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.     

Über geordnete Perowskite mit Kationenfehlstellen. XI. Verbindungen vom Typ ABB□1/4WVIO6 ≙ ABIIB□WO24 mit AII,BII = Ba,Sr

On Ordered Perovskites with Cationic Vacancies. XI. Compounds of Type A B B □_1/4W^VIO₆ ? A B^IIB □W O₂₄ with A^II, B^II = Ba, Sr Depending on the ionic radii of the two and three valent cations in the perovskites of type ABB □_1/4W^VIO₆ ?; AB^IIB □WO₂₄ order disorder phenomena are present. The results of the x-ray and vibrational spectroscopic investigations as well as the diffuse reflectance spectra and the visible photoluminescence are reported.     

Über geordnete Perowskite mit Kationenfehlstellen. X. Verbindungen vom Typ ABB□1/4MVIO6 ≙ ABIIB□MO24 mit AII,BII = Ba,Sr, Ca und MVI = U,W

On Ordered Perovskites with Cationic Vacancies. X. Compounds of Type A B B □_1/4M^VIO₆ ? A B^IIB □M O₂₄ with A^II, B^II = Ba, Sr, Ca and M^VI = U, W Perovskites of type Ba₈B^IIB₂^III□UO₂₄ show polymorphic phase transformations of order disorder type. An 1:1 ordered orthorhombic HT form is transformed into a higher ordered LT modification with a fourfold cell content (four formula units Ba₈B^IIB□U₄O₂₄), compared to cubic 1:1 ordered perovskites A₂BMO₆. In the series Ba₈BaB□W₄O₂₄ and Sr₈SrB□W₄O₂₄ different ordering phenomena are observed. In comparison with 1:1 ordered cubic perovskites A₂BMO₆, the cell contains eight formula units AB^IIB□W₄O₂₄. The higher ordered cells with U^VI and W^VI are face centered, which has its origin in an ordering of cationic vacancies.     

Die Kristallstruktur von Perowskiten ANiIIMVIO6. II. Das Sr2NiWO6

The Crystal Structure of Perovskites A Ni^IIM^VIO₆. II. Sr₂NiWO₆ The results of an X-ray single crystal study of the perovskite Sr[Ni^IIW^VI]⁽⁶⁾O₆, ordered in the octahedral sites, are given. While Sr[Ni^IITe^VI]⁽⁶⁾O₆ crystallizes in a monoclinically deformed structure of the perovskite (elpasolite) type, showing a phase transition to a tetragonal lattice at 675 °K, Sr[Ni^IIW^VI]⁽⁶⁾O₆ is tetragonal already at 298°K (space group: C; a = b = 5.559 Å; c = 7.918 Å; Z = 2). The Ni? O distances found for the tungsten compound are nearly identical with those of the tellurium perovskite. In contradiction to crystal field theory very different values of the ligand field parameter Δ (ca. 25%) are observed for these two compounds however. Obviously this effect is caused by the rather different kind of bonding within the NiO₆ polyhedra in the two compounds. On the basis of the structural results the Ni? O-bonding in the two perovskites is discussed in dependence of the next nearest cationic environment.     

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.     

Darstellung,Kristallstruktur und Schwingungsspektren von (n-Bu4N)2[(Mo6I)(NCS)]

Synthesis, Crystal Structure, and Vibrational Spectra of (n-Bu₄N)₂[(Mo₆I)(NCS)] By treatment of [(Mo₆I)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(Mo₆I)(NCS)]^2– is formed. The X-ray structure determination of (n-Bu₄N)₂[(Mo₆I)(NCS)] · 2 Me₂CO (monoclinic, space group P2₁/c, a = 13.168(5), b = 11.964(5), c = 24.636(5) Å, β = 104.960(5)°, Z = 2) shows, that the thiocyanate groups are coordinated exclusively via N atoms with Mo–N bond lengths of 2.141–2.150 Å, Mo–N–C angles of 166–178° and N–C–S-angles of 174–180°. The vibrational spectra exhibit characteristic innerligand vibrations at 2073–2054 (ν_CN), 846–844 (ν_CS) and 480–462 cm^–1 (δ_NCS).     

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.     

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.     

Darstellung,Schwingungsspektrum und Kristallstruktur von (n‐Bu4N)2[(W6Cl)F] · 2 CH2Cl2 und 19F‐NMR‐spektroskopischer Nachweis der gemischten Clusteranionen [(W6Cl)FCl]2–, n = 1–6

Synthesis, Vibrational Spectra, and Crystal Structure of ( n ‐Bu₄N)₂[(W₆Cl )F ] · 2 CH₂Cl₂ and ¹⁹F NMR Spectroscopic Evidence of the Mixed Cluster Anions [(W₆Cl )F Cl ]^2–, n = 1–6 The reaction of (n‐Bu₄N)₂[(W₆Cl)Cl] with CF₃COOH in dichloromethane gives intermediately a mixture of the cluster anions [(W₆Cl)(CF₃COO)Cl]^2–, n = 1–6. By treatment with NH₄F the outer sphere coordinated trifluoracetato ligands are easily substituted and the components of the series [(W₆Cl)FCl], n = 1–6 are formed and characterized by their distinct ¹⁹F NMR chemical shifts. An X‐ray structure determination has been performed on a single crystal of (n‐Bu₄N)₂[(W₆Cl)F] · 2 CH₂Cl₂ (orthorhombic, space group Pbca, a = 15.628(4), b = 17.656(3), c = 20.687(4) Å, Z = 4). The low temperatur IR (60 K) and Raman (20 K) spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(WW) = 1.89, f_d(WF) = 2.43 and f_d(WCl) = 0.93 mdyn/Å.     

Über Perowskite ABBWVIO6

On Perovskites A B B W^VIO₆ Compounds of type ABBW^VIO₆ can be obtained with A^II ? Ba; B^I ? Li, Na and B^III ? La, Nd, Sm, Gd, Y, In, Sc just as with A^II ? Sr, B^I ? Li and B^III ? La, Nd, Sm, Gd, Y, In (all cubic ordered perovskites). For the cubic perovskites Sr₂Na_0,5La_0,5WO₆ and Sr₂Na_0,5Nd_0,5WO₆ additional superlattice reflections are observed (a ∽ 16.4 Å). The compounds Sr₂Na_0,5BWO₆ crystallize with B^III ? Sm, Gd in a monoclinic and with B^III ? Y, In in a rhombic distorted perovskite lattice. For the perovskites with A = Sr — dependent on ionic radii of the B ions — two different lattice types are present.     

Interactions Magnetiques dans quelques Ferrites Oxyfluores a Structure Spinelle de Formule ZnxMFe2−xO4–xFx (M ? Fe,Co, Ni)

Magnetic interactions in some oxyfluoroferrites of spinel structure with the formula Zn_xMe_2?xO_4?xFx (M = Fe, Co, Ni) Whereas the ferromagnetic spin arrangement of the B-cations is not modified by the Zn²⁺?Fe³⁺ substitution in the ZnFe[Fe₂₊Fe³⁺]O_4?xF_x (0 ≤ x ≤ 0,50) spinel, this same substitution leads to a spin canting in the ZnFe[Co₂₊Fe³⁺]O_4?xF_x and ZnFe[Ni₂₊Fe³⁺]O_4?xF_x (0 ≤ x ≤ 0,80) simples. The difference in the magnetic behaviors with regard to the AB and BB interactions can be explained on the basis of the magnetic exchange theory.     

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.     

19F-NMR-spektroskopischer Nachweis und Berechnung der statistischen Bildung der gemischten Clusteranionen [(Mo6BrCl)F]2−, n = 0 – 8

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆Br Cl )F ]^2?, n = 0 – 8 The complete system of the innersphere mixed clusters (Mo₆BrCl)⁴⁺ is formed by exchange of innersphere bound Clⁱ against outersphere bound Br^a on tempering the solid [(Mo₆Cl)Br] at 500°C for 16 h. After conversion with conc. HCl into (H₃O)₂[(Mo₆BrCl)Cl] and precipitation of the outer Cl^a with AgBF₄ in ethanol, treatment with tetrabutylammonium(TBA)fluoride yields (TBA)₂ [(Mo₆BrCl)F], a mixture of 22 different species. According to the sets of chemical equivalent fluorine atoms in total 55 ¹⁹F nmr signals are expected, which are really observed in the high resolution 1D-¹⁹F-nmr spectrum. Using increments of chemical shifts, peak intensities and multiplet structures as well as the 2D-¹⁹F/¹⁹F-COSY spectrum the complete and unambiguous assignment of all resonances is achieved. From the measured integral intensities the distribution of the different compounds is determined, revealing statistical formation of the geometrical isomers.     

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].     

19F-NMR-spektroskopischer Nachweis und statistische Untersuchung zur Bildung der gemischten Clusteranionen [(Mo6ICl)F]2−, n = 0–7, und Darstellung von (TBA)2[(Mo6I)F]

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆I Cl )F ]^2?, n = 0–7, and Preparation of (TBA)₂[(Mo₆I )F ] The octa-μ₃-iodo-hexafluoro-hexamolybdate(2?)ion [(Mo₆I)F]^2? is prepared for the first time. The system of the 21 innersphere mixed clusters (Mo₆ICl)⁴⁺, n = 0–7 is formed by exchange of innersphere bound Clⁱ against outersphere bound I^a on tempering solid [(Mo₆Cl)I] at 400°C. Prolonged tempering leads to increasing average n values of the mixture, which is converted into the tetrabutylammonium salt (TBA)₂[(Mo₆ICl)F]. Using increments of chemical shifts and integral peak intensities the 54 ¹⁹F-nmr signals of the 21 species (compound n = 8 is absent) are assigned and confirmed by the 2 D-¹⁹F/¹⁹F-COSY spectrum. From the measured intensities the distribution of the different compounds is determined and proves significant deviation from statistical occupation, revealing the preference of isomers with iodine atoms occupying edges of the innersphere cube and discrimination of those sharing diagonals of the faces. Moreover all compounds with n = 3 and 4 are present overaverage in comparison to the others.     

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.     

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.     

The crystal structure of tris (ethylenediamine), cobalt(III) hexacyanoferrate(III)dihydrate,Co(C2H8N2)3[Fe(CN)6] · 2H2O

The crystal structure of the title compound has been determined from three dimensional x-ray data obtained by the multiple film method. The space group is P2_l/n and the cell dimensions are: a = 14.90, b = 16.84, c = 8.38 Å; β = 93.5° Z = 4. The structure is formed by discrete Co (en) and Fe(CN) ions, both of which have an octahedral configuration. The Fe(CN) ions are approximately octahedrally surrounded by the Co (en) ions while arrangement of Fe (CN) ions around the Co(en) ions completely differs from an octahedron. The mean Fe? C and Co? C dustances are 1.91 and 2.01 Å, respectively. The water molecules do not play an important role in the structure and all distances between oxygen and other atoms indicate the presence of very weak hydrogen bonds. The salts M (en)₃ Q(CN)₆ · H₂O, where M = Co and Cr and Q = Cr, Mn, Fe and Co, are all isomorphous.     

NaAuIn2, ein ternäres Aurid mit ethananalogen In2Au6-Baueinheiten und [In2/2]-Ketten

NaAuIn₂, a Ternary Auride with Ethane Analogous In₂Au₆ Building Units and [In_2/2] Chains Silver coloured, brittle single crystals of NaAuIn₂ were synthesized by the reaction of NaN₃, gold-sponge and indium at 500°C. The structure was determined from X-ray single-crystal diffractometry data: space group Cmcm, Z = 4, a = 4.482(1) Å, b = 10.366(2) Å, c = 7.869(2) Å, R/R_w(w = 1) = 0.017/0.020, Z(F) ≥ 3σ(F) = 547 and N(var.) = 16. NaAuIn₂ crystallizes in the MgCuAl₂-structure type. Gold and indium form a framework structure. [AuIn_6/3] layers with trigonal prismatically coordinated gold are connected via In—In contacts along [010] which consist of ethane analogous In₂Au₆-building units. The In-partial structure consists of saw tooth like [In_2/2] chains along [001]. The sodium atoms occupy channel-like cavities within the Au—In framework structure.     

Subgroup 4 (Ti,Zr, Hf) derivatives of Cobalt Carbonyls

Bimetallic and trimetallic compounds containing unsupported bonds of subgroup 4 metals (M = Ti, Zr, Hf) and Co were prepared by hydride elimination (A) from RM derivatives (R¹ = PhCH₂; RN; R² = Me, Et)) and by salt elimination (B) from RMX (X = Cl, Br; R.¹ = PhCH₂, RN and R³O; R³= i-Pr, n-Bu)) by reaction with HCo(CO)₄ and Na[Co(CO)₄], respectively. Compounds RMCo(CO)₄ with R¹ = PhCH₂, RM[Co(CO)₄]₂ R.¹ = PhCH₂, were prepared both by methods A and B, while (R³O)₄-n Ti[Co(Co)₄]n (n = 1, 2) compounds were obtained by reaction B. Several tertiary phosphine and phosphite derivatives of the former two types were obtained by substitution of a carbonyl group by PR ligand or by A type reaction of HCo(CO)³(PR with RM compounds.