Pb3Fe2F12: A new fluorometallate with a tetrameric structural unit

Pb₃Fe₂F₁₂ grown by hydrothermal synthesis, crystallizes in the triclinic system, space group P1 , with a = 7.403(2) Å, b = 7.621(2) Å, c = 9.890(3) Å, α = 110.45(2)°, β = 107.98(1)°, γ = 95.92(2)°, V = 483.12(4) ų, Z = 2. The structure was solved from single crystal data using 3 913 independent reflections (R = 0.045 and R_w = 0.045). Characteristical of this structure is the presence of isolated tetrameric groups [Fe₄F₂₀]^8? in form of “rings” as previously observed in Ba₃Al₂F₁₂. “Independent” fluorine ions are also located and their cationic coordination is discussed. In contrast to Ba₃Fe₂F₁₂, all the rings are parallel in the structure.     

Synthesis and structure of trinuclear clusters (Et4N)2[(μ3-Se)]Fe3(CO)9, [(μ-H)2Fe3(μ3-Se)(CO)9], and [(μ3-Se)FeMo2(η5-C5H5)2(CO)7]

The cluster anion [Fe₃(μ₃-Se)(CO)₉]^2- (I) was isolated as a salt (Et₄N)₂[I] by the reaction of Fe(CO)₅ with Na₂Se in isopropanol. The protonated form, (μ-H)₂Fe₃(μ₃-Se)(CO)₉ (II), was obtained by acidifying the reaction mixture and used for the synthesis of the heterometallic cluster FeMo₂(μ₃-Se)(CO)₇Cp₂ (III), CP=η⁵-C₅H₅. The structure of I and III was established by X-ray diffraction analysis. Crystals I are monoclinic, a=14.210(3), b=11.547(3), c=19.831(2), Å, β=90.92(2)°, V_cell=3254(1) ų, space group P2/c, Z=4, d_calc=1.550 g/cm³, Syntex P2₁, λCuK_α, R(F)=0.1333 for 1264 F_hkl>6σ(F_hkl). Crystals III are monoclinic, a=20.440(5), b=12.771(3), c=16.342(4) Å, β=113.80(2)°, V_cell=3903(2) ų, space group P2₁/c, Z=8, d_calc=2.222 g/cm³, Syntex P2₁, λCuK_α, R(F)=0.0734 for 1116 F_hkl>4σ(F_hkl). The structure of II was inferred from the Mössbauer, IR, and¹H and⁷⁷Se NMR spectroscopy data.     

Reactivity of fac-[PPN][Fe(CO)3(TePh)3]: Structure of Fe2(μTePh)2(NO)4

Addition of NOBF₄ to fac-[PPN][Fe(CO)₃(TePh)₃] in THF at ambient temperature results in formation of Fe₂(μ-TePh)₂(NO)_4l Fe₂(?TePh)₂(CO)₆ and organic products. Methylation of fac-[PPN][Fe(CO)₃- (TePh)₃] by Mel or [Me₃O][BF₄] leads to the known dimer Fe₂(μ.-TePh)₂(CO)₆ and organic products. Fe₂(μ-TePh)₂(NO)₄ crystallizes in the orthorhombic space group P bca, with a = 12.701(5) Å, b = 6.7935(16) Å, c = 21.299(9) Å, V = 1837.8(11) ų, and Z = 4. The core geometry of Fe₂(μ-TePh)₂(NO)₄ is best described as a Fe₂Te₂ planar rhombus with Te-Fe-Te bond angle 112.09(4)°. A Fe-Fe bond (length 2.827(2) Å) is proposed for Fe₂(μ-TePh)₂(NO)₄ on the basis of the 18-electron rule. The iron atom adopts a distorted tetrahedral geometry with acute bridge Fe-Te-Fe angles 67.91(3)°, and bridging Fe-Te bond of length 2.53(1) Å.     

Alkoholyse von [Fe2(OtBu)6] als einfacher Weg zu neuen Eisen(III)‐Alkoxo‐Verbindungen: Synthesen und Kristallstrukturen von [Fe2(OtAmyl)6], [Fe5OCl(OiPr)12], [Fe5O(OiPr)13], [Fe5O(OiBu)13], [Fe5O(OCH2CF3)13], [Fe5O(OnPr)13] und [Fe9O3(OnPr)21] · iPrOH

Alcoholysis of [Fe₂(O^tBu)₆] as a Simple Route to New Iron(III)‐Alkoxo Compounds: Synthesis and Crystal Structures of [Fe₂(O^tAmyl)₆], [Fe₅OCl(OⁱPr)₁₂], [Fe₅O(OⁱPr)₁₃], [Fe₅O(OⁱBu)₁₃], [Fe₅O(OCH₂CF₃)₁₃], [Fe₅O(OⁿPr)₁₃], and [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH New alkoxo‐iron compounds can be synthesized easily by alcoholysis of [Fe₂(O^tBu)₆] ( 1 ). Due to different bulkyness of the alcohols used, three different structure types are formed: [Fe₂(OR)₆], [Fe₅O(OR)₁₃] and [Fe₉O₃(OR)₂₁] · ROH. We report synthesis and crystal structures of the compounds [Fe₅OCl(OⁱPr)₁₂] ( 2 ), [Fe₂(O^tAmyl)₆] ( 3 ), [Fe₅O(OⁱPr)₁₃] ( 4 ), [Fe₅O(OⁱBu)₁₃] ( 5 ), [Fe₅O(OCH₂CF₃)₁₃] ( 6 ), [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH ( 7 ) and [Fe₅O(OⁿPr)₁₃] ( 8 ). Crystallographic Data: 2 , tetragonal, P 4/n, a = 16.070(5) Å, c = 9.831(5) Å, V = 2539(2) ų, Z = 2, d_c = 1.360 gcm^?3, R₁ = 0.0636; 3 , monoclinic, P 2₁/c, a = 10.591(5) Å, b = 10.654(4) Å, c = 16.740(7) Å, β = 104.87(2)°, V = 1826(2) ų, Z = 2, d_c = 1.154 gcm^?3, R₁ = 0.0756; 4 , triclinic, , a = 20.640(3) Å, b = 21.383(3) Å, c = 21.537(3) Å, α = 82.37(1)°, β = 73.15(1)°, γ = 61.75(1)°, V = 8013(2) ų, Z = 6, d_c = 1.322 gcm^?3, R₁ = 0.0412; 5 , tetragonal, P 4cc, a = 13.612(5) Å, c = 36.853(5) Å, V = 6828(4) ų, Z = 4, d_c = 1.079 gcm^?3, R₁ = 0.0609; 6 , triclinic, , a = 12.039(2) Å, b = 12.673(3) Å, c = 19.600(4) Å, α = 93.60(1)°, β = 97.02(1)°, γ = 117.83(1)°, V = 2600(2) ų, Z = 2, d_c = 2.022 gcm^?3, R₁ = 0.0585; 7 , triclinic, , a = 12.989(3) Å, b = 16.750(4) Å, c = 21.644(5) Å, α = 84.69(1)°, β = 86.20(1)°, γ = 77.68(1)°, V = 4576(2) ų, Z = 2, d_c = 1.344 gcm^?3, R₁ = 0.0778; 8 , triclinic, , a = 12.597(5) Å, b = 12.764(5) Å, c = 16.727(7) Å, α = 91.94(1)°, β = 95.61(1)°, γ = 93.24(2)°, V = 2670(2) ų, Z = 2, d_c = 1.323 gcm^?3, R₁ = 0.0594.     

Zur Kristallstruktur von Cu2M(BO3)O2 (M = Fe3+, Ga3+)

The Crystal Structure of Cu₂M(BO₃)O₂ (M = Fe³⁺, Ga³⁺) Single Crystals of the compounds Cu₂M(BO₃)O₂ (M = Fe³⁺ (I), Ga³⁺ (II)) were obtained by a B₂O₃ flux-technique. They crystallize in a monoclinic distorted variant of a Ludwigite structure with a partly ordered metal distribution. X-ray investigations on single crystals led to the space group C–P2₁/c (No. 14); I: a = 3.108(1); b = 12.003(1); c = 9.459(3) Å; b? = 96.66(3)°; Z = 4 and II: a = 3.1146(2); b = 11.921(3); c = 9.477(2) Å; b? = 97.91(2)°; Z = 4. All metal-sites are distorted octahedraly coordinated by oxygen-ions. The structure contains isolated planar BO₃-units and oxygen which is not coordinated to boron.     

Ba7Fe6F32 · 2H2O: Original isolated trimers [Fe3F16]7− in a new defective jarlite-type compound

Ba₇Fe₆F₃₂ · 2H₂O was prepared from HF aqueous solution in a teflon bomb (Berghof) at 180°C. A partial exchange F^?/OH^? can be realized in more diluted HF medium and leads to Ba₇Fe₆F_32–x(OH)_x · 2H₂O. The compounds crystallize in the monoclinic system, space group C2/m (Z = 2) with a = 17.023(1) Å, b = 11.482(1) Å, c = 7.624(1) Å, β = 101.13(1)° for x = 0 and a = 17.036(2) Å, b = 11.489(1) Å, c = 7.620(2) Å, β = 101.48(1)° for x ≈? 5.3. The structures were determined from 2 256 and 1 343 independent reflections for x = 0 and x ≈? 5.3 respectively, collected with a Siemens AED2 four-circle diffractometer with the MoKα radiation (R = 0.0235 and R_w = 0.0240 for x = 0 and R = 0.0324 and R_w = 0.0335 for x ≈? 5.3). The structure, closely related to that of the Jarlite-type, is built up from isolated octahedra trimers [Fe₃F₁₆]^7?, connected together by Ba²⁺-cations. The location of anions and water molecules is discussed from bond valence calculations. Magnetic and Mössbauer studies are reported and discussed.     

Alkoxo‐Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe2(OtBu)6], [Fe2Cl2(OtBu)4], [Fe2Cl4(OtBu)2] und [N(nBu)4]2[Fe6OCl6(OMe)12]

Alkoxo Compounds of Iron(III): Syntheses and Characterization of [Fe₂(OtBu)₆], [Fe₂Cl₂(OtBu)₄], [Fe₂Cl₄(OtBu)₂] and [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] The reaction of iron(III)chloride in diethylether with sodium tert‐butylat yielded the homoleptic dimeric tert‐‐butoxide Fe₂(OtBu)₆ ( 1 ). The chloro‐derivatives [Fe₂Cl₂(OtBu)₄] ( 2 ), and [Fe₂Cl₄(OtBu)₂] ( 3 ) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1 , 2 , and 3 consists of two edge‐sharing tetrahedrons, with two tert‐butoxo‐groups as μ₂‐bridging ligands. For the synthesis of the alkoxides 1 , 2 , and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl₃(OEt₂)₂ ( 4 ) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo‐chloro‐oxo‐hexairon cluster [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] ( 5 ). Crystal structure data: 1 , triclinic, P1¯, a = 9.882(2) Å, b = 10.523(2) Å, c = 15.972(3) Å, α = 73.986(4)°, β = 88.713(4)°, γ = 87.145(4)°, V = 1594.4(5) ų, Z = 2, d_c = 1.146 gcm^—1, R₁ = 0.044; 2 , monoclinic, P2₁/n, a = 11.134(2) Å, b = 10.141(2) Å, c = 12.152(2) Å und β = 114.157(3)°, V = 1251.8(4) ų, Z = 2, d_c = 1.377 gcm^—1, R₁ = 0.0581; 3 , monoclinic, P2₁/n, a = 6.527(2) Å, b = 11.744(2) Å, c = 10.623(2), β = 96.644(3)°, V = 808.8(2) ų, Z = 2, d_c = 1.641 gcm^—1, R₁ = 0.0174; 4 , orthorhombic, Iba2, a = 23.266(5) Å, b = 9.541(2) Å, c = 12.867(3) Å, V = 2856(2) ų, Z = 8, d_c = 1.444 gcm^—1, R₁ = 0.0208; 5 , trigonal, P3₁, a = 13.945(2) Å, c = 30.011(6) Å, V = 5054(2) ų, Z = 6, d_c = 1.401 gcm^—1; R_c = 0.0494.     

Syntheses and structural study of trinuclear iron acetates [Fe3O(CH3COO)6(H2O)3]Cl· 6H2O and [Fe3O(CH3COO)6(H2O)3] [FeCl4]· 2CH3COOH

The structure of two trinuclear iron acetates [Fe₃O(CH₃COO)₆(H₂O)₃]Cl· 6H₂O (I) and [Fe₃O(CH₃COO)₆(H_2O)₃][FeCl₄] · 2CH₃COOH (II) was determined by X-ray diffraction analysis. Crystals I and II are ionic and belong to the orthorhombic system with parameters a = 13.704(3), b = 23.332(5), c = 9.167(2) Å, R = 0.0355, space goup P2₁2₁2 for I and a = 10.145(4), b = 15.323(6), c = 22.999(8) Å, R = 0.0752, space group Pbc2₁ for II. The complex cation [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ has a μ₃-O-bridged structure typical for trinuclear iron (III) compounds. As shown by Mössbauer spectroscopy, the iron(III) ions are in the high-spin state. In trinuclear cations, antiferromagnetic exchange interaction takes place between the Fe(III) ions with the exchange parameter J = -26.69 cm^?1 for II (Heisenberg-Dirac-Van Vleck model for D_3h, symmetry).     

Synthesis and crystal structure of two fluorophosphated compounds with different infinite sheets: Sr2Ga(HPO4)(PO4)F2 and Sr2Fe2(HPO4)(PO4)2F2

New compounds, Sr₂Ga(HPO₄)(PO₄)F₂ and Sr₂Fe₂(HPO₄)(PO₄)₂F₂, have been prepared by hydrothermal synthesis (700°C, 180 MPa, 24 h) and characterized by single-crystal X-ray diffraction. Sr₂Ga(HPO₄)(PO₄)F₂ crystallizes in the monoclinic space group P2₁/n with a = 8.257(1) Å, b = 7.205(1) Å, c = 13.596(2) Å, β = 108.02(1)°, V = 769.2(2) ų and Z = 4 and Sr₂Fe₂(HPO₄)(PO₄)₂F₂ in the triclinic space group P2₁/n with a = 8.072(1) Å, b = 8.794(1) Å, c = 8.885(1) Å, α = 102.46(1)°, β = 115.95(1)°, γ = 89.95(1)°, V = 550.6(1) ų and Z = 2. Structures are both based on different sheets involving corner-linkage between octahedra and tetrahedra. The sheets are linked by Sr²⁺ cations. Structural relationships exist between the descloizite mineral and the title compounds.     

Zur Kenntnis von Ba10Fe8Pt2Cl2O25

About Ba₁₀Fe₈Pt₂Cl₂O₂₅ The crystal structure of Ba₁₀Fe₈Pt₂Cl₂O₂₅ has been solved by direct methods, using intensity data collected by means of an automatic diffractometer (MoKα). It crystallizes in the hexagonal space group D–P6₃/mmc: a = 5.8034(4) Å, c = 24.997(5) Å, Z = 1. Fe³⁺ ions occur in both octahedral and tetrahedral coordination. Two types of Ba²⁺ ions are formed, with ten and twelve neighbouring atoms. The structure consists of plane connected FeO₆ and PtO₆ octahedra which are connected by corner shared FeO₄ tetrahedra.     

The phase relations in the In2O3A2O3BO systems at elevated temperatures [A: Fe or Ga, B: Cu or Co]

The phase relations in the In₂O₃Fe₂O₃CuO system at 1000°C, the In₂O₃Ga₂O₃CuO system at 1000°C, the In₂O₃Fe₂O₃CoO system at 1300°C, and the In₂O₃Ga₂O₃CoO system at 1300°C were determined by means of a classical quenching method. InFeCuO₄ (a = 3.3743(4) Å, c = 24.841(5) Å), InGaCuO₄ (a = 3.3497(2) Å, c = 24.822(3) Å), and InGaCoO₄ (a = 3.3091(2) Å, c = 25.859(4) Å) having the YbFe₂O₄ crystal structure, In₂Fe₂CuO₇ (a = 3.3515(2) Å, c = 28.871(3) Å), In₂Ga₂CuO₇ (a = 3.3319(1) Å, c = 28.697(2) Å), and In₂FeGaCuO₇ (a = 3.3421(2) Å, c = 28.817(3) Å) having the Yb₂Fe₃O₇ crystal structure, and In₃Fe₃CuO₁₀ (a = 3.3432(3) Å, c = 61.806(6) Å) having the Yb₃Fe₄O₁₀ crystal structure were found as the stable ternary phases. There is a continuous series of solid solutions between InFeCoO₄ and Fe₂CoO₄ which have the spinel structure at 1300°C. The crystal chemical roles of Fe³⁺ and Ga³⁺ in the present ternary systems were qualitatively compared.     

Fe4Si2Sn7O16: Eine Kombination von FeSn6-Oktaedern mit Schichten von (Fe3Sn)O6-Oktaedern; Präparation,Eigenschaften und Kristallstruktur [1]

Fe₄Si₂Sn₇O₁₆: A Combination of FeSn₆-Octahedra with Layers of (Fe₃Sn)O₆-Octahedra; Preparation, Properties, and Crystal Structure Fe₄Si₂Sn₇O₁₆ has been prepared by a solid state reaction at 900 °C from a mixture of Fe₂O₃, SnO₂, Sn, and Si. The compound is a paramagnetic semiconductor. Results of Mössbauer and suszeptibility measurements as well as bond length-bond strength calculations lead to the possible ionic formulation Fe₄²⁺Si₂⁴⁺Sn₁²⁺Sn₁⁴⁺O₁₆^2–. The compound crystallizes in the trigonal space group P3m1 (no. 164), with one formula unit per cell. Lattice parameters obtained by powder measurements are: a = 6.8243(6) Å, c = 9.1404(6) Å, γ = 120°, V = 368.6(1) ų. The structure consists of layers of edge linked oxygen octehedra exactly centered by Sn and Fe in the ratio 1 : 3. Three plains of isolated SiO₄ tetrahedra, FeSn₆ octahedra and again SiO₄ terahedra are inserted between two such layers. The layers are stacked along [001] and linked three-dimensionally by oxygen.     

Syntheses and Crystal Structures of Ca3Fe2(SeO3)6 and Sr3Fe2(SeO3)6

The new compounds M₃Fe₂(SeO₃)₆ (M = Ca, Sr) were obtained as crystalline precipitates from aqueous solutions of the respective ions, kept in Teflon-coated vessels at a temperature of 227(2)°C for several days. The crystal data are: space group R3 c, a = 8.531(2), 8.802(2) Å; c = 38.89(1), 39.00(1) Å; V = 2451.1, 2616.7 ų, Z = 6. The crystal structures have been refined by single-crystal X-ray diffraction methods to R1 = 0.021, 0.023; wR2 = 0.038, 0.039. The framework structure is built up by two types of FeO₆ octahedra as well as by MO₈ groups and SeO₃ trigonal pyramids by corner- and edge-linkage of the polyhedra.     

Synthesis and crystal structure of (Et4N)[{μ 3-SbI}Fe3(η 5-C5H5)(CO)10]

Crystal structure of (Et₄N)[{μ ₃-SbI}Fe₃-SbI}Fe₃Cp(CO)₁₀] was determined by X-ray diffraction analysis. The compound was synthesized by the reaction between (Et₄N)₂[Fe₂(CO)₈] and CpFe(CO)₂SbI₂ in a THF solution with cooling in an argon atmosphere. The crystals are monoclinic, a=12.792(2), b=14.152(3), c=17.373(3) Å, β=92.32(1)°, V_cell=3143(1) ų, space group P2₁/n, Z=4, d_calc=1.885 g/cm³, Syntex P2₁, λCuK_α radiation, R(F)=0.0744 for 877 F_hkl>6σ(F_hkl). The data were corrected for crystal decomposition according to the drop in the intensities of control reflections (by 23% during 29 h X-ray exposure). In the cluster anion, the Sb?Fe distances (ave. 2.57(1) Å) and the I?Sb?Fe and Fe?Sb?Fe angles (ave. 102.7(6) and 115.4(4)°) have virtually the same values as in other known complexes containing HalSbFe₃ and SbFe₄ fragments. The Fe...Fe distances of 4.312-4.369 Å indicate that the metal-metal bonds are absent.     

Crystal Structures of (Et4N)3M2F9 (M = V,Cr, Fe) determined by X‐Ray Single‐Crystal and Powder Diffraction: A New Structure Type for A3M2X9 Compounds

The syntheses and X‐ray structure determinations of single crystals and powders are reported for the compounds (Et₄N)₃M₂F₉ (M = V³⁺, Cr³⁺, Fe³⁺). The compounds are isostructural and represent a new structure type for A₃M₂X₉ compounds. They crystallize in the hexagonal space group P6₃/m with Z = 2. Their lattice parameters are (Et₄N)₃V₂F₉: a = 13.3017(3), c = 10.7714(2) Å; (Et₄N)₃Cr₂F₉: a = 13.2691(3), c = 10.7148(3) Å; and (Et₄N)₃Fe₂F₉: a = 13.3040(3), c = 10.7650(3) Å.     

Synthesis,Structure and Magnetic Properties of a Cyclic Heterotetranuclear Co3Fe Complex of 2-Mercaptophenol (H2mp) with tri-n-Butylphosphine Participation

Neutral heterotetranuclear complex Co₃Fe(mp)₄(Hmp)(PBuⁿ₃)₃ 2 (PBuⁿ₃ = tri-n-butylphosphine) of 2-mercaptophenol (H₂mp) was synthesized in a molar ratio of CoCl₂:FeCl₃:H₂mp:NaOMe:PBuⁿ₃ = 0.75:0.25:1:2:1 under anaerobic conditions. It represents partially Fe^III-substituted form of the asymmetric mixed-valence tetracobalt complex Co₄(mp)₄(Hmp)(PBuⁿ₃)₃ (1). 2 crystallizes in the triclinic space group Pl?, with a = 12.373(2) Å, b = 15.677(3) Å, c = 20.571(4) Å, α = 93.59(3)° β = 93.45(3)° γ = 112.30(3)°, V = 3669 ų, and Z = 2. The molecule exhibits a cyclic skeleton of Co₃FeS₄O₃ with two doubly μ₂-S bridges, one doubly μ₂-O bridge, and one singly μ₂-O bridge. The four mp^2? ligands display two different modes, O_bS_b-T and O_tS_b, while the monoanion Hmp^? is only terminally chelated to Fe³⁺ ion in HO_tS_t fashion (b stands for bridge, t for terminal, and T for trinuclear). The three Co centers are located in approximately square-based pyramidal environments, and the Fe atom in distorted trigonal bipyramidal geometry. Three types of main fragment ions were observed in the FAB mass spectrum of 2. The dissociation of the fragments follows the order: PBuⁿ₃ first, then Hmp and mp ligands. Moreover, the dissociation of Fe(Hmp) is first, followed by Co(mp) and Co(mp)₂, according with the fact that Fe(Hmp) is only loosely bonded. Variable-temperature magnetic susceptibility measurements showed that 2 exhibits weak magnetic exchange interactions.     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.     

Macrocyclic Cr3+, Mn2+ and Fe3+ complexes of a mimic SOD moiety: Design,structural aspects,DFT, XRD,optical properties and biological activity

A novel SOD-like macrocycle “H₂DPD” and its trivalent chromium, iron and divalent manganese complexes have been isolated and characterized using the conventional tools. The macrocycle was prepared by 2:2 condensation of P-phenylenediamine with 5,5-dimethyl1,3-cyclohexanedione. IR and electronic spectral data suggested that H₂DPD coordinates to the metal ion as N₄ tetradentate donor with two Cl⁻ occupying the remaining two sites of the distorted octahedron. XRD spectrum of Cr³⁺ complex indicated that the complex crystallizes in a face-centered monoclinic structure with lattice parameters: a = 10.9380 Å; b = 12.4870 Å; c = 12.4600 Å, α = γ = 90° and β = 111.430 with space group P 1 21/c 1 (14). The energy gap (E_HOMO-E_LUMO), molecular electrostatic potential map (EPM) of title compounds, bond length, bond angle, as well as global and local reactivity were estimated using DFT method. The E_g values obtained from electronic spectra of Cr³⁺, Mn²⁺ and Fe³⁺ complexes were found to be 1.284, 1.220 and 1.138 eV, respectively which are in accordance with those evaluated by DFT revealing semiconductor nature. Also, the thermal degradation of all title compounds was carried out and the kinetic parameters were evaluated using Coats-Redfern and Horowitz-Metzger equations. Moreover, the compounds have screened for antibacterial as well as superoxide mimic activities. Cr³⁺ complex exhibited the most significant potent activity against all bacterial strains. With respect to SOD-like activity, the macrocycle showed the most remarkable SOD-like activity comparable to the standard drug, ascorbic acid.     

Ein neuer Bautyp der Oxohalogenoferrate: Ba3 Fe2 O5 Cl2 und Ba3 Fe2 O5 Br2

New Structure Type of the Two Oxohalogenoferrites: Ba₃Fe₂O₅Cl₂ and Ba₃Fe₂O₅Br₂ The hitherto unknown compounds Ba₃Fe₂O₅Cl₂ (A) and Ba₃Fe₂O₅Br₂ (B) are pre-pared and examined by single crystal techniques. (A) and (B) crystallizes in the cubic space group I2₁ 3-T⁵; (A) a = 9.9705(3) and (B) a = 10.0039(8) Å, Z = 4. The new structure consists of 10 corner-shared tetrahedra which are connected to a two-dimensional ring system. The differences to the previously investigated compound Sr₃Fe₂O₅Cl₂ are discussed.     

Syntheses,Structures, and Properties of New Quaternary Gold-Chalcogenides: K2Au2Ge2S6, K2Au2Sn2Se6, and Cs2Au2SnS4

The new compounds K₂Au₂Ge₂S₆ ( 1 ), K₂Au₂Sn₂Se₆ ( 2 ), and Cs₂Au₂SnS₄ ( 3 ) have been synthesized through direct reaction of the elements with a molten polyalkalithiogermanate(stannate) flux at 650, 550, and 400 °C, respectively. Their crystal structures have been determined by single crystal X-ray diffraction techniques. 1 crystallizes in the monoclinic space group P2₁/n with a = 10.633(2) Å, b = 11.127(2) Å, c = 11.303(2) Å, β = 115,37(3)°, V = 1208,2(3) ų and Z = 4, final R(Rw) = 0.045(0.106). 2 crystallizes in the tetragonal space group P4/mcc with a = 8.251(1) Å, c = 19.961(4) Å, V = 1358,9(4) ų and Z = 4, final R(Rw) = 0.040(0.076). 3 crystallizes in the orthorhombic space group Fddd with a = 6.143(1) Å, b = 14.296(3) Å, c = 24.578(5) Å, V = 2158.4(7) ų and Z = 4, final R(Rw) = 0.039(0.095). The structures of 1 , 2 , and 3 consist of infinite, one-dimensional anionic chains containing X₂Q₆^4– units linked by Au⁺ ions and charge balancing K⁺/Cs⁺ ions situated between the chains. All compounds were investigated with differential thermal analysis, FT-IR, and solid state UV/VIS diffuse reflectance spectroscopy.