within the {MnO₆}-Group ist remarkable with Mn ? O = 1.93 (4×), 2.40 (2 ×) Å. NaMnO₂ posesses temperature indepent paramagnetism: +_Mol =+3450 · 10^?6 cgs. The Madelung Part of Lattice Energy is calculated and discussed.     

Synthesis and structure of The Novel Layered Phase CsTi2Cl7

Reactions in the CsCl? TiCl₃? Ti system afford CsTiCl₃ (CsNiCl₃ type, a = 7.3086(7) Å, c = 6.0670(8) Å) and the new phase CsTi₂Cl₇, the structure of which was determined by single crystal X-ray diffraction means (P2/c, Z = 2, a = 7.0076(4) Å, b = 6.2256(4) Å, c = 12.000(2) Å, β = 92.175(6)°, R/R_w = 0.026/0.035 for 1403 reflections, 2Θ ≤ 60°, MoKα). The structure can be generated by condensation of TiCl₆ groups first through cis edges to form TiCl₂Cl_4/2 ribbons and then by interconnection of these with one chlorine per titanium to give layers, viz., [Ti(Cl)Cl_4/2Cl_1/2]^?. The remaining, singly bonded chlorine projects into the interlayer region and has a Ti? Cl distance 0.208 Å less than the average for the five, 2.466 Å, reflecting significant pi bonding of the chlorine to titanium. Possible interaction of the d orbitals on adjacent titanium(III) atoms is also considered.     

Die Kristallstruktur von NaBiO2

The crystal structure of NaBiO₂ NaBiO₂ crystallizes monoclinic in C with a = 7.39₄, b = 7.26₂, c = 5.88₆ Å, β = 127.7°; Z = 4. Parameters were refined by least-squares (555 hkl with |h?l| = 0 to 4; R = 10.9%). Angular groups [BiO₂] are twisted by 180°, forming chains [BiO_2/2O_2/2] along [001]. The MADELUNG part of lattice energy (MAPLE) is calculated and discussed.     

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.     

Die Kristall- und MolekülStruktur von (S4N3)2SbCI5

The structure of (S₄N₃)₂SbCI₅ has been determined by X-ray methods using least-squares′ refinement. The compound crystallises monoclinic; C–P2₁/c, a = 9.24 Å, b = 17.77 Å, c = 11.29 Å, β = 110.06°, Z = 4. The antimony atom has a fivefold coordination the geometry being derived from a deformed octahedron, the S₄N-rings retained their planar shape.     

Darstellung und Kristallstruktur von Na2Mn3O7

Synthesis and Crystal-Structure of Na₂Mn₃O₇ Single crystals of Na₂Mn₃O₇ have been grown hydrothermally applying high oxygen pressure (p = 2 kbar). The new compound cystallizes triclinic; space group P1 ; a = 6.636(6) Å, b = 6.854(6) Å, c = 7.548(6) Å, α = 105.76(6)°, β = 106.86(6)°, γ = 111.60(6)°; Z = 2. The crystal structure has been solved and refined to R = 7.9% and R_w = 6.2% (diffractometer data, 1044 independent reflexions). The crystal structure consists of Mn₃O₇^2? anions with manganese coordinated octahedrally by oxygen. These layered anions are hold together by Na⁺ ions (coordination numbers 5 and 6).