Synthesis,Structural Characterization,and Physical Properties of Cs2Ga2S5, and Redetermination of the Crystal Structure of Cs2S6

The reaction of CsN₃ with GaS and S at elevated temperatures results in Cs₂Ga₂S₅. Its crystal structure was determined from single‐crystal X‐ray diffraction data. The colorless solid crystallizes in space group C2/c (no. 15) with V=1073.3(4) ų and Z=4. Cs₂Ga₂S₅ is the first compound that features one‐dimensional chains ${{{\hfill 1\atop \hfill \infty }}}$ [Ga₂S₃(S₂)^2?] of edge‐ and corner‐sharing GaS₄ tetrahedra. The vibrational band of the S₂^2? units at 493 cm^?1 was revealed by Raman spectroscopy. Cs₂Ga₂S₅ has a wide bandgap of about 3.26 eV. The thermal decomposition of CsN₃ yields elemental Cs, which reacts with sulfur to provide Cs₂S₆ as an intermediate product. The crystal structure of Cs₂S₆ was redetermined from selected single crystals. The red compound crystallizes in space group ${P\bar 1}$ with V=488.99(8) ų and Z=2. Cs₂S₆ consists of S₆^2? polysulfide chains and two Cs positions with coordination numbers of 10 and 11, respectively. Results of DFT calculations on Cs₂Ga₂S₅ are in good agreement with the experimental crystal structure and Raman data. The analysis of the chemical bonding behavior revealed completely ionic bonds for Cs, whereas Ga?S and S?S form polarized and fully covalent bonds, respectively. HOMO and LUMO are centered at the S₂ units.     

Modular Metal Chalcogenide Chemistry: Secondary Building Blocks as a Basis of the Silicate‐Type Framework Structure of CsLiU(PS4)2

The novel uranium thiophosphate CsLiU(PS₄)₂ has been synthesized by reacting uranium metal, Cs₂S, Li₂S, S, and P₂S₅ at 700 °C in an evacuated silica tube. The crystal structure was determined by single‐crystal X‐ray diffraction techniques. CsLiU(PS₄)₂ crystallizes in the rhombohedral space group R$\bar{3}$ c (a = 15.2797(7) Å; c = 28.778(2) Å, V = 5818.7(5) ų, Z = 18). The structure ofCsLiU(PS₄)₂ is a unique three‐dimensional U(PS₄)₂^2– framework with large tunnels with an approximate diameter of 6.6 Å running parallel to the crystallographic c axis. The tunnels are filled with Cs⁺ cations. The smaller Li⁺ cations are located at tetrahedral sites at the periphery of the channels. In the structure of CsLiU(PS₄)₂ the uranium atoms are coordinated by thiophosphate groups in a pseudotetrahedral fashion, and the PS₄ groups act as linear connectors. Topologically, CsLiU(PS₄)₂ may be regarded a chalcogenide analogue of silicate frameworks, with the uranium atoms and PS₄ groups replacing silicon and oxygen atoms. Alternatively, CsLiU(PS₄)₂ may be viewed as a coordination polymer, which is formed in salt melts by the solid state equivalent of the “self‐assembly” reactions in solution. Magnetic susceptibility measurements indicated Curie–Weiss‐type behavior between 4 K and 300 K. The μ_eff of 2.83 μ_B at 300 K is in agreement with an f² configuration of U⁴⁺.     

Cs2B2S4 – Ein Salz der dimeren Metathioborsäure

Cs₂B₂S₄ – A Derivative of the Dimeric Metathioboric Acid Cs₂B₂S₄ (structure: I4₁/acd; a = 7.270(1) Å, c = 35.737(7) Å; Z = 8; substructure: I4/mmm; a′ = 5.141(1) Å, c′ = 17.868(4) Å, Z = 2) is prepared by the reaction of cesium sulfide with stoichiometric amounts of boron and sulfur (effective molar ratio M:B:S = 2:2:4) at 600°C and subsequent annealing. The crystal structure contains isolated [B₂S₄]^2? groups consisting of four-membered B₂S₂ rings with two exocyclic sulfur atoms on each of the boron atoms. The cesium cations are nine-coordinate between these rings. The structural feature of two edge-sharing BS₃ groups forming an isolated anion appears for the first time in thioborate chemistry, although it is known as a part of the polymeric network in B₂S₃.     

New compounds in the cesium sulfobromide rhenium octahedral cluster chemistry: syntheses and crystal structures of Cs4Re6S8Br6 and Cs2Re6S8Br4

The exploration of the CsReSBr system, in order to identify new phases based on octahedral cluster anions, has produced single crystals of Cs₄Re₆S₈Br₆ (1) (trigonal, space group P-6c2, a=9.7825 (3) Å, c=18.7843 (5) Å, V=1556.77 (1) ų, Z=2, density=5.09 g cm⁻³, μ=36.07 mm⁻¹) and Cs₂Re₆S₈Br₄ (2) (monoclinic, space group P2₁/n, a=6.3664 (1) Å, b=18.4483 (4) Å, c=9.3094 (2) Å, β=104.2618 (8)°, V=1059.69 (4) ų, Z=2, density=6.14 g cm⁻³, μ=45.83 mm⁻¹). These two compounds have been obtained by high-temperature solid state route. Their structures have been solved and refined from single crystal X-ray diffraction data. The structure of Cs₄Re₆S₈Br₆ presents isolated anionic cluster units inscribed in a (Cs⁺)₁₂ cuboctahedron and the one of Cs₂Re₆S₈Br₄ exhibits ReS^i-a,a-iRe inter-unit bridges. The framework of the latter presents then a strongly 1-D character.     

Darstellung und Kristallstruktur des Quecksilber(II)-thiodiphosphats Hg2P2S7

Preparation and Crystal Structure of Mercury (II) Thiodiphosphate Hg₂P₂S₇ Hg₂P₂S₇ crystallizes monoclinic with a = 10.887(8); b = 5.827(3); c = 8.132(6) Å und β = 103.83(6)° in space group C2.The crystal structure was determined from four-circle diffractometer data by means of the heavy atom method and refined by least squares to R = 0.094 for 1119 intensities. The structure contains P₂S₇ group which are arranged in layer parallel to the (001) plane and connected by Hg atoms to form a three-dimensional network. The Hg atoms are surrounded by four S atoms in a deformed tetrahedral arrangement (means distance Hg? S: 2.591 Å). The P₂S₇ group are composed of two PS₄ tetrahedra sharing one corner (mean distance P? S: 2.048 Å; ? P? S? P: 108.6°). According to the structural data Hg₂P₂S₇ may be interpreted as mercury(II) thiodiphosphate. The bond distance and the structural relationships between Hg₂P₂S₇ and Ag₄P₂S₇ are discussed. Hg₂P₂S₇ represents a new defect tetrahedral structural type.     

BaB2S4: Das erste nicht‐oxidische Chalkogenoborat mit trigonal‐planar und tetraedrisch koordiniertem Bor

BaB₂S₄: The first non‐oxidic Chalcogenoborate with Boron in a trigonal‐planar and tetrahedral Coordination Hitherto we know boron in a trigonal‐planar and a tetrahedral coordination within one crystal structure from boron oxides in various compounds. With the novel bariummetathioborate BaB₂S₄ we now report a crystal structure containing BS₃ and BS₄ units in the ratio 1 : 1 forming infinite chains along [001]. BaB₂S₄ was synthesized in a solid state reaction at a temperature of 800 °C from barium sulfide, amorphous boron and sulfur and crystallizes in the monoclinic space group Cc (no. 9) with the following lattice parameters: a = 6.6465(5) Å, b = 15.699(1) Å, c = 6.0306(5) Å, β = 110.96(1)°, Z = 4.     

Preparation and Crystal Structure of the Clathrate‐I Cs8–xGe44+y□2–y

The clathrate‐I phase Cs_8–xGe_44+y□_2–y (space group Pm$\bar{3}$ n) was prepared by high‐pressure high‐temperature reactions of Cs₄Ge₄ and α‐Ge. Different reaction conditions were found to have a strong influence on the lattice parameter of the clathrate‐I phase ranging from 10.8070(2) Å to 10.8493(3) Å. A single crystal with composition Cs₈Ge_44.40(2)□_1.60(2) was obtained from a sample with a = 10.8238(2) Å (niobium ampoule, p = 3.4 GPa, T_max = 1400 °C). Structure analysis based on X‐ray single crystal data shows unambiguously an excess of germanium atoms with respect to the electron balanced composition Cs₈Ge₄₄□₂ on basis of the Zintl concept.     

Synthese und Kristallstruktur von K2Mn3S4

Synthesis and Crystal Structure of K₂Mn₃S₄ Single crystals of K₂Mn₃S₄ have been prepared by a fusion reaction of potassium carbonate with manganese in a stream of hydrogen sulfide at 900 °C. K₂Mn₃S₄ crystallizes in a new monoclinic layered structure type (P2/c, a = 7.244(2) Å, b = 5.822(1) Å, c = 11.018(5) Å, β = 112.33(3)°, Z = 2) which can be described as a stacking variant of the orthorhombic Cs₂Mn₃S₄ structure type. Measurements of the magnetic susceptibilities show antiferro‐magnetic interactions.     

A 1:2 complex of mercury(II) chloride with 1,3‐imidazole‐2‐thione

The Hg atom in the title monomeric complex, di­chloro­bis(3‐imidazolium‐2‐thiol­ato‐S)­mercury(II), [HgCl₂(C₃H₄N₂S)₂], is four‐coordinate having an irregular tetrahedral geometry composed of two Cl atoms [Hg—Cl 2.622 (2) and 2.663 (2) Å] and two thione S atoms [Hg—S 2.445 (2) and 2.462 (2) Å]. The monodentate thione ligand adopts a zwitterionic form and exists as the 3‐imidazolium‐2‐thiol­ate ion. The bond angle S1—Hg—S2 of 130.87 (8)° has the greatest deviation from ideal tetrahedral geometry. Intermolecular hydrogen bonds between two of the four N—H groups and one of the Cl atoms [3.232 (8) and 3.238 (7) Å] stabilize the crystal structure, while the other two N—H groups contribute through the formation of N—H?Cl intramolecular hydrogen bonds with the other Cl atom [3.121 (7) and 3.188 (7) Å].     

Synthesis and Characterization of Copper Hexathiometadiphosphate Cu2P2S6

Copper hexathiometadiphosphate, Cu₂P₂S₆, was synthesized and characterized. Brick‐red copper hexathiometadiphosphate Cu₂P₂S₆ crystallizes in the tetragonal space group P4₂/mnm (no. 136) with a = b = 5.2565(7), c = 15.066(3) Å and V = 416.3(1) ų in a novel structure type. This is the first hexathiometadiphosphate, whose crystal structure is based on a slightly distorted cubic closest packing of sulfur atoms. 1/3 of the tetrahedral voids are occupied by Cu and P in an ordered fashion, thus resulting in a layered structure. The structural motif of layers composed of corner‐sharing CuS₄ tetrahedra (comparable to red HgI₂) that are separated by [P₂S₆]^2– anions orientated perpendicular to these layers, is rarely found in solid state chemistry. The compound is diamagnetic and shows negligible electronic conductivity. Electronic structure calculations and UV/Vis measurements point to a bandgap in the visible range and explain the red color of the compound. Additionally, the oxidation state +1 for Cu was confirmed by the electronic structure calculations. The thermal properties of Cu₂P₂S₆ were investigated by DTA.     

New Thioantimonates(III) with Different Sb:S Ratios: Solvothermal Syntheses and Crystal Structures of [(C3H10NO)(C3H10N)][Sb8S13], [(C2H8NO)(C2H8N)(CH5N)][Sb8S13], [(C6H16N2)(C6H14N2)][Sb6S10], and [C8H22N2][Sb4S7]

Four new thioantimonates(III) with compositions [(C₃H₁₀NO)(C₃H₁₀N)][Sb₈S₁₃] ( 1 ) (C₃H₉NO = 1‐amino‐3‐propanol, C₃H₉N = propylamine), [(C₂H₈NO)(C₂H₈N)(CH₅N)][Sb₈S₁₃] ( 2 ) (C₂H₇NO = ethanolamine, C₂H₇N = ethylamine, CH₅N = methylamine), [(C₆H₁₆N₂)(C₆H₁₄N₂)][Sb₆S₁₀] ( 3 ) (C₆H₁₄N₂ = 1,2‐diaminocyclohexane) and [C₈H₂₂N₂][Sb₄S₇] ( 4 ) (C₈H₂₀N₂ = 1,8‐diaminooctane) were synthesized under solvothermal conditions. Compound 1 : triclinic space group P$\bar{1}$ , a = 6.9695(6) Å, b = 13.8095(12) Å, c = 18.0354(17) Å, α = 98.367(11), β = 96.097(11) and γ = 101.281(11)°; compound 2 : monoclinic space group P2₁/m, a = 7.1668(5), b = 25.8986(14), c = 16.0436(11) Å, β = 96.847(8)°; compound 3 : monoclinic space group P2₁/n, a = 11.6194(9), b = 10.2445(5) Å, c = 27.3590(18) Å, β = 91.909(6)°; compound 4 : triclinic space group P$\bar{1}$ , a = 7.0743(6), b = 12.0846(11), c = 13.9933(14) Å, α = 114.723(10), β = 97.595(11), γ = 93.272(11)°. The main structural feature of the two atoms thick layered [Sb₈S₁₃]^2– anion in 1 are large nearly rectangular pores with dimensions 11.2 × 11.7 Å. The layers are stacked perpendicular to [100] to form tunnels being directed along [100]. In contrast to 1 the structure of 2 contains a [Sb₈S₁₃]^2– chain anion with Sb₁₂S₁₂ pores measuring about 8.9 × 11.5 Å. Only if longer Sb–S distances are considered as bonding interactions a layered anion is formed. The chain anion [Sb₆S₁₀]^2– in compound 3 is unique and is constructed by corner‐sharing SbS₃ pyramids. Two symmetry‐related single chains consisting of alternating SbS₃ units and Sb₃S₃ rings are bound to Sb₄S₄ rings in chair conformation. Finally, in the structure of 4 the SbS₃ and SbS₄ moieties are joined corner‐linked to form a chain of alternating SbS₄ units and (SbS₃)₃ blocks. Neighboring chains are connected into sheets that contain relatively large Sb₁₀S₁₀ heterorings. The sheets are further connected by sulfur atoms generating four atoms thick double sheets.     

[1,2‐P2S8]2− – a New Member of the Thiophosphate Family: Synthesis,Crystal Structure and Vibrational Spectrum of [NH4(2.2.2‐cryptand)]2[1,2‐P2S8] and [NH4(18‐crown‐6)]2[1,2‐P2S8]·H2O

Colourless block‐shaped crystals of [(NH₄)₂(2.2.2‐cryptand)₂][P₂S₈] ( 1 ) and [(NH₄)₂(18‐crown‐6)₂][P₂S₈]·H₂O ( 2 ) could be obtained by the reaction of an aqueous solution of ammonium hexathiohypodiphosphate, (NH₄)₄P₂S₆·2 H₂O, with sulfur and 2.2.2‐cryptand or 18‐crown‐6. The crystal structures of both compounds have been determined by single‐crystal X‐Ray diffraction analysis. Compound 1 crystallizes in the monoclinic space group C2/c with a = 2032.7(2), b = 1243.6(2), c = 2244.6(2) pm, β = 98.64(1)°, and Z = 8, whereas compound 2 crystallizes also monoclinic in the space group P2₁/c with a = 2121.3(2), b = 865.5(1), c = 2345.4(2) pm, β = 91.96(1)°, and Z = 4. It could be established that the title compounds contain a new type of six‐membered [1,2‐P₂S₄] ring with P – P bond and three S – S linkages. The tetrahedral environment of each phosphorus is completed by a (formally) single and double bonded sulfur atom attached externally to the [1,2‐P₂S₄] ring. These terminal PS₂ units are mesomerically stabilized according to their P – S distances. FT‐IR and FT‐Raman spectra of the title compounds are recorded and interpreted.     

The Crystal and Molecular Structure of γ‐P4S6

The crystal and molecular structure of γ‐P₄S₆ was determined from single‐crystal X‐ray diffraction. It crystallizes monoclinically in the space group P2₁/m (No. 11) with a = 6.627(3) Å, b = 10.504(7) Å, c = 6.878(3) Å, β = 90.18(4)°, V = 478.8(4) ų, and Z = 2. The structure consists of cage‐like P₄S₆ molecules with C_S symmetry arranged with the topology of a cubic close packing.     

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.     

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.     

Single-crystal structure of Cs2Re6S6Br8 rhenium thiobromide with acentric Re6 octahedral cluster units

Cs₂Re₆S₆Br₈ (trigonal, a = 10.001(5) Å, c = 14.676(5) Å) exhibits the same structure as Cs₂Mo₆Cl₈Br₆ and Cs₂Mo₆Br₁₄ that were described in a noncentro-and centrosymmetric space groups, respectively. The structure has been refined in P31c space group from a single crystal of actual composition Cs_1.95(1)Re₆S_5.82(3)Br_8.19(3) close to the cesium-rich end of the solid solution Cs₂Re₆S₆Br₈ — CsRe₆S₅Br₉. The centrosymmetry is respected by almost all the atoms of the asymmetric unit, but it is clearly broken by significant differences in the S/Br statistical distribution of the disordered “inner” ligands around the Re₆ cluster. Structural refinements from data collected at 100 K revealed that the Cs cation disorder is static. From the structure refinements, the stable isomers of the [Re₆S₆Br₂] and [Re₆S₅Br₃] cluster cores have been unambiguously determined.     

Synthesis and Crystal Structures of Cs5Nb2S4X9 – Double Salts Containing New Cluster Anions [Nb2(μ-S2)2X8]4– (X = Cl,Br)

Bis(disulfide)bridged Nb(+4) cluster halide complexes [Nb₂S₄X₈]^4– (X = Cl, Br) were prepared by acid hydrolysis of [Nb₂S₄(NCS)₈]^4– in concentrated aqueous HCl or HBr, solution from which they can be isolated as double salts Cs₅[Nb₂S₄X₈]X (X = Cl, 1 ; X = Br, 2 ). The crystal structures of 1 and 2 were determined. The isolation and X-ray structure of oxonium salt (H₃O)₅ [Nb₂S₄Cl₈]Cl ( 3 ) is also reported. 1 – 3 contain new [Nb₂S₄X₈]^4– anions which can also be viewed as excised building blocks of polymeric solids NbS₂X₂. The extra halogen resides in the center of octahedron formed by six Cs⁺ or H₃O⁺ ions. All the three salts are isostructural and crystallize in tetragonal space group Immm with the following parameters: a = 10.269(2), b = 16.343(2), c = 7.220(1) Å for 1 , a = 10.934(1), b = 16.613(2), c = 7.470(1) Å for 2 , a = 9.639(1), b = 16.031(1), c = 7.071(1) Å for 3 . The parameters of the Nb₂S₄ core are only slightly affected by the change from Cl to Br.     

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.     

RbGa3S5 und CsGa3S5 – Zwei neue Strukturtypen

RbGa₃S₅ and CsGa₃S₅ – Two New Structure Types The title compounds RbGa₃S₅ and CsGa₃S₅ were synthesized by a solid state reaction starting from GaS, S and MN₃ (M = Rb, Cs) as alkaline metal source. They crystallize in the space group P2₁/c with comparable lattice parameters but with completely different structures (RbGa₃S₅: a = 7,1530(6), b = 12,715(1), c = 10,1282(9) Å, β = 102,43(1)°, Z = 4; CsGa₃S₅: a = 10,6717(8), b = 12,763(1), c = 6,9265(6) Å, β = 91,168(9)°, Z = 4). In RbGa₃S₅ Rb together with S shows the topology of a hexagonal close packing in which Ga occupies 3/12 of the tetrahedral holes. The GaS₄ tetrahedra are connected by common corners and edges forming a 3D‐network. The structure of CsGa₃S₅ is characterized by corrugated layers of edge‐ and corner‐sharing GaS₄‐tetrahedra. Both compounds represent so far unknown structure types and thus two further structural alternatives for compounds with the composition MM₃′Ch₅.     

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.