Redetermination of the Crystal Structure of the 1,2,4,7-anti-tetramethylbicyclo[2.2.1]heptan-2-yl cation at 110 K

The structure of the 1,2,4,7-anti-tetramethylbicyclo[2.2.1]heptan-2-yl cation ( 1 ) was redetermined by X-ray crystal structure analysis of its Sb₂F₁₁ salt at 110 K (P2₁/c, R1 = 5.76%). The most important structural features of 1 are: C(1)? C(2) = 1.409(9), C(1)? C(6) = 1.710(8), and C(2)…C(6) = 2.113(9) Å and C(2)? C(1)? C(6) = 84.7(4)°. These results agree with those obtained earlier by other methods for the rapidly equilibrating, partially s?-delocalized 1,2-dimethylbicyclo[2.2.1]heptan-2-yl cation ( 2 ). The detailed experimental procedure for the preparation of crystalline 1 · Sb₂F₁₁ and the crystal selection and mounting are described.     

Die Kristallstrukturen von (DDI)2[Sb2F6O] und (DDI)2[Sb3F7O2] (DDI = 1, 3‐Diisopropyl‐4, 5‐dimethylimidazolium) — Ein Beitrag zur Hydrolyse von SbF3 [1]

The Crystal Structures of (DDI)₂[Sb₂F₆O] and (DDI)₂[Sb₃F₇O₂] (DDI = 1,3‐Diisopropyl‐4,5‐dimethylimidazolium) — a Contribution to the Hydrolysis of SbF₃ [1] The salts (DDI)₂[Sb₂F₆O] ( 2 ) and (DDI)₂[Sb₃F₇O₂] ( 3 ), (DDI = 1,3‐diisopropyl‐4,5‐dimethylimidazolium) are obtained by hydrolysis of C₁₁H₂₀N₂SbF₃ ( 1 ). The anion [Sb₂F₆O]^2? consists of two SbF₂ fragments linked by a symmetrical oxygen bridge and two unsymmetrical fluorine bridges to form a distored ψ‐octahedral coordination sphere at the antimony atoms. In [Sb₃F₇O₂]^2?, two SbF₂ units are linked by a symmetrical fluorine bridge, while the third antimony atom is connected with each SbF₂ fragment by a symmetrical oxygen and an unsymmetrical fluorine bridge. The antimony atoms adopt the centres of strongly distored ψ‐polyhedra.     

Synthese,IR-Spektrum und Kristallstruktur von Sb12O18(OH)2Cl22 · 2CH2Cl2

Synthesis, IR Spectrum, and Crystal Structure of Sb₁₂O₁₈(OH)₂Cl₂₂ · 2CH₂Cl₂ The title compound has been prepared by the reaction of Sb₅O₇Cl₁₁ with dichloromethane at 20°C, forming colourless, moisture sensitive crystals. Sb₁₂O₁₈(OH)₂Cl₂₂ · 2CH₂Cl₂ crystallizes monoclinically in the space group P2₁/n with two formula units per unit cell. Structure solution with 2696 unique observed reflections, R = 0.042. Lattice dimensions at 19°C: a = 1350.2, b = 1466.7, c = 1392.9 pm, b? = 97.925°. The distorted octahedrally coordinated antimony atoms, bridged by oxygen atoms, exhibit a molecular array which may be seen as a fragment of the rutile type structure, isolated by terminal chloride ligands. The solvate molecule is associated by a hydrogen bridge OH···Cl.     

Dimers of Ag2+ Ions – Synthesis and Characterization of the Quaternary Silver Fluoride Ag2ZnZr2F14 with [Ag2F7]3– Units

Deep blue‐violet colored powder samples of Ag₂ZnZr₂F₁₄ were synthesized by heating Zn(NO₃)₂·4H₂O, Ag and ZrOCl₂·8H₂O at 300 °C under fluorine atmosphere. The crystal structure of Ag₂ZnZr₂F₁₄ was refined from X‐ray powder diffraction data using the Rietveld method (C2/m, a = 9.0206(1) Å, b = 6.6373(1) Å, c = 9.0563(1) Å, β = 90.44(1)°, Z = 2). The structure is derived from the isotypic Ag₃Zr₂F₁₄ by replacing only one of the two crystallographically different Ag²⁺ ions with Zn²⁺ ions, thus leading to discrete Ag₂F₇ dimers. These dimers are connected via nearly linear Ag–F···F–Ag bridges with short F···F distances of 2.33 Å to form two‐legged ladders. Magnetic susceptibility measurements and density functional calculations show that the two Ag²⁺ ions in each Ag₂F₇ dimer are strongly coupled antiferromagnetically.     

Synthesis and crystal structure of new sodium oxothiocyanofluoroantimonate(III) Na2Sb5F9O3(NCS)2

Na₂Sb₅F₉O₃(NCS)₂, a new complex, has been synthesized from NaSCN and SbF₃ aqueous solutions and studied by chemical, X-ray diffraction, and thermal analyses and IR, ^121,123Sb NQR, and ¹⁹F NMR spectroscopy. Its layered structure (triclinic symmetry system, a = 6.9998(1) Å, b = 9.4180(1) Å, c = 13.1094(2) Å, α = 74.815(1)°, β = 78.188(1)°, γ = 82.779(1)°, Z = 2, space group P $\bar 1$ ) is built of Na⁺ cations and [Sb₁₀F₁₈O₆(NCS)₄]^4? decanuclear complex anions that consist of two [Sb₅F₉O₃(NCS)₂]^2? pentanuclear complex anions linked by two weak Sb-F ionic bonds (2.529(2) Å). Decanuclear complex anions are linked into layers by secondary Sb…F bonds and Na-F bonds. Van der Waals interactions link these layers into a framework. The complex is stable up to 200°C.     

[Sb11]3− and [As11]3−: Synthesis and Crystal Structure of Two New Ammoniates containing Trishomocubane‐like Polyanions

The ammoniates [K(18‐crown‐6)(NH₃)₂]₃Sb₁₁ · 5.5NH₃ ( 1 ) and [Cs(18‐crown‐6)]₂CsAs₁₁ · 8NH₃ ( 2 ) (18‐crown‐6 = 18C6: 1,4,7,10,13,16‐Hexaoxacyclooctadecan) were synthesized by either the reaction of K₃Sb₇ with SbPh₃ in liquid ammonia or by extraction of Cs₃As₁₁ with liquid ammonia. Single crystals were isolated and characterized by low temperature X‐ray structure analysis. [K(18‐crown‐6)(NH₃)₂]₃Sb₁₁ · 5.5NH₃ crystallizes in the space group with a = 13.31(2) Å, b = 15.161(2) Å, c = 22.521(3) Å, α = 99.23(1)°, β = 100.99(1)° and γ = 105.03(1)°. [Cs(18‐crown‐6)]₂CsAs₁₁ · 8NH₃ crystallizes in the monoclinic space group C2/c with a = 20.009(3) Å, b = 17.024(1) Å, c = 19.838(2) Å and β = 119.732(9)°. While 1 contains isolated [Sb₁₁]^3? anions and [K(18‐crown‐6)(NH₃)₂]⁺ complexes, cesium–arsenic contacts lead to one–dimensionally infinite chains in 2 .     

Li2CrO4 · 2H2O: Ungewöhnliche Wasserstoffbrückenbindung und Koordination der O-Liganden des Anions CrO42−

Li₂CrO₄ · 2H₂O: Unusual Hydrogen Bridge Bonding and Coordination for Oxygen of the Anions CrO₄^2? The crystal structure of Li₂CrO₄ · 2H₂O was solved including the positions of hydrogen by X-ray methods. Li₂CrO₄ · 2H₂O: P2₁2₁2₁, Z = 4, a = 5.503(1) Å, b = 7.733(2) Å, c = 11.987(2) Å, Z(F_o) with (F_o)² ? 3σ(F_o)² = 2284, Z (parameter) = 99, R/R_w = 0.025/0.029 LiCrO₄ · 2H₂O contains a locally bordered hydrogen bridge bonding system between water molecules as donors and two O of CrO₄^2? as acceptors. This system connects anions in the direction [010]. It is noticeable that oxygen ligands of the anion CrO₄^2? have strongly differing coordination.     

A S8‐like [Sb8]8− Zintl Anion in the Ammoniate [K17(Sb8)2(NH2)] · 17.5NH3

The ammoniate [K₁₇(Sb₈)₂(NH₂)] · 17.5NH₃ was synthesized by reduction of antimony with potassium in liquid ammonia. Single crystals were isolated and characterized by low temperature X‐ray structure analysis. [K₁₇(Sb₈)₂(NH₂)] · 17.5NH₃ crystallizes in the space group P2₁/c (No. 14) with a = 12.976(1) Å, b = 24.536(1) Å, c = 22.858(1) Å and β = 99.17(1)°. The ammoniate contains crown‐shaped [Sb₈]^8? Zintl anions which are analogous to S₈ rings. The presence of amide NH₂^? as an additional anion is deduced from coordination observations and the close similarity of structural features to the structure of KNH₂.     

Anionische Antimon(III)-Fluorokomplexe mit protonierten Azakronenethern als Gegenionen. Strukturen und Mößbauerspektren von [H2cyclam]2[Sb4F16] · 2 H2O, [H4cyclam][Sb2F10] · 2 HF und [H4(tetramethyl)cyclam]2[Sb4F15][HF2][F]4 (cyclam = 1,4,7,11-Tetraazacyclotetradecan)

Anionic Antimony(III) Fluoro Complexes with protonated Azacrownethers as Counterions. Crystal Structures and Mößbauer Spectra of [H₂cyclam]₂[Sb₄F₁₆] · 2H₂O, [H₄cyclam][Sb₂F₁₀] · 2 HF, and [H₄(tetramethyl)cyclam]₂[Sb₄F₁₅][HF₂][F]₄ (cyclam = 1,4,7,11-Tetraazacyclotetradecane) The title compounds are formed by reaction of SbF₃ with the respective azacrownether. [H₂cyclam]₂[Sb₄F₁₆] · 2 H₂O contains tetrameric anions which weakly associate to chains. The [H₂cyclam]²⁺ ions possess an unusual conformation due to intramolecular hydrogen bonds. [H₄cyclam][Sb₂F₁₀] · 2HF contains the dimeric hitherto unknown [Sb₂F₁₀]^4? ion; two HF molecules are attached to it by hydrogen bonds. The structure of [H₄(tetramethyl)cyclam]₂[Sb₄F₁₅][HF₂][F]₄ is made up of the two dimensional polymeric [HSb₄F₁₇]^4? anion. The tetra-protonated tetramethylcyclam ions form host-guest complexes with fluoride ions.     

Mise en évidence de l'entité Sb2F4O dans un composé d'addition moléculaire avec l'urée étude structurale de [(NH2)2CO]2,Sb2F4O

The X-ray structure determination of [NH₂)₂CO]₂ · Sb₂F₄O shows the existence of linked units urea-Sb₂F₄O which show the Sb₂F₄O entity, not yet known. Crystal structure was solved with a singlecrystal X-ray diffraction study (the final R value is 0.046). The Sb₂F₄O unit is composed of a symmetric and short SbOSb bridge, and of four fluorine atoms, two being bonded to each antimony atom and situated in trans position relative to the SbOSb bridge. The bridge bond strength is assigned to a pπdπ overlap.     

Phosphaniminato-Komplexe des Antimons. Die Kristallstrukturen von [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN und [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN

Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN and [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl₂(NPMe₃) and SbCl₂(NPPh₃), respectively, which themselves are synthesized by reaction of antimony trichloride with Me₃SiNPR₃ (R = Me, Ph). The complexionic compounds are characterized by ¹²¹Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN: Space group P4₁, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl₆^? ions and cations [Sb₂Cl₅(NPMe₃)₂(CH₃CN)]⁺, in which one Sb^III atom and one Sb^V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl₆^? ions and centrosymmetric cations [SbCl(NPPh₃)(CH₃CN)₂]₂²⁺, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.     

Verbindungen in den Systemen Kalium(Rubidium)/Gold/Antimon: K3Au3Sb2, Rb3Au3Sb2 und K1,74Rb0,26RbAu3Sb2

Compounds in the Systems Potassium(Rubidium)/Gold/Antimony: K₃Au₃Sb₂, Rb₃Au₃Sb₂, and K_1,74Rb_0,26RbAu₃Sb₂ Brittle, silver coloured single crystals of K₃Au₃Sb₂, Rb₃Au₃Sb₂ and K_1,74Rb_0,26RbAu₃Sb₂ were obtainded by reaction of the alkali metal azides (KN₃, RbN₃) with gold and antimon powder at 550°C. The structures of the isotypic compounds (R3 m, Z = 3) were determined by X-ray single-crystal diffractometer data: K₃Au₃Sb₂, a = 6,198(2) Å, c = 21,520(5) Å, R/R_w (w = 1) = 0,046/0,058, Z(F) ? 3σ(F) = 175, Z(Var.) = 14; Rb₃Au₃Sb₂, a = 6,443(3), c = 21,69(2), R/R_w (w = 1) = 0,059/0,082, Z(F) ? 3σ(F₀²) = 258, Z(Var.) = 14; K_1,74Rb_0,26RbAu₃Sb₂, a = 6,288(2) Å, c = 21,617(5) Å, R/R_w (w = 1) = 0,049/0,069, Z(F) ? 3σ(F) = 390, Z(Var) = 14. The compounds crystallize with the K₃Cu₃P₂-structure type. The Au? Sb partial structures consist of [AuSb_2/3] layers with linear Sb? Au? Sb dumb-bells and SbAu₃ pyramids. The layers are separated by two crystallographically independent alkali metal atoms along [001].     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

The Role of Chloro Substituents in Solid Inclusion Formation. Crystal Structures Formed by a Bulky Hydroxy Host with Ethyl Acetate (2:1) and Cyclohexylamine (1:2) as Guest

Abstract

Two inclusion compounds of the 11-[bis(p‐chlorophenyl)hydroxymethyl]-9,10-dihydro-9,10-ethanoanthracene host (1) have been studied by X-ray diffraction in order to find an explanation of the exceptional clathrate formation ability of the present chloro-containing host as compared with that of closely related chlorine-free host analogues. Crystal data: 1·ethyl acetate (2:1), C₂₇H₂₂OCl₂·½(C₄H₈O₂), M_w = 501.45, P2_1/c, a = 8.9060(5), b = 11.1109(6), c = 25.642(1) Å, β = 99.03(1)°, Z = 4, R = 0.047 for 2029 F values with I>2σ(I); 1·cyclohexylamine (1:2), 2[C₂₉H₂₂OCI₂·2(C₆H₁₃N)], M_w = 1311.50, Pc, a = 12.144(2), b = 12.689(3), c =23.119(8) Å, β = 91.68(1)°, Z = 2, R = 0.054 for 3073 F values with I>2σ(I). Although the two solid inclusion compounds differ in host‐guest stoichiometry, space group symmetry and also in host‐guest recognition mode, both co-crystals are held together by numerous C?H…X (X = O, N or Cl) interactions, in which the chloro-substituents of 1 play a very active role. The observed frequent participation of chlorine in intermolecular interactions in these compounds suggests an ability of the (C?)Cl substituents to effectively enhance the crystal formation in the absence of more dominant forces.     

Synthesen und Schwingungsspektren der homoleptischen Acetonitrilkomplex-Kationen [Au(NCCH3)2]+, [Pd(NCCH3)4]2+, [Pt(NCCH3)4]2+ und des Adduktes CH3CN · SbF5. Kristallstrukturen der Salze [M(NCCH3)4][SbF6]2 · CH3CN,M = Pd,Pt

The Syntheses and Vibrational Spectra of the Homoleptic Metal Acetonitrile Cations [Au(NCCH₃)₂]⁺, [Pd(NCCH₃)₄]²⁺, [Pt(NCCH₃)₄]²⁺, and the Adduct CH₃CN · SbF₅. The Crystal and Molecular Structures of [M(NCCH₃)₄][SbF₆]₂ · CH₃CN, M = Pd or Pt Solvolyses of the homoleptic metal carbonyl salts [M(CO)₄][Sb₂F₁₁]₂, M = Pd or Pt, in acetonitrile leads at 50 °C both to complete ligand exchange for the cations as well as to a conversion of the di-octahedral anion [Sb₂F₁₁]^– into [SbF₆]^– and the molecular adduct CH₃CN · SbF₅ according to: [M(CO)₄][Sb₂F₁₁]₂ + 7 CH₃CN → [M(NCCH₃)₄][SbF₆]₂ · CH₃CN + 2 CH₃CN · SbF₅ + 4 CO M = Pd, Pt The monosolvated [M(NCCH₃)₄][SbF₆]₂ · CH₃CN are obtained as single crystals from solution and are structurally characterized by single crystal x-ray diffraction. Both salts are isostructural. The cations are square planar but the N–C–C-sceletial groups of the ligands depart slightly from linearity. The new acetonitrile complexes as well as [Au(NCCH₃)₂][SbF₆] and the adduct CH₃CN · SbF₅ are completely characterized by vibrational spectroscopy.     

Temperature Influence on the Formation of Selenidoantimonates: Solvothermal Syntheses,Crystal Structures and Thermal Properties of [Ni(dien)2]2Sb2Se6, [Mn(dien)2]2(SbSe4)(Cl), [Co(dien)2]2(SbSe4)(Br), and [Co(dien)2]3(SbSe4)2

New selenidoantimonats [Ni(dien)₂]₂Sb₂Se₆ ( 1 ), [Mn(dien)₂]₂(SbSe₄)(Cl) ( 2 ), [Co(dien)₂]₂(SbSe₄)(Br) ( 3 ), and [Co(dien)₂]₃(SbSe₄)₂ ( 4 ) (dien = diethylenetriamine) were solvothermally synthesized in dien solvent at 180 °C. The crystal structure of 1 consists of two octahedral [Ni(dien)₂]²⁺ cations and a mixed‐valent [Sb₂Se₆]^4? anion. The isolated [Sb₂Se₆]^4? anion is formed by a Sb^IIISe₃ trigonal pyramid and a Sb^VSe₄ tetrahedron sharing a common corner. 2 and 3 are composed of octahedral [M(dien)₂]²⁺ cations, tetrahedral [SbSe₄]^3? anions and halide ions forming an extended network through hydrogen‐bonding interactions. In 4 the [Co(1)(dien)₂]²⁺, [Co(2)(dien)₂]²⁺ and [SbSe₄]^3? ions form layered structures via N–H···Se hydrogen bonds. The [Co(3)(dien)₂]²⁺ ion is located between the layers, and interacts with the layers by N–H···Se bonds. The synthesis and solid state structural studies on the title compounds show that the higher reaction temperature is helpful for the formation of selenidoantimonate(V) compounds in the synthesis of selenidoantimonate from the M²⁺/Sb/Se/dien system. 1 – 4 start to decompose at temperature about 210 °C in N₂ atmosphere. They lose dien ligands at a wide temperature range of 210–450 °C with multisteps for 1 – 3 and a single step for 4 .     

Molecular and crystal structure of 1-hydroxy-2-methyl-11-methylene-tricyclo (5.3.1.0)2,7-undecan-5-one, C13O2H18

The title compound is orthorhombic witha = 26·132(6),b = 11·023(2),c = 8·317(5), ?; space group Iba2;Z = 8,D _m = 1·21(1),D _c = 1·192 Mg m⁻³, 1/2(H₂O) per molecule in asymmetric unit; λ (MoKα) = 0·7107A; μ = 0·46 cm⁻¹; F(000) = 936. The structure was solved by direct methods and refined to R(F) value of 0·069 using 327 reflections withF ≥ 5σ(F) out of 727 independent reflections for2τ max = 46°. Thetrans fused cyclohexane and cyclohexanone rings form layers along thea-b plane. The axial methyl attached at the bridge-head, interlocks with the translated methylene of the cyclobutane fused across the cyclohexane ring. The equatorial hydroxyl at the bridge-head adjacent to the methyl junction and the water molecule on the two-fold form a water bridge along thez axis. The packing is reminiscent of that observed for the cholesterols used in membrane structure studies.     

Earth Alkaline Tetrathiosquarates: Syntheses and Crystal Structures of MgC4S4 · 6 H2O and CaC4S4 · 4 H2O

Concentrated aqueous solutions of magnesium chloride and calcium nitrate, respectively, allow on addition of the potassium salt of tetrathiosquarate, K₂C₄S₄ · H₂O, the isolation of the earth alkaline salts MgC₄S₄ · 6 H₂O ( 1 ) and CaC₄S₄ · 4 H₂O ( 2 ) as orange and red crystals. The crystal structure determinations ( 1 : monoclinic, C2/c, a = 17.2280(7), b = 5.9185(2), c = 13.1480(4) Å, β = 104.730(3)°, Z = 4; 2 : monoclinic, P2₁/m, a = 7.8515(3), b = 12.7705(5), c = 10.6010(4) Å, β = 93.228(2)°, Z = 4) show the presence of C₄S₄^2? ions with almost undistorted D_4h symmetry having average C–C and C–S bond lengths of 1.451Å and 1.659Å for 1 and 1.451Å and 1.655Å for 2 . The structure of 1 contains discrete, octahedral [Mg(H₂O)₆]²⁺ complexes. Several O–H····O and O–H····S bridges with H····O and H····S distances of less than 2.50Å connect cations and anions. The structure of 2 is built of concatenated, edge‐sharing Ca(H₂O)₆S₂ polyhedra. The Ca²⁺ ions have the coordination number eight, C₄S₄^2? act as a chelating ligands towards Ca²⁺ with Ca–S distances of 3.14Å. The infrared and Raman spectra show bands typical for the molecular building units of the two compounds.     

The First Titanium Molybdenum Antimonide: Ti5.42Mo2.58Sb9, a Substitution Variant of Zr2V6Sb9

The new ternary antimonide Ti_5.42(2)Mo_2.58Sb₉ was uncovered by a reaction of the elements under exclusion of air at 1150 °C. It crystallizes in a ternary substitution variant of the V_7.5Sb₉ type, a structure not known to exist in either the Ti/Sb or the Mo/Sb system. The crystal structure of Ti_5.42Mo_2.58Sb₉ was determined from single crystal X‐ray data: space group P4/nmm, with a = 9.8178(8) Å, c = 7.1857(8) Å, V = 692.6(1) ų, Z = 2, R1 = 0.025, wR2 = 0.052 (all data). The structure contains four metal atom sites, two thereof occupied solely by Ti atoms, and two by different Ti/Mo mixtures. The former two correspond to the Zr sites, and the latter two to the V sites of the isostructural antimonide Zr₂V₆Sb₉. The crystal structure is comprised of chains of face‐sharing TiSb₈ square antiprisms, Ti/Mo tetrahedra and Sb atom pairs and squares. The electronic structure, computed with the LMTO approximation, is indicative of metallic properties. In addition to the dominating metal–Sb bonds, strong metal–metal and Sb–Sb bonds exist as well in Ti_5.42Mo_2.58Sb₉. The Mo content per metal site increases with increasing metal–metal interactions.     

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.