New Hexachalcogeno–Hypodiphosphates of the Alkali Metals: Synthesis,Crystal Structure and Vibrational Spectra of the Hexathiodiphosphate(IV) Hydrates K4[P2S6] · 4 H2O,Rb4[P2S6] · 6 H2O,and Cs4[P2S6] · 6 H2O

The new hexathiodiphosphate(IV) hydrates K₄[P₂S₆] · 4 H₂O ( 1 ), Rb₄[P₂S₆] · 6 H₂O ( 2 ), and Cs₄[P₂S₆] · 6 H₂O ( 3 ) were synthesized by soft chemistry reactions from aqueous solutions of Na₄[P₂S₆] · 6 H₂O and the corresponding heavy alkali‐metal hydroxides. Their crystal structures were determined by single crystal X‐ray diffraction. K₄[P₂S₆] · 4 H₂O ( 1 ) crystallizes in the monoclinic space group P 2₁/n with a = 803.7(1), b = 1129.2(1), c = 896.6(1) pm, β = 94.09(1)°, Z = 2. Rb₄[P₂S₆] · 6 H₂O ( 2 ) crystallizes in the monoclinic space group P 2₁/c with a = 909.4(2), b = 1276.6(2), c = 914.9(2) pm, β = 114.34(2)°, Z = 2. Cs₄[P₂S₆] · 6 H₂O ( 3 ) crystallizes in the triclinic space group with a = 742.9(2), b = 929.8(2), c = 936.8(2) pm, α = 95.65(2), β = 112.87(2), γ = 112.77(2)°, Z = 1. The structures are built up by discrete [P₂S₆]^4? anions in staggered conformation, the corresponding alkali‐metal cations and water molecules. O ··· S and O ··· O hydrogen bonds between the [P₂S₆]^4? anions and the water molecules consolidate the structures into a three‐dimensional network. The different water‐content compositions result by the corresponding alkali‐metal coordination polyhedra and by the prefered number of water molecules in their coordination sphere, respectively. The FT‐Raman and FT‐IR/FIR spectra of the title compounds have been recorded and interpreted, especially with respect to the [P₂S₆]^4? group. The thermogravimetric analysis showed that K₄[P₂S₆] · 4 H₂O converted to K₄[P₂S₆] as it was heated at 100 °C.     

Drei Alkalimetall‐Erbium‐Thiophosphate: Von der Schichtstruktur bei KEr[P2S7] zur dreidimensionalen Vernetzung in NaEr[P2S6] und Cs3Er5[PS4]6

Three Alkali‐Metal Erbium Thiophosphates: From the Layered Structure of KEr[P₂S₇] to the Three‐Dimensional Cross‐Linkage in NaEr[P₂S₆] and Cs₃Er₅[PS₄]₆ The three alkali‐metal erbium thiophosphates NaEr[P₂S₆], KEr[P₂S₇], and Cs₃Er₅[PS₄] show a small selection of the broad variety of thiophosphate units: from ortho‐thiophosphate [PS₄]^3? and pyro‐thiophosphate [S₃P–S–PS₃]^4? with phosphorus in the oxidation state +V to the [S₃P–PS₃]^3? anion with a phosphorus‐phosphorus bond (d(P–P) = 221 pm) and tetravalent phosphorus. In spite of all differences, a whole string of structural communities can be shown, in particular for coordination and three‐dimensional linkage as well as for the phosphorus‐sulfur distances (d(P–S) = 200 – 213 pm). So all three compounds exhibit eightfold coordinated Er³⁺ cations and comparably high‐coordinated alkali‐metal cations (CN(Na⁺) = 8, CN(K⁺) = 9+1, and CN(Cs⁺) ≈ 10). NaEr[P₂S₆] crystallizes triclinically ( ; a = 685.72(5), b = 707.86(5), c = 910.98(7) pm, α = 87.423(4), β = 87.635(4), γ = 88.157(4)°; Z = 2) in the shape of rods, as well as monoclinic KEr[P₂S₇] (P2₁/c; a = 950.48(7), b = 1223.06(9), c = 894.21(6) pm, β = 90.132(4)°; Z = 4). The crystal structure of Cs₃Er₅[PS₄] can also be described monoclinically (C2/c; a = 1597.74(11), b = 1295.03(9), c = 2065.26(15) pm, β = 103.278(4)°; Z = 4), but it emerges as irregular bricks. All crystals show the common pale pink colour typical for transparent erbium(III) compounds.     

Chemische und cyclovoltammetrische Untersuchung der Redoxreaktionen der Decahalogendecaborate closo‐[B10X10]2– und hypercloso‐[B10X10]· – (X = Cl,Br). Kristallstrukturanalyse von Cs2[B10Br10] · 2 H2O

Chemical and Cyclovoltammetric Investigation of the Redoxreactions of the Decahalodecaborates closo ‐[B₁₀X₁₀]^2– and hypercloso ‐[B₁₀X₁₀]^{· –} (X = Cl, Br)¹⁾. Crystal Structure Analysis of Cs₂[B₁₀Br₁₀] · 2 H₂O The oxidation of the decachloro‐closo‐decaborates(2–) Cs₂[B₁₀Cl₁₀] or [Me₄N]₂[B₁₀Cl₁₀] with Tl(CF₃COO)₃ leads to the corresponding radical monoanion hypercloso‐[B₁₀Cl₁₀] ^{· –}, which was characterized by ESR and UV/Vis spectroscopy. [B₁₀Cl₁₀] ^{· –} does not dimerize like [B₁₀H₁₀] ^{· –} but it is reduced by acetonitrile to the dianion [B₁₀Cl₁₀]^2–. Cs₂[B₁₀Cl₁₀] reacts with stronger oxidation agents like CoF₃ (in dichloromethane) or XeF₂ (in perfluorhexane), respectively, to yield B₉Cl₉ and, in traces, B₈Cl₈. In opposite to this, the decabromoderivative Cs₂[B₁₀Br₁₀] does not show any reaction with Tl(CF₃COO)₃ in acetonitrile or with CoF₃ in CH₂Cl₂. The oxidation of the dianions [B₁₀X₁₀]^2– (X = Cl, Br) was studied by electroanalytical methods (cyclic voltammetry, chronoamperometry, chronocoulometry). Formal potentials were determined for the two steps of the reaction, which do not seem to be affected by structural rearrangements. The crystal structure of Cs₂[B₁₀Br₁₀] · 2 H₂O was analyzed by single‐crystal X‐ray diffraction. Cs₂[B₁₀Br₁₀] · 2 H₂O crystallizes monoclinic (space group I2/a, (no. 15), Z = 8, a = 1361.54(9) pm, b = 1215.89(5) pm, c = 3108.4(2) pm, α = 90°, β = 97.916(8)°, γ = 90°). The closo‐cluster B₁₀Br₁₀^2– has a bicapped square antiprismatic structure with idealized D_4d symmetry.     

Alkalimetall‐Stannid‐Silicate und ‐Germanate: ‘Doppelsalze’ mit dem Zintl‐Anion [Sn4]4—

Alkaline Metal Stannide‐Silicates and ‐Germanates: ‘Double Salts’ with the Zintl Anion [Sn₄]^4— The crystal structures of the tetrelid tetrelates A₁₂[Sn₄]₂[GeO₄] (A = Rb/Cs: monoclinic, P2₁/c, a = 1289.1(2) / 1331.72(7), b = 2310.1(4)/ 2393.6(1), c = 1312.6(2)/ 1349.21(7) pm, β = 119.007(3)/ 118.681(1)°, Z = 4, R1 = 0.1049/0.0803) and Cs₂₀[Sn₄]₂[SiO₄]₃ (monoclinic, Cc, a = 2331.9(1), b = 1340.1(2), c = 1838.9(2) pm, β= 102.61(3)°, R1 = 0.0763) contain the Zintl anions [Sn₄]^4— and isolated oxotetrelate ions [MO₄]^4— (M = Si, Ge). The high temperature form of CsSn crystallizes with the KGe type (cubic, P4¯3n, a = 1444.7(1) pm, R1 = 0.0395).     

Hydrothermal Synthesis and Crystal Structures of Na2Be3(SeO3)4·H2O and Cs2[Mg(H2O)6]3(SeO3)4

The selenites, Na₂Be₃(SeO₃)₄ · H₂O and Cs₂[Mg(H₂O)₆]₃(SeO₃)₄, were synthesized under hydrothermal conditions. The crystal structures of Na₂Be₃(SeO₃)₄ · H₂O and Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ were determined by single‐crystal X‐ray diffractions. Na₂Be₃(SeO₃)₄ · H₂O crystallizes in the triclinic space group P1 (no. 2) with unit cell parameters a = 4.8493(9), b = 12.013(2), c = 12.077(2) Å, and Z = 2, whereas Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ crystallizes in the monoclinic space group C2/m (no. 12) with lattice cell parameters a = 12.596(6), b = 7.297(4), c = 16.914(8) Å, and Z = 2. Na₂Be₃(SeO₃)₄ · H₂O features a three‐dimensional open framework structure formed by BeO₄ tetrahedra and SeO₃ trigonal pyramids. Na cations and H₂O molecules are located in different tunnels. Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ has a structure composed of isolated [Mg(H₂O)₆] octahedra and SeO₃ trigonal pyramids interacted by hydrogen bonds, and Cs cations are resided in‐between. Both compounds were characterized by thermogravimetric analysis and FT‐IR spectroscopy.     

A Novel 3‐D Heterobimetallic Cyano‐bridged Coordination Polymer Incorporating Ag···Ag Interaction: [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2]

A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)₂]₂[Ag₂(CN)₃][Ag(CN)₂] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P2₁/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]²⁺ units bridged by [Ag(CN)₂]^— to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)₂]^— link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer.     

Efficient Synthesis and Properties of Single‐Crystalline [SnTe4]4− Salts

Single‐crystalline K⁺, Rb⁺, and Cs⁺ salts of the ortho‐tellurostannate anion have been prepared by a very efficient fusing/extraction/evaporation method. The resulting compounds with the general composition [A₄(H₂O)_n][SnTe₄] can be transferred into mixed H₂O/en solvates by solving the hydrates in 1,2‐diaminoethane (en) and ensuing layering by toluene. A mixed Rb⁺/Ba²⁺ salt results from a partial cation exchange of the Rb⁺ hydrate phase in solution. All hydrates react to polytellurides when exposed to air and represent useful starting materials for the synthesis of transition metal complexes with [SnTe₄]^4? groups as binary main group elemental ligands. [K₄(H₂O)_0.5][SnTe₄] ( 1 ), [Rb₄(H₂O)₂][SnTe₄] ( 2 ), [Cs₄(H₂O)₂][SnTe₄] ( 3 ), [K₄(H₂O)(en)][SnTe₄] ( 4 ), [Rb₄(H₂O)_0.67(en)_0.33][SnTe₄] ( 5 ), [Cs₄(H₂O)_0.5(en)_0.5][SnTe₄] ( 6 ), and [Rb₂Ba(H₂O)₁₁][SnTe₄] ( 7 ) were characterized by means of X‐ray diffractometry and optical absorption spectroscopy.     

Synthesis and Structure of a Novel Organic-Inorganic Hybrid Polyoxovanadate, [Ni（bpp）2]2（V4O12） （bpp= 1,3-bi-4-pyridylpropane）

A novel organic-inorganic hybrid polyoxovanadate, [Ni（bpp）2]2（V4O12） （bpp= 1,3-bi-4-pyridylpropane）, was hydrothermally synthesized from a mix.ture of NiCl2＊6H2O, NH4VO3, bpp, EtOH and H2O. The crystal structure consists of ∞^2[Ni（bpp）2]^2＋, two-dimensional networks interpenetrating perpendicularly with each other, and （V4O12）^4-, cyclic tetranuclear clusters linking the ∞^2[Ni（bpp）2]^2＋ networks to form a three-dimensional coordination framework. The crystal belongs to tetragonal space group I41/a with unit cell parameters, a= 2.14705 nm, c= 1.29293 nm. UV-Vis-NIR reflectance spectroscopy study revealed insulator nature for the crystal with an optical energy gap of 2.70 eV.     

Cs2[PdCl4] — neue Ergebnisse zu einer „altbekannten”︁ Verbindung

Hochtemperatur‐Cs₂[PdCl₄] — New Results on a “wellknown” Compound Two modifications of Cs₂[PdCl₄] have been characterized by X‐ray powder and single crystal diffraction, respectively. The crystal structures are described and the group‐subgroup‐relations between these structures are discussed. In addition to the tetragonal (P4/mmm (No. 123), a = 7.4158(8) Å, c = 4.6792(6) Å) and the orthorhombic (Cmcm (No. 63), a = 10.529(1) Å, b = 10.310(1) Å, c = 9.460(1) Å) modification DSC investigations and high‐temperature X‐ray diffraction experiments with synchrotron radiation show the existence of another modification or of yet unknown decomposition products. The phase transformation from the orthorhombic to the tetragonal polymorph is completely finished at 100 °C. The second effect is detected at 319 °C.     

Synthesis,Crystal Structures,and Vibrational Spectra of Novel Azidopalladates of the Alkali Metals Cs2[Pd(N3)4] and Rb2[Pd(N3)4]·2/3H2O

The transparent dark orange compounds Cs₂[Pd(N₃)₄] and Rb₂[Pd(N₃)₄]·²/₃H₂O are synthesized by reaction of the respective binary alkali metal azides with K₂PdCl₄ in aqueous solutions. According to single‐crystal X‐ray diffraction investigations, the novel ternary azidopalladates(II) crystallize in the monoclinic space group P2₁/c (no. 14) with a = 705.7(2) pm, b = 717.3(2) pm, c = 1125.2(5) pm, β = 104.58(2)°, mP30 for Cs₂[Pd(N₃)₄] and a = 1041.4(1) pm, b = 1292.9(2) pm, c = 1198.7(1) pm, β = 91.93(1)°, mP102 for Rb₂[Pd(N₃)₄]·²/₃H₂O, respectively. Predominant structural features of both compounds are discrete [Pd^II(N₃)₄]^2– anions with palladium in a planar coordination by nitrogen, but differing in point group symmetries., The vibrational spectra of the compounds are analyzed based on the idealized point group C_4h of the spectroscopically relevant unit, [Pd(N₃)₄]^2– taking into account the site symmetry splitting due to the symmetry reduction in the solid phase.     

Ce3Cl5[SiO4] und Ce3Cl6[PO4]: Ein chloridreiches Chloridsilicat und ‐phosphat des Cers im Vergleich

Ce₃Cl₅[SiO₄] and Ce₃Cl₆[PO₄]: A Chloride‐Rich Chloride Silicate of Cerium as Compared to the Phosphate By reacting CeCl₃ with CeO₂, cerium and SiO₂, or P₂O₅, respectively, in molar ratios of 5 : 3 : 1 : 3 or 8 : 3 : 1 : 2, respectively, in sealed evacuated silica tubes (7 d, 850 °C) colorless, rod‐shaped single crystals of Ce₃Cl₅[SiO₄] (orthorhombic, Pnma; a = 1619.7(2), b = 415.26(4), 1423.6(1) pm; Z = 4) and Ce₃Cl₆[PO₄] (hexagonal, P6₃/m; a = 1246.36(9), c = 406.93(4) pm; Z = 2) are obtained as products insensitive to air and water. Excess cerium trichloride as flux promotes crystal growth and can be rinsed off again with water after the reaction. The crystal structures are determined by discrete [SiO₄]^4– or [PO₄]^3– tetrahedra as isolated units. Both, the chloride silicate Ce₃Cl₅[SiO₄] and the chloride phosphate Ce₃Cl₆[PO₄], exhibit structural similarities to CeCl₃ (UCl₃ type), when four or three Cl^– anions are each substituted formally by one [SiO₄]^4– or [PO₄]^3– unit, respectively, in the tripled formula (Ce₃Cl₉). The coordination number for Ce³⁺ is thus raised from nine in CeCl₃ to ten in Ce₃Cl₅[SiO₄] and Ce₃Cl₆[PO₄], along with a drastic reduction of the molar volume with the transition from Ce₃Cl₉ (V_m = 186.17 cm³/mol) to Ce₃Cl₅[SiO₄] (V_m = 144.15 cm³/mol) and Ce₃Cl₆[PO₄] (V_m = 164.84 cm³/mol). The polyhedra of coordination around Ce³⁺ can be described as quadruple‐capped trigonal prisms, which in addition to seven Cl^– anions each also show another three oxygen atoms of two ortho‐silicate or ortho‐phosphate tetrahedra, respectively.     

Cs4[La(NO3)6](NO3). HNO3: Das erste Salpetersäureaddukt eines ternären Alkali-Lanthanidnitrats

Cs₄[La(NO₃)₆](NO₃) · HNO₃: The First Nitric Acid Adduct of a Ternary Alkali Lanthanide Nitrate In the crystal structure of Cs₄[La(NO₃)₆](NO₃). HNO₃ (monoclinic, P2₁/c, Z = 2, a = 787.3(2); b = 1353.0(3); c = 1141.8(7) pm; β = 94,37(3)°) La³⁺ has a coordination number of twelve (six bidentate nitrate ligands). The structure may be viewed at as a layer structure: Layers of the composition [Cs(1)₄La₂(NO₃)₁₂]^2?, and [Cs(2)₄(NO₃)₂(HNO₃)₂]²⁺ are stacked alternatively in the [100] direction.     

Die Kristallstrukturen der Hexachlorometallate NH4[SbCl6], NH4[WCl6], [K(18‐Krone‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 und (PPh4)2[WCl6]·4CH3CN

Crystal Structures of the Hexachlorometalates NH₄[SbCl₆], NH₄[WCl₆], [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ and (PPh₄)₂[WCl₆]·4CH₃CN The crystal structures of the title compounds were determined by single crystal X‐ray methods. NH₄[SbCl₆] and NH₄[WCl₆] crystallize isotypically in the space group C2/c with four formula units per unit cell. The NH₄⁺ ions occupy a twofold crystallographic axis, whereas the metal atoms of the [MCl₆]^— ions occupy a centre of inversion. There exist weak interionic hydrogen bridges. [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ crystallizes in the orthorhombic space group R3¯/m with Z = 3. The compound forms centrosymmetric ion triples, in which the potassium ions are coordinated with a WCl₃ face each. In trans‐position to it the chlorine atom of a CH₂Cl₂ molecule is coordinated so that, together with the oxygen atoms of the crown ether, coordination number 10 is achieved. (PPh₄)₂[WCl₆]·4CH₃CN crystallizes in the monoclinic space group P2₁/c with Z = 4. This compound, too, forms centrosymmetric ion triples, in which in addition the acetonitrile molecules are connected with the [WCl₆]^2— ion via weak C—H···Cl contacts.     

Neue Alkalimetall‐halogenopalladate(II) mit Iodeinlagerung — Kristallstrukturen,Phasenübergänge und Spektroskopie

New Alkaline Halogenopalladates(II) with Incorporated Iodine Dumb‐Bells — Crystal Structures, Phase‐Transitions, and Vibrational Spectra Dark‐reddish crystals of Cs₂[PdBr₄]I₂, Cs₂[PdCl₄]I₂, and black crystals of Rb₂[PdBr₄]I₂ were obtained by solvothermal reaction from diluted hydrohalogenic acids and crystallize in space group I4/mmm with Z = 2. Unitcell parameters for Cs₂[PdBr₄]I₂ are a = 848.96(1) pm, c = 908.53(2) pm; Cs₂[PdCl₄]I₂ a = 814.65(2) pm, c = 899.10(1) pm and for Rb₂[PdBr₄]I₂ a = 840.9(1) pm, c = 902.3(1) pm. The compounds contain isolated [PdX₄] building units (X = Cl, Br) which are supplemented by embedded iodine dumb‐bells. Cs₂[PdBr₄]I₂ and Cs₂[PdCl₄]I₂ show reversible pressure induced phase transitions above 78 kbar and 199 kbar, respectively.     

Syntheses,Crystal Structures,and Properties of Lead(II), ­Zinc(II), and Manganese(II) Complexes Constructed from 2, 3, 5, 6‐Tetraiodo‐1, 4‐benzenedicarboxylic Acid

Three new coordination compounds, [Pb(HBDC‐I₄)₂(DMF)₄]( 1 ) and [M(BDC‐I₄)(MeOH)₂(DMF)₂]_n (M = Zn^II for 2 and Mn^II for ( 3 ) (H₂BDC‐I₄ = 2, 3, 5, 6‐tetraiodo‐1, 4‐benzenedicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X‐ray single crystal structure analysis. Single‐crystal X‐ray diffraction reveals that 1 crystallizes in the monoclinic space group C2/c and has a discrete mononuclear structure, which is further assembled to form a two‐dimensional (2D) layer through intermolecular O–H ··· O and C–H ··· O hydrogen bonding interactions. The isostructural compounds 2 and 3 crystallize in the space group P2₁/c and have similar one‐dimensional (1D) chain structures that are extended into three‐dimensional (3D) supramolecular networks by interchain C–H ··· π interactions. The Pb^II and Zn^II complexes 1 and 2 display similar emissions at 472 nm in the solid state, which essentially are intraligand transitions.     

Four Complexes with the Rigid Ligand 1,4‐Bis(1H‐imidazol‐4‐yl)benzene and Varied Carboxylate Ligands

Four metal‐organic coordination polymers [Co₂(L)₃(nipa)₂]·6H₂O ( 1 ), [Cd(L)(nipa)]·3H₂O ( 2 ), [Co(L) (Hoxba)₂] ( 3 ) and [Ni₂(L)₂(oxba)₂(H₂O)]·1.5L·3H₂O ( 4 ) were synthesized by reactions of the corresponding metal(II) salts with the rigid ligand 1,4‐bis(1H‐imidazol‐4‐yl)benzene (L) and different derivatives of 5‐nitroisophthalic acid (H₂nipa) and 4,4′‐oxybis(benzoic acid) (H₂oxba), respectively. The structures of the complexes were characterized by elemental analysis, FT‐IR spectroscopy and single‐crystal X‐ray diffraction. Complexes 1 and 3 have the same one‐dimensional (1D) chain while 2 is a 6‐connected twofold interpenetrating three‐dimensional (3D) network with α ‐Po 4¹²·6³ topology based on the binuclear Cd^II subunits. Compound 4 features a puckered two‐dimensional (2D) (4,4) network, and the large voids of the packing 2D nets have accommodated the uncoordinated L guest molecules. An abundant of N–H···O, O–H···O and C–H···O hydrogen bonding interactions exist in complexes 1–4 , which contributes to stabilize the crystal structure and extend the low‐dimensional entities into high‐dimensional frameworks. Lastly, the photoluminiscent properties of compounds 2 were also investigated.     

Er4F2[Si2O7][SiO4]: Das erste Selten‐Erd‐Fluoridsilicat mit zwei verschiedenen Silicat‐Anionen

Er₄F₂[Si₂O₇][SiO₄]: The First Rare‐Earth Fluoride Silicate with Two Different Silicate Anions By the reaction of Er₂O₃ with ErF₃ and SiO₂ at 700 °C in sealed tantalum capsules using CsCl as flux (molar ratio 5 : 2 : 3 : 20), the compound Er₄F₂[Si₂O₇][SiO₄] (triclinic, P 1; a = 648.51(5), b = 660.34(5), c = 1324.43(9) pm, α = 87.449(8), β = 85.793(8), γ = 60.816(7)°; V_m = 148.69(1) cm³/mol, Z = 2) is obtained as pale pink platelets or lath‐shaped single crystals. It consists of disilicate anions [Si₂O₇]^6– in eclipsed conformation, ortho‐silicate anions [SiO₄]^4– and isolated [Er₄F₂]¹⁰⁺ units comprising two edge‐shared [Er₃F] triangles. Er³⁺ is surrounded by 7 + 1 (Er1) or 7 (Er2–Er4) anionic neighbors, respectively, of which two are F^– in the case of Er1 and Er4 but only one for Er2 and Er3. The other ligands recruit from oxygen atoms of the different oxosilicate groups. The crystal structure can be described as simple rowing up of the three building groups ([SiO₄]^4–, [Er₄F₂]¹⁰⁺, and [Si₂O₇]^6–) along [001]. The necessity of a large excess of fluoride for a successful synthesis of Er₄F₂[Si₂O₇][SiO₄] will be discussed.     

Stabilization of Highly Reactive “Naked Anions”: Synthesis,Crystal Structure and Vibrational Spectrum of [Na(12‐crown‐4)2]2 [P2S6] · CH3CN

The novel thiodiphosphate, [Na(12‐crown‐4)₂]₂[P₂S₆] · CH₃CN, bis[di(12‐crown‐4)sodium] hexathiodiphosphate(V) acetonitrile solvate ( 1 ) has been synthesized by the reaction of Na₂[P₂S₆] with 12‐crown‐4 in dry acetonitrile. The title compound crystallizes in the tetragonal space group P4₂/mbc (no. 135), with a = 15.184(1) Å, c = 21.406(2) Å and Z = 4 and final R1 = 0.0671 and wR2 = 0.0809. The crystal structure is characterized by discrete sodium‐bound crown‐ether sandwich cations, [Na(12‐crown‐4)₂]⁺ and [P₂S₆]^2? ions with D_2h symmetry. Sodium ion is coordinated by the eight oxygen atoms of two crown‐ether molecules to form a square antiprisma. Solvent molecules of CH₃CN are statistically disordered. Distances and angles of the [P₂S₆]^2? unit are similar to those in [K(18‐crown‐6)]₂ [P₂S₆] · 2 CH₃CN, and in K₂[P₂S₆] and Cs₂[P₂S₆]. The FT‐Raman and FT‐IR spectrum of the title compound has been recorded and interpreted, especially with respect to the P₂S₆ group and in comparison to the few known metal hexathiodiphosphates(V).     

Polysulfonylamine. CLXV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 14 [1] Cs3Ag[(MeSO2)2N]4 und CsAg[(MeSO2)2N]2: Ein dreidimensionales und ein schichtförmiges Koordinationspolymer mit Bis(dimesylamido‐N)argentat‐Baugruppen

Polysulfonylamines. CLXV. Crystal Structures of Metal Di(methanesulfonyl)amides. 14. Cs₃Ag[(MeSO₂)₂N]₄ and CsAg[(MeSO₂)₂N]₂: A Three‐Dimensional and a Layered Coordination Polymer Containing Bis(dimesylamido‐N)argentate Building Blocks Serendipitous formation pathways and low‐temperature X‐ray structures are reported for the coordination compounds Cs₃A₂[AgA₂] ( 1 ) and Cs[AgA₂] ( 2 ), where A^— represents the pentadentate dimesylamide ligand (MeSO₂)₂N^—. Both phases (monoclinic, space group C2/c, Z′ = 1/2) contain inversion‐symmetric bis(dimesylamido‐N)argentate units displaying exactly linear N—Ag—N cores and short, predominantly covalent Ag—N bonds [ 1 : 213.5(2), 2 : 213.35(12) pm]; in each case, the coordination number of the silver ion is extended to 2 + 6 by four internal and two external Ag···O secondary interactions. The three‐dimensional coordination polymer 1 is built up from alternating layer substructures [{Cs(1)}{A}_4/2]^— with Cs(1) lying on twofold rotation axes and [{Cs(2)}₂{AgA₂}_4/4]⁺ with Cs(2) occupying general positions. Within the substructural layers, both types of cesium cation have approximately planar O₄ environments, whereas the final coordination spheres including interlayer bonds are extended to O₆ for Cs(1) and to O₈N for Cs(2). Compound 2 , in contrast, forms a genuine layer structure. The layers are constructed from Cs⁺ chains located on twofold rotation axes, alternating with [AgA₂]^— stacks reinforced by Ag···O secondary interactions and weak C—H···O hydrogen bonds; Cs⁺ is embedded in an O₈ environment. Both structures are pervaded by a three‐dimensional C—H···O network.     

Das gemischtvalente ternäre Oxoferrat(II,III) K3[Fe2O4] – eine aufgefüllte Variante des K2[Fe2O4]‐Typs

The Mixed‐Valent Oxoferrate(II,III) K₃[Fe₂O₄] – A Stuffed Variant of the K₂[Fe₂O₄] Type of Structure K₃[Fe₂O₄] has been obtained by tempering “Cs₃K₃CdO₄” in sealed Fe containers (36 d at 450–480 °C) as dark red transparent single crystals of rectangular shape. The structure determination (IPDS diffractometer data, MoKα, 1891 collected reflections, 234 symmetry independent, R1 = 0.033, wR2 = 0.088) confirms the space group Fddd; a = 596.11(9), b = 1140.3(1), c = 1717.9(3) pm; Z = 8. K₃[Fe₂O₄] exhibits a structure with [FeO₄] tetrahedra connected via corners leading to a three‐dimensional network closely related to the KFeO₂ type of structure. From the oxidation at 520 °C of iron metal with KO₂ in the presence of Na₂O black single crystal of K₂[Fe₂O₄] have been obtained. K₂[Fe₂O₄] crystallizes in the space group Pbca with Z = 8 and a = 559.18(7), b = 1122.1(1), c = 1592.8(2) pm (IPDS diffractometer data, MoKα, collected refelctions: 9543, 1213 symmetry independent, R1 = 0.043, wR2 = 0.102).