Hydrothermal synthesis,crystal structure and photoluminescent properties of 2D layered zinc phosphate intercalated with 4,4ˈbiphenyl dicarboxylic acid (ZnPO-BDA)

Herein, we report a new inorganic-organic hybrid, (H₃tren)₂?[Zn₃(PO₄)₄(BDA)]?xH₂O (ZnPO-BDA) prepared under hydrothermal conditions. This hybrid structure of zinc phosphate layers pillared with 4,4′-biphenyl-dicarboxylic acid (BDA) was characterized by single-crystal X-ray diffraction. The compound, ZnPO-BDA, crystallizes in the monoclinic crystal system (space group C2) with a = 14.9348(3) Å, b = 8.7058(2) Å, c = 17.6455(5) Å, β = 111.6760(10), V = 2132.02(9) ų, Z = 2. The crystalline host of the 2D zinc phosphate framework was built with vertex linked ZnO₄ and PO₄ tetrahedra and anchored with tris(2-aminoethyl)amine (H₃tren). Biphenyl dicarboxylic acid (BDA) molecules stack between the phosphate framework layers by means of strong hydrogen bonding, resulting in an interlayer distance of 16.4 Å. ZnPO-BDA displayed blue photoluminescence with an emission maximum at 404 nm on photoexcitation at 340 nm.     

Formation and thermal decomposition of pyridine intercalates of α- and γ-zirconium phosphates

The intercalation of pyridine into α-ZrP takes place with an accompanying uptake of one more mole of water to form a dihydrate Zr(HPO₄)_1.55(C₅H₅NHPO₄)_0.45 · 2 H₂O which has an interlayer spacing of 10.9 Å and contains two types of water with different thermostabilities. The pyridine intercalate of γ-ZrP with 12.3 Å spacing is formed by the replacement of interlayer water by the gest molecules without any appreciable change in interlayer spacing and its composition is Zr(HPO₄)_1.56 (C₅H₅NHPO₄)_0.44 · 0.7 H₂O. The α-intercalate undergoes dehydration at below 140°C, accompanied by its separation into a pyridine-free phase (ζ-ZrP) and a pyridine enriched one, and this dehydration is immediately followed by the desorption of pyridine, resulting in the overall conversion of the initial phase to ζ-ZrP. The γ-intercalate, on the other hand, releases its water without any phase separation at similar temperatures but its depyridination temperature at 250°C is about 110°C higher than that for the other. A molecular packing model is proposed to explain the interlayer spacings, compositions, and thermal decomposition properties of both intercalates.     

Tripotassium Trichrome (III) Tetraphosphate K3Cr3(PO4)4: Synthèse, Étude Structurale,Caractérisation et Conductivité Ionique

The potassium chromium (III) phosphate K₃Cr₃(PO₄)₄ is prepared by a solid state reaction at 1173 K from a mixture of K₂CO₃, NH₄H₂PO₄, and (NH₄)Cr₂O₇. It is structurally characterized by single-crystal X-ray diffraction. It crystallizes in the Cmca (n°64) space group with a = 10.524(4) Åi, b = 20.466(6) Åi, c = 6.374(2) Åi, V = 1372.9(8) Åi³, Z = 4, R(F²) = 0.0452, and R _W (F²) = 0.1184 for 790 reflections with I > 2σ(I). The structure consists of CrO₆ octahedra and PO₄ tetrahedra sharing corners and edges to form a two-dimensional framework. The K⁺ cations are located in the interlayer space. Conductivity measurement leads to σ = 47.32 10^?5 Ω^?1 m^?1 at 729 K. K₃Cr₃(PO₄)₄ is a better ionic conductor than K₃Cr₃(AsO₄)₄ at the same temperature.     

A novel way to study the initial stages of soap-free emulsion polymerizations: The intercalation of polystyrene oligomers into hydrotalcite

The dominant species in the early stages of an emulsifier-free emulsion polymerization of styrene has been found to be an oligomer of two to three monomer units using a novel trapping technique. This involved the intercalation of charged primary oligomers between the layers of a hydrotalcite, [Mg₄Al₂(OH)₁₂]²⁺[A]^2- (where A = dianion). Hydrotalcites are an important class of lamellar, inorganic compounds whose interlayer spacing can be mod-ified by anion exchange. Our approach first involved preparing a hydrotalcite precursor in which the layers were propped apart by an organic dianion (terephthalate = TA). This material was then used to capture the negatively charged polystyrene oligomers from the emulsion polymerization reaction mixture. We found that TA was rapidly ion-exchanged for the charged oligomers. The resulting pillared hydrotalcite material was characterized using XRD and SEC. We found that the interlayer spacing between the hydroxide layers increased to 23.2 Å on exposure to the emulsion reaction mixture. This represents an interlayer expansion of 18.3 Å (after subtraction of the hydroxide layer contribution), which is cnsistent with intercalation of oligomers with two to three monomer units arranged in a bilayer. This size estimate was confirmed by the results of size exclusion chromatography. © 1995 John Wiley & Sons, Inc.     

Embedding Alkyldiamine into Layered α-Titanium Phosphate via Direct-Ion Exchange and its Application in EuIII Removal from Water

Diamine-pillared α-titanium phosphate (α-TiP) was prepared via direct ion exchange method. Moreover, 1,3-propanediamine, as the pillaring agent, was used to investigate the effect of pH, content and temperature on the interlayer distance of α-TiP. The structure and properties of the samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Field Emission Scanning Electron Microscopy (SEM), and Differential Thermal Analysis (TG). The results show that the interlayer distance of α-TiP was enlarged from 7.6 Å to 16.18 Å as the carbon chain of the intercalating diamine increased from (NH₂(CH₂)_nNH₂) (n = 2 to 7). The layer space structure consists of monomolecular alkyl chains with an average tilt angle of 75.6°. The uptake values for these five alkyldiamine cations were 3.780, 3.261, 2.443, 2.175, and 1.954 mmol, per gram of TiP, respectively. Also, we found that the direct ion exchange method is more effective in a weak acidic environment. The variation of interlayer distance was a consecutive process, and unaffected by temperature. The 1,3-propanediamine intercalation product (α-TiPPda) showed excellent performance towards Eu^III adsorption in water with removal efficiencies ≥ 99 %.     

Thermal decomposition of hydrotalcitewith hexacyanoferrate(II) and hexacyanoferrate(III) anions in the interlayer

The thermal decompositions of hydrotalcites with hexacyanoferrate(II) and hexacyanoferrate(III) in the interlayer have been studied using thermogravimetry combined with mass spectrometry. X-ray diffraction shows the hydrotalcites have a d(003) spacing of 11.1 and 10.9 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. XRD was also used to determine the products of the thermal decomposition. For the hydrotalcite decomposition the products were MgO, Fe₂O₃ and a spinel MgAl₂O₄. Dehydration and dehydroxylation take place in three steps each and the loss of cyanide ions in two steps.     

Primitive cubic packing of anions in Cs4[Re6Te8(CN)6]· 2H2O and Ba2[Re6Te8(CN)6] · 12H2O crystals

Crystal structures of Cs₄[Re₆Te₈(CN)₆]·2H₂O (1) and Ba₂[Re₆Te₈(CN)₆]· 12H₂O (2) are determined. Crystals 1 are orthorhombic, a = 14,282(1), b = 12.910(1), c = 18.040(1) Å, V_cell = 3326.3(8) ų, space group Pbcn, Z = 4, d_calc = 5.715 g/cm³, R(F) = 0.0482 for 3193 F_hkl > 4σ(F). Crystals 2 are triclinic, a = 9.671(3), b = 9.697(4), c = 11.039(4) Å, α = 89.86(3), β = 72.34(3), γ = 82.46(3)°, V_cell = 977.2(6) ų, space group P1, Z = 1, d^calc = 4.733 g/cm³, R(F) = 0.0490 for 3226 F_hkl > 4σ(F). In both structures, the [Re₆Te₈(CN)₆]^4? anions form a distorted primitive cubic packing with distances between the centers 9.02-9.63 Å in 1 and 9.70-11.04 Å in 2. The Cs⁺ cations in 1 lie near the face centers of the cubes formed by the onions. In 2, cation pairs (Ba²⁺)₂ bonded to two solvate water molecules are formed; the pairs lie at the centers of the anion cubes. In structures 1 and 2, there are shortened contacts between the tellurium atoms belonging to the neighboring anions (3.75-4.09 and 3.95-4.22 Å, respectively).     

Synthesis and Characterization of [Fe3(As3)3(As4)]3−, a Binary Fe/As Zintl Cluster With an Fe3 Core

We report here the synthesis and structural characterization of the first binary iron arsenide cluster anion, [Fe₃(As₃)₃(As₄)]³⁻, present in both [K([2.2.2]crypt)]₃[Fe₃(As₃)₃(As₄)] ( 1 ) and [K(18-crown-6)]₃[Fe₃(As₃)₃(As₄)]⋅en ( 2 ). The cluster contains an Fe₃ triangle with three short Fe−Fe bond lengths (2.494(1) Å, 2.459(1) Å and 2.668(2) Å for 1 , 2.471(1) Å, 2.473(1) Å and 2.660(1) Å for 2 ), bridged by a 2-butene-like As₄ unit. An analysis of the electronic structure using DFT reveals a triplet ground state with direct Fe−Fe bonds stabilizing the Fe₃ core.     

Formation of the high-pressure modification of hydrated talc at 450°C and 4 GPa: <Emphasis Type="Italic">In situ</Emphasis> diffraction study

The formation of the high-pressure hydrous phase Mg₃Si₄O₁₀(OH)₂?xH₂O (10 Å phase) through the reaction “talc + water” at 450°C and 4 GPa was studied using diamond anvil cell. The powder diffraction measurements in situ, performed at the Siberian Center of Synchrotron and Terahertz Radiation (SSTRC), were applied to refine the lattice parameters, atomic coordinates and the occupancy of interlayer H₂O site in the structure of 10 Å phase at 450°C and 4 GPa. The lattice parameters are a = 5.234(1) Å, b = 9.053(2) Å, c = 10.87(1) Å, β = 99.2(1)°, and V = 508.5(6) ų (space group C2/m). The results of Rietveld refinement show the best fit for the trioctahedral mica structure with split position Ow of the interlayer H₂O molecule. The half occupancy of the Ow site corresponds to one H₂O molecule per formula unit.     

Low‐dimensional compounds containing cyano groups. VI.

The title compound, [Cu₂(C₄H₁₂N₂)₂{Ag(CN)₂}₄(NH₃)]·2H₂O or [Ag₄Cu₂(CN)₈(C₄H₁₂N₂)₂(NH₃)]·2H₂O, contains two crystallographically different Cu^II atoms lying on twofold axes. The first Cu atom is hexacoordinated in the form of an elongated tetragonal bipyramid and is part of a plane in which Cu atoms are connected by two bridging di­amino­butane mol­ecules [Cu—N = 2.033 (4) Å] and two di­cyano­argentate anions [Cu—N = 2.622 (6) Å]. The ammine ligand stands perpendicular to this plane [Cu—N = 2.011 (6) Å] in a trans position to it. Another [Ag(CN)₂]⁻ anion connects the hexacoordinated Cu atom [Cu—N = 1.997 (8) Å] with the second Cu atom [Cu—N = 2.026 (7) Å], which is pentacoordinated in the form of a slightly distorted trigonal bipyramid by two monodentate di­cyano­argetate anions [Cu—N = 2.040 (5) Å]. The axial positions are occupied by two bridging di­amino­butane mol­ecules [Cu—N = 2.011 (4) Å] that connect the Cu atoms into chains parallel to the above plane. The water mol­ecules remain uncoordinated and thus a unique combination of two‐ and one‐dimensional structures is formed.     

Synthesis and crystal structure of divaleratobis(nicotinamide)copper(II)

A copper(II) valerate complex with nicotinamide (L) [CuL₂(C₄H₉COO)₂] (I) has been synthesized and studied by IR spectroscopy and thermogravimetry. The crystal structure has been determined. The crystals of 1 are monoclinic, a = 11.297(1) Å, b = 6.666(1) Å, c = 16.873(2) Å, b = 108.50(1)°, V = 1204.9(3) ų, Z = 2, space group P2₁/c. The structural units of the crystal of I are centrosymmetric tetragonal bipyramidal (4+2) complex molecules. The equatorial positions of the bipyramid are occupied by trans-arranged pairs of O (Cu-O, 1.973 Å) and N (Cu-N, 2.006 Å) atoms, and the axial positions are occupied by the second O atoms of the valerate anions located at longer distances (Cu-O, 2.506 Å). The supramolecular associates formed in the crystal are layers of hydrogen-bonded complexes. The disordered hydrocarbon “tails” of the valerate groups point toward the interlayer space.     

FeII2(PO4)(OH), a synthetic analogue of wolfeite

This paper reports the hydrothermal synthesis and crystal structure refinement of diiron(II) phosphate hydroxide, Fe^II₂(PO₄)(OH), obtained at 1063 K and 2.5 GPa. This phosphate is the synthetic analogue of the mineral wolfeite, and has a crystal structure topologically identical to those of minerals of the triplite–triploidite group. The complex framework contains edge‐ and corner‐sharing FeO₄(OH) and FeO₄(OH)₂ polyhedra, linked via corner‐sharing to the PO₄ tetrahedra (average P—O distances are between 1.537 and 1.544 Å). Four five‐coordinated Fe sites are at the centers of distorted trigonal bipyramids (average Fe—O distances are between 2.070 and 2.105 Å), whereas the coordination environments of the remaining Fe sites are distorted octahedra (average Fe—O distances are between 2.146 and 2.180 Å). The Fe—O distances are similar to those observed in natural Mg‐rich wolfeite, except for two Fe—O bond distances, which are significantly longer in synthetic Fe²⁺₂(PO₄)(OH).     

Structure and spectral characteristics of (NH4)2[Re2(HPO4)4 · 2H2O]

The compound (NH₄)₂[Re₂(HPO₄)₄ · 2H₂O] has been synthesized and characterized by electronic and vibrational spectroscopy. The molecular structure has been determined by X-ray diffraction (MoK _α radiation, λ = 0.71073 Å). The (NH₄)₂[Re₂(HPO₄)₄ · 2H₂O] coordination units form centrosymmetrical binuclear ordering with each metal atom being coordinated in a distorted octahedron incorporating one rhenium atom, one oxygen atom of the water molecule, and four phosphate oxygen atoms in the equatorial plane. The rhenium-rhenium bond length (2.2207 Å) corresponds to a quadruple bond between the atoms. The [Re₂(HPO₄)₄ · 2H₂O]^2- complex anions in the crystal are associated through strong hydrogen bonds formed by the phosphate O-H···O groups. The stability of dirhenium(III) tetra-μ-phosphates in aqueous solutions is considered.     

Overloaded elution band profiles of ionizable compounds in reversed‐phase liquid chromatography: Influence of the competition between the neutral and the ionic species

The parameters that affect the shape of the band profiles of acido‐basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pK_a are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 μL) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C₁₈‐bonded packing materials, including the 5 μm Xterra‐C₁₈ (121 Å), 5 μm Gemini‐C₁₈ (110 Å), 5 μm Luna‐C₁₈(2) (93 Å), 3.5 μm Extend‐C₁₈ (80 Å), and 2.7 μm Halo‐C₁₈ (90 Å). The mobile phase was an aqueous solution of methanol buffered at a constant _W^WpH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3‐phenyl 1‐propanol, 2‐phenyl butyric acid, amphetamine, aniline, benzylamine, p‐toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pK_a and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution.     

Synthesis and structure of alkali metal zirconium vanadate phosphates

Mixed vanadate phosphates in the systems MZr₂(VO₄) _x (PO₄)_{3 ? x} , where M is an alkali metal, were synthesized and studied by X-ray diffraction, electron probe microanalysis, and IR spectroscopy. Substitutional solid solutions with the structure of the mineral kosnarite (NZP) are formed at the compositions 0 ≤ x ≤ 0.2 for M = Li; 0 ≤ x ≤ 0.4 for M = Na; 0 ≤ x ≤ 0.5 for M = K; 0 ≤ x ≤ 0.3 for M = Rb; and 0 ≤ x ≤ 0.2 for M = Cs. Apart from the high-temperature NZP modification, lithium vanadate phosphates LiZr₂(VO₄) _x (PO₄)_{3 ? x} with 0 ≤ x ≤ 0.8 synthesized at temperatures not exceeding 840°C crystallize in the scandium tungstate type structure. The crystal structures of LiZr₂(VO₄)_0.8(PO₄)_2.2 (space group P2₁/n, a = 8.8447(6) Å, b = 8.9876(7) Å, c = 12.3976(7) Å, β = 90.821(4)○, V = 985.4(1) ų, Z = 4) and NaZr₂(VO₄)_0.4(PO₄)_2.6 (space group $R\bar 3c$ = 8.8182(3) Å, c = 22.7814(6) Å, V = 1534.14(1) ų, Z = 6) were refined by the Rietvield method. The framework of the vanadate phosphate structure is composed of tetrahedra (that are statistically occupied by vanadium and phosphorus atoms) and ZrO₆ octahedra. The alkali metal atoms occupy extra-framework sites.     

Darstellung,Kristallstrukturen und Eigenschaften der Chrom(II)-phosphat-halogenide Cr2(PO4)Br und Cr2(PO4)I

Synthesis, Crystal Structures, and Properties of the Chromium(II) Phosphate Halides Cr₂(PO₄)Br and Cr₂(PO₄)I The new compounds Cr₂(PO₄)Br and Cr₂(PO₄)I have been obtained by reaction of CrPO₄, Cr and Br₂ or I₂ in evacuated silica tubes at elevated temperatures (Cr₂(PO₄)Br: 900 °C, Cr₂(PO₄)I: 700 °C). Single crystals of deep blue Cr₂(PO₄)Br and turquoise Cr₂(PO₄)I with edge-lengths up to 2 mm and 0.3 mm, respectively, have been grown in experiments involving the gaseous phase. Single crystal data have been used for structure determination and refinement. Though being not isotypic, the two crystal structures are closely related. Two crystallographically independent Cr²⁺, in polyhedra [Cr1O₃X₃] and [Cr2O₅X], form dimers [Cr1₂O₂O_2/2X₄] and [Cr2₂O₈X₂]. Distances are 1.978 Å ≤ d(Cr–O) ≤ 2.096 Å (for the iodide: 1.959 Å ≤ d(Cr–O) ≤ 2.105 Å), 2.587 Å ≤ d(Cr–Br) ≤ 3.158 Å and 2.867 Å ≤ d(Cr–I) ≤ 3.327 Å. The structures of bromide and iodide can be distinguished by the different way of connection of the Cr1 containing dimers. The phosphate group shows slightly distorted tetrahedral geometry with 1.491 Å ≤ d(P–O) ≤ 1.559 Å (1.486 Å ≤ d(P–O) ≤ 1.567 Å) and angles of 106.48° ≤ ∠(O–P–O) ≤ 111.69° (106.57° ≤ ∠(O–P–O) ≤ 111.72°. IR-spectra of Cr₂(PO₄)Br and Cr₂(PO₄)I, the Raman-spectrum of Cr₂(PO₄)Br and electronic spectra of the two compounds in the UV/vis region at low temperature are reported and discussed.     

Phase composition,formation parameters,and morphology of precipitates in the LiVO<Subscript>4</Subscript>-VOSO<Subscript>4</Subscript>-H<Subscript>2</Subscript>O system

The phase and chemical compositions of the precipitates formed in the LiVO₃-VOSO₄-H₂O system at initial pH within 1 ≤ pH ≤ 4 and 90°C were studied. The following phases were prepared: an α phase Li_1.4(VO)_1.3[H₂V₁₀O₂₈] · nH₂O and a β phase Li_{0.6 ? x} H_{1.4 + x} [V₁₂O_{31 ? y/2}] · nH₂O (0 ≤ x ≤ 0.5, 1.3 ≤ y ≤ 2.0) with a layered structure. Li_0.4V₂O₅ · H₂O nanorods with the interlayer distance 10.30 ± 0.08 Å were synthesized at 180°C in an autoclave. The morphology, IR spectra, and main formation processes for these polyvanadates were studied.     

[{Cu(trien)}<Subscript>2</Subscript>Re<Subscript>4</Subscript>Te<Subscript>4</Subscript>(CN)<Subscript>12</Subscript>]·3.5H<Subscript>2</Subscript>O: Synthesis and crystal structure

The crystals of a cluster complex of rhenium [{Cu(trien)}₂Re₄Te₄(CN)₁₂]· 3.5H₂O were synthesized by the reaction of aqueous K₄[Re₄Te₄(CN)₁₂] with an aqueous ammonia solution of copper chloride in the presence of a polydentate ligand triethylenetetraamine (trien). The structure of the compound was established by X-ray single crystal analysis (a = 14.2617(11) Å, b = 15.7220(7) Å, c = 21.8554(16) Å, β = 98.554(2)°, V = 4846.0(6) ų, Z = 4, space group P2₁/n, R = 0.0436). Two copper cations in the complex are coordinated to one cluster anion [Re₄Te₄(CN)₁₂]^4?. The copper atoms have typical five-coordinated surroundings formed by the nitrogen atom of the bridging cyanide ligand and four amino groups of the tetradentate trien.     

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H3O)2[(UO2)2(SO4)3­(H2O)]·7H2O and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O,and a Uranyl Selenate‐Selenite [C5H6N][(UO2)(SeO4)(HSeO3)]

Two uranyl sulfate hydrates, (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 7H₂O (NDUS) and (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 4H₂O (NDUS1), and one uranyl selenate‐selenite [C₅H₆N][(UO₂)(SeO₄)(HSeO₃)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L ‐cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P2₁/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4) Å, β = 112.778(1)°, V = 2153.52(9) ų,Z = 4, the tetragonal space group P4₃2₁2, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) ų, Z = 8, and in the monoclinic space group P2₁/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) ų, Z = 4, respectively.The structural units of NDUS and NDUS1 are two‐dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two‐dimensional uranyl selenate‐selenite sheets with a U/Se ratio of 1/2. In‐situ reaction of the L ‐cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H₃O⁺ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C₅H₆N⁺ cations result from the cyclization of the carboxyl groups of L ‐cystine, balancing the charge of the sheets.     

Mono and Poly‐nuclear Silver(I) Complexes with Thiosaccharin and Triphenylphosphine. Synthesis,Spectroscopic and Structural Characterization of Thiosaccharinato‐bis(triphenylphosphine)silver(I) and Tetrakis{thiosaccharinato(triphenylphosphine)silver(I)}

The reaction of Ag₆(tsac)₆ ( 1 ) (tsac = thiosaccharinate anion) with triphenylphosphine gives rise to the already reported [Ag(tsac)(PPh₃)₃] complex ( 2 ) and to two new silver‐thiosaccharinate‐phosphine complexes, [Ag(tsac)(PPh₃)₂] ( 3 ) and [Ag₄(tsac)₄(PPh₃)₄] ( 4 ) (PPh₃= triphenylphosphine). Spectroscopic characterization was carried out using IR, UV‐Visible and NMR techniques and confirmed by single crystal X‐ray diffraction. In each complex a singular coordination mode for the thiosaccharinate ligand is observed. The most important features of the different coordination modes of the thionates are discussed. Compound 3 crystallizes in monoclinic system, space group Pn, with a = 11.2293(3) Å, b = 12.7282(3) Å, c = 13.6056(4) Å, β = 94.985(2)°, Z = 2; while crystals of compound 4 are monoclinic, space group P2₁/n, a = 15.024(3) Å, b = 14.681(3) Å, c = 21.914(4) Å, β = 95.31(3)°, Z = 2. The coordination around the silver atoms in both complexes consists of almost trigonal‐planar arrangements, AgP₂S in 3 and AgS₂P in 4 .