Benzodithiazolium‐Chlorooxomolybdate(V): Darstellung und Kristallstruktur von (C6H4NS2)[MoOCl4] und (C6H4NS2)[MoOCl4·H2O]

Benzodithiazolium Chlorooxomolybdate(V): Preparation and Crystal Structure of (C₆H₄NS₂)[MoOCl₄] and (C₆H₄NS₂)[MoOCl₄·H₂O] Red benzo‐1,3,2‐dithiazolium‐chlorooxomolybdate(V) (C₆H₄NS₂)[MoOCl₄] ( 1 ) was obtained by the reaction of benzo‐1,3,2‐dithiazoliumchloride and molybdenum(V)chloride oxide in dichlormethane under solvothermal conditions at 70 °C. In the presence of small amounts of concentrated hydrochloric acid the yellow compound (C₆H₄NS₂)[MoOCl₄·H₂O] ( 2 ) is formed under analogue conditions. Both crystal structures ( 1 : monoclinic, C2/c, a = 799.2(1), b = 2091.5(2), c = 791.5(1) pm, β = 102.2(1)°, Z = 4; 2 : monoclinic, Cc, a = 953.7(1), b = 2468.9(3), c = 608.1(1) pm, β = 112.5(1)°, Z = 4) contain the planar benzo‐1,3,2‐dithiazolium ion. Within the structure of 1 the molybdenum atoms in the [MoOCl₄]^? ions are coordinated in a square pyramidal fashion with an oxygen atom in apical position and the basal plane formed by chlorine atoms. The nitrogen atom of the cation, which bears a partial negativ charge, expands the coordination to a distorted octahedron. The structure therefore is made up of ionic pairs {(C₆H₄NS₂)⁺ [MoOCl₄]^?} with a Mo–N distance of 266 pm. 1 is paramagnetic with a magnetic moment of 1.7 B.M. corresponding to one unpaired electron per formula unit. In the structure of 2 the coordination of the [MoOCl₄]^? ion is expanded by the oxygen atom of a coordinating water molecule. The structure is dominated by hydrogen bonds between the oxygen atoms of the [MoOCl₄·H₂O]^? ions which cause the concatenation of the anions to infinite chains.     

Darstellung und Kristallstruktur von β-[SeCl3][MoOCl4]

Preparation and Crystal Structure of β-[SeCl₃][MoOCl₄] The reaction of Se₄[MoOCl₄] and Te₄[MoOCl₄] with SOCl₂ as solvent at 150 °C and 80 °C yields [SeCl₃][MoOCl₄] and [TeCl₃][MoOCl₄] respectively within 3 to 6 days as yellow-brown, moisture-sensitive crystals. [TeCl₃][MoOCl₄] was obtained in the already known monoclinic form, while β-[SeCl₃][MoOCl₄] crystallizes in a new polymorphic triclinic form (P1¯, Z = 2, a = 752.7(2), b = 812.8(2), c = 956.9(3) pm, α = 92.55(3)°, β = 111.63(2)°, γ = 107.39(3)°). The structure contains centrosymmetric tetranuclear units ([SeCl₃]₂[Mo₂O₂Cl₈]) which are analogous to the entities found in the structure of [SCl₃][MoOCl₄]. The packing of the molecules in β-[SeCl₃][MoOCl₄] and [SCl₃][MoOCl₄] is distinctely different.     

Über Thallium(I)-chlorooxomolybdate: Synthese und Kristallstrukturen von Tl[MoOCl4(NCCH3)], Tl[Mo2O2Cl7] und Tl2[Mo4O4Cl14] und die Struktur von Tl2[MoCl6]

On Thallium(I)-oxochloromolybdates: Synthesis and Crystal Structures of Tl[MoOCl₄(NCCH₃)], Tl[Mo₂O₂Cl₇], and Tl₂[Mo₄O₄Cl₁₄] and the Structure of Tl₂[MoCl₆] Black crystals of Tl₂[MoCl₆] are formed in the reaction of TlCl with MoOCl₃ in a sealed evacuated glass ampoule at 350 °C. The crystal structure analysis shows that Tl₂[MoCl₆] (cubic, Fm 3¯m, a = 986.35(7) pm) adopts the K₂[PtCl₆] structure with a Mo–Cl bond length of 236.6 pm. Tl[MoOCl₄(NCCH₃)] was obtained by the reaction of TlCl with MoOCl₃ in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl⁺ cations and octahedral [MoOCl₄(NCCH₃)]^– anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl₃ in dichloromethane yields Tl[Mo₂O₂Cl₇] and Tl₂[Mo₄O₄Cl₁₄] as green moisture sensitive crystals. The structure of Tl[Mo₂O₂Cl₇] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl⁺ cations and dinuclear [Mo₂O₂Cl₇]^– anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl₂[Mo₄O₄Cl₁₄] (triclinic, P1¯, a = 692.8(1), b = 919.6(1), c = 998.9(1) pm, α = 104.94(1)°, β = 90.31(1)°, γ = 108.14(1)°) is build of Tl⁺ cations and [Mo₄O₄Cl₁₄]^2– anions which form tetramers of distorted octahedral, edgesharing (MoOCl₅) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges.     

(Se4)2[Mo2O2Cl8][MCl6](M = Zr,Hf) — Tetraselenium(2+)Halometalates with two Different Anions

The reaction of Se₄[Mo₂O₂Cl₈] with Se₄[MCl₆] (M = Zr, Hf) or of Se, SeCl₄, MoOCl₄, and MCl₄ (M = Zr, Hf) at 120 °C in sealed evacuated glass ampoules gives (Se₄)₂[Mo₂O₂Cl₈][MCl₆] (M = Zr, Hf) in the form of dark‐green, air sensitive crystals in quantitative yield. The crystal structure analyses of both isotypic compounds (monoclinic, P2₁/c, Z = 2, a = 1336(2), b = 716(1), c = 1518(4) pm, β = 106.0(2)° for M = Zr; a = 1334.1(8), b = 715.03(9), c = 1518.2(3) pm, β = 106.00(2)° for M = Hf) show the presence of square‐planar Se₄²⁺, of dinuclear [Mo₂O₂Cl₈]^2—, and of almost regular octahedral [MCl₆]^2— ions. X‐ray crystallographic investigations on (Se₄)₂[Mo₂O₂Cl₈][ZrCl₆] give no hint for solid state phase transitions between —160 and 200 °C. This is in contrast to the related compounds Se₄[Mo₂O₂Cl₈] and Se₄[ZrCl₆] which both undergo phase transitions accompanied by reorientation of the cations and anions. (Se₄)₂[Mo₂O₂Cl₈][ZrCl₆] is paramagnetic and obeys the Curie‐Weiss law with a Weiss constant of —4(7) K indicating only weak interaction between the paramagnetic centres. The magnetic moment of 1.7(1) μ_B is consistent with the presence of Mo^V (d¹ configuration) and supports the ionic formula.     

Synthesis and Thermal Behaviour of Compounds in the System [Ph4P]Cl/BiCl3 and the Crystal Structures of [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 and [Ph4P]2[Bi2Cl8] · 2 CH3COCH3

Six polynuclear chlorobismuthates are formed in the reaction between BiCl₃ and Ph₄PCl by variation of the molar ratio of the educts, the solvents and the crystallisation methods: [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂, [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃, [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃, [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN, [Ph₄P]₄[Bi₆Cl₂₂], and [Ph₄P]₄[Bi₈Cl₂₈]. We report the crystal structure of [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ which crystallises with triclinic symmetry in the S. G. P1 No. 2, with the lattice parameters a = 13.080(3) Å, b = 14.369(3) Å, c = 21.397(4) Å, α = 96.83(1)°, β = 95.96(1)°, γ = 95.94(2)°, V = 3943.9(1) ų, Z = 2. The anion is formed from two face‐sharing BiCl₆‐octahedra. [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃ crystallises with monoclinic symmetry in the S. G. P2₁/n, No. 14, with the lattice parameters a = 14.045(5) Å, b = 12.921(4) Å, c = 17.098(3) Å, β = 111.10(2)°, V = 2894.8(2) ų, Z = 2. The anion is a bi‐octahedron of two square‐pyramids, joined by a common edge. The octahedral coordination is achieved with two acetone ligands. [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN crystallises in the triclinic S. G., P1, No. 2, with the lattice parameters a = 14.245(9) Å, b = 17.318(6) Å, c = 24.475(8) Å, α = 104.66(3)°, β = 95.93(3)°, γ = 106.90(4)°, V = 5486(4) ų, Z = 2. Two Bi₂Cl₈ dimers in syn‐position form the cubic anion. Lattice parameters of [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ are also given. The solvated compounds are desolvated at approximately 100 °C. [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ and [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ show the same sequence of phase transitions after desolvation. All compounds melt into a liquid in which some order is observed and transform on cooling into the glassy state.     

Syntheses and Crystal Structures of the Novel Ternary Thioborates Na3BS3, K3BS3, and Rb3BS3

The orthothioborates Na₃BS₃, K₃BS₃ and Rb₃BS₃ were prepared from the metal sulfides, amorphous boron and sulfur in solid state reactions at temperatures between 923 and 973 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction experiments. Na₃BS₃ crystallizes in the monoclinic space group C2/c (No. 15) with a = 11.853(14) Å, b = 6.664(10) Å, c = 8.406(10) Å, β = 118.18(2)° and Z = 4. K₃BS₃ and Rb₃BS₃ are monoclinic, space group P2₁/c (No. 14) with a = 10.061(3) Å, b = 6.210(2) Å, c = 12.538(3) Å, β = 112.97(2) and a = 10.215(3) Å, b = 6.407(1) Å, c = 13.069(6) Å, β = 103.64(5)°, Z = 4. The potassium and rubidium compounds are not isotypic. All three compounds contain isolated [BS₃]^3– anions with boron in a trigonal‐planar coordination. The sodium cations in Na₃BS₃ are located between layers of orthothioborate anions, in the case of K₃BS₃ and Rb₃BS₃ stacks of [BS₃]^3– entities are connected via the corresponding cations. X‐ray powder patterns were measured and compared to calculated ones obtained from single crystal X‐ray structure determinations.     

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.     

Synthesis,Crystal Structure,and Characterization of three New Letrozole Complexes

Three new letrozole complexes {[Cu(Le)₄Cl₂] · (H₂O)} ( 1 ), {[Ni(Le)₄Cl₂] · (H₂O)}( 2 ) and {[Co(Le)₄Cl₂] · (H₂O)} ( 3 ) (Le = letrozole = 1‐[bis(4‐cyanophenyl)methyl]‐1, 2, 4‐triazole) were obtained from self‐assembly of CuCl₂, NiCl₂ · 6H₂O, and CoCl₂ · 6H₂O with medicine letrozole. All compounds were characterized by IR spectroscopy, elemental, single‐crystal as well as powder X‐ray diffraction, and thermogravimetric analyses. The analyses of the structures indicate that all crystals belong to monoclinic system, space group C2/c, for complex 1 with crystal data a = 34.501(18) Å, b = 12.724(7) Å, c = 16.116(9) Å, β = 114.958(7) °, V = 6414(6) Å ³, Z = 4, F(000) = 2660, R₁ = 0.0668, wR₂ = 0.1574; for complex 2 , a = 34.769(6) Å, b = 12.7267(18) Å, c = 16.046(2) Å, β = 115.281(3) °, V = 6420.1(16) Å ³, Z = 4, F(000) = 2656, R₁ = 0.0510, wR₂ = 0.0896; for complex 3 , a = 35.063(8) Å,b = 12.658(3) Å, c = 16.056(4) Å, β = 115.387(3) °, V = 6438(2) ų, Z = 4, F(000) = 2652, R₁ = 0.0528, wR₂ = 0.1205. The local arrangements around central metal atoms (Cu^II, Ni^II, and Co^II) can be best described as distorted octahedra which are constructed by two chlorine atoms and four monodentate nitrogen atoms from different letrozole ligands. XRD results of 1 – 3 show that all peaks displayed in the measured patterns at room temperature closely match those in the simulated patterns generated from single‐crystal diffraction data, indicating single phases of 1 – 3 were formed.     

Crystal Structure and Thermal Behaviour of K2[CrF5·H2O]

K₂[CrF₅·H₂O] is monoclinic: a = 9.6835(3) Å, b = 7.7359(2) Å, c = 7.9564(3) Å, β = 95.94(1)°, Z = 4, space group C2/c (n^o 15). Its crystal structure was solved from its X‐ray powder pattern recorded on a powder diffractometer, using for the refinement the Rietveld method. It is built up from isolated octahedral [CrF₅·OH₂]^2? anions separated by potassium cations. The dehydration of K₂[CrF₅·H₂O] leads to anhydrous orthorhombic K₂CrF₅: a = 7.334(2) Å, b = 12.804(4) Å, c = 20.151(5) Å, Z = 16, space group Pbcn (n^o 60), isostructural with K₂FeF₅.     

Hydrothermal Synthesis and X‐ray Crystal Structure of Four Inorganic‐Organic Hybrid Compounds in Vanadium /Copper Iodate Family

Four inorganic‐organic hybrid compounds with the formulae (1,10‐phen)(VO₂)(IO₃) ( 1 ), (2,2′‐bipy)(VO₂)(IO₃) ( 2 ), [Cu₃(2,2′‐bipy)₃Cl₃(IO₃)₂]·I_1.5 ( 3 ), and [Cu(2,2′‐bipy)(H₂O)(IO₃)₂]· (H₂O)₂ ( 4 ) are hydrothermally synthesized at 120 °C for 6 d and characterized by single‐crystal X‐ray diffraction. The use of two different bidentate organodiamine ligands 1,10‐phen and 2,2′‐bipy in the V/I/O system gives rise to compounds 1 and 2 , which crystallize in a monoclinic system with the space group C2/c, a = 17.8131(6) Å, b = 15.0470(7) Å, c = 12.9902(4) Å, β = 133.095(2)°, V = 2542.49(17) ų for 1 and space group P2₁/c, a = 13.3095(5) Å, b = 15.0993(8) Å, c = 13.0454(4) Å, β = 116.971(2)°, V = 2335.88(17) ų for 2 . The use of the bidentate organodiamine ligand 2,2′‐bipy in the Cu/I/O system gives rise to the variety in the structure of products 3 and 4 , which crystallize in a triclinic system with the same space group . a = 8.5143(2) Å, b = 10.4908(3) Å, c = 22.8420(6) Å, α = 93.769(10)°, β = 91.723(10)°, γ = 112.111(10)°, V = 1882.83(9) ų for 3 and a = 6.731(6) Å, b = 10.110(4) Å, c = 12.899(6) Å, α = 106.00(5)°, β = 95.45(4)°, γ = 107.69(6)°, V = 788.4(9) ų for 4 . The solid‐state structures of the compounds 1 and 2 have chains with repeat units of alternative corner sharing of [VO₄N₂] octahedra and [IO₃] pyramids. Compound 3 is a chain containing [IO₃] pyramids and [VO₄N] square pyramids and compound 4 consists of Cu(2,2′‐bipy)²⁺ linked by one water molecule and two [IO₃] pyramids. The thermal stabilities of the compounds are investigated.     

Selen‐Polykationen stabilisiert durch polymere Chlorobismutat‐Anionen: Synthesen und Kristallstrukturen von Se4[Bi4Cl14] und Se10[Bi5Cl17]

Selenium Polycations Stabilized by Polymeric Chlorobismuthate Anions: Syntheses and Crystal Structures of Se₄[Bi₄Cl₁₄] and Se₁₀[Bi₅Cl₁₇] Reactions of selenium with selenium(IV) chloride and bismuth(III) chloride in sealed evacuated glass ampoules at temperatures between 110 and 155 °C yield a series of compounds which are composed of discrete selenium polycations and polymeric chlorobismutate anions. Besides the already known Se₈[Bi₄Cl₁₄] two new compounds have been identified by crystal structure analyses as Se₄[Bi₄Cl₁₄] (tetragonal, P4/n, a = 1089.1(2) pm, c = 993.7(2) pm, Z = 2) and Se₁₀[Bi₅Cl₁₇] (monoclinic, P2₁/c, a = 1079.24(8) pm, b = 2062.9(2) pm, c = 1676.1(2) pm, β = 90.87(1)°, Z = 4). Se₄[Bi₄Cl₁₄] was obtained as red transparent platelike crystals and is the first example of a compound with (chalcogen₄)²⁺ ions of exact square‐planar symmetry and molecular point group D_4h in the solid state. The cations are surrounded by layers of two‐dimensional polymeric anions [Bi₄Cl₁₄]^2–. Se₁₀[Bi₅Cl₁₇] forms dark grey crystals with a reddish luster. The structure contains the known bicyclic polycation Se₁₀²⁺ which is disordered over two positions and the first three‐dimensional polymeric chlorobismutate anion [Bi₅Cl₁₇]^2–. The different BiCl_x polyhedra are linked by sharing common vertices, edges, and faces.     

Ein Beitrag zu Rhenium(II)‐, Osmium(II)‐ und Technetium(II)‐Thionitrosylkomplexen vom Typ [M(NS)Cl4py]—: Darstellung,Strukturen und EPR‐Spektren

A Contribution to Rhenium(II)‐, Osmium(II)‐, and Technetium(II)‐Thionitrosyl‐Complexes: Preparation, Structures, and EPR‐Spectra The reaction of [Re^VINCl₄]^— and [Os^VINCl₄]^— with S₂Cl₂ leads to the formation of the thionitrosyl complexes [M^II(NS)Cl₄]^— (M = Re, Os) which could not be isolated as pure compounds. Addition of pyridine to the reaction mixture results in the formation of the stable compounds trans‐(Ph₄P)[Os^II(NS)Cl₄py], trans‐(Hpy)[Os^II(NS)Cl₄py], trans‐(Ph₄P)[Re^II(NS)Cl₄py], and cis‐(Ph₄P)[Re^II(NS)Cl₄py]. The crystal structure analyses show for trans‐(Ph₄P)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 12.430(3)Å, b = 18.320(4)Å, c = 15.000(3)Å, β = 114.20(3)°, Z = 4), trans‐(Hpy)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 7.689(1)Å, b = 10.202(2)Å, c = 20.485(5)Å, β = 92.878(4)°, Z = 4), trans‐(Ph₄P)[Re^II(NS)Cl₄py] (triclinic, P1¯, a = 9.331(5)Å, b = 12.068(5)Å, c = 15.411(5)Å, α = 105.25(1)°, β = 90.23(1)°, γ = 91.62(1)°, Z = 2), and cis‐(Ph₄P)[Re^II(NS)Cl₄py] (monoclinic, P2₁/c, a = 10.361(1)Å, b = 16.091(2)Å, c = 17.835(2)Å, β = 90.524(2)°, Z = 4) M‐N‐S angles in the range 168‐175°. This indicates a nearly linear coordination of the NS ligand. The metal atom is octahedrally coordinated in all cases. The rhenium(II) thionitrosyl complexes (5d⁵ “low‐spin” configuration, S = 1/2) are studied by EPR in the temperature range 295 > T > 130 K. In addition to the detection of the complexes formed during the reaction of [Re^VINCl₄]^— with S₂Cl₂ EPR investigations on diamagnetically diluted powders and single crystals of the system (Ph₄P)[Re^II/Os^II(NS)Cl₄py] are reported. The ^{185, 187}Re hyperfine parameters are used to get information about the spin‐density distribution of the unpaired electron in the complexes under study. [Tc^VINCl₄]^— reacts with S₂Cl₂ under formation of [Tc^II(NS)Cl₄]^— which is not stable and decomposes under S₈ elimination and rebuilding of [Tc^VINCl₄]^— as found by EPR monitoring of the reaction.     

Crystal Structures of Alkali Metal Peroxodiphosphates

Peroxodiphosphates of alkali metals can be prepared from K₄P₂O₈, which is synthesized by electrolysis, in metathesis reactions with the corresponding perchlorates. Single crystals have been obtained by diffusion of methanol into aqueous solutions of the peroxodiphosphates. The crystal structures of Li₄P₂O₈·4H₂O (P2₁/n; a = 8.057(2) Å, b = 5.074(1) Å, c = 12.288(3) Å, β = 100.53(2)°; V = 493.9(2) ų; Z = 2), Na₄P₂O₈·18H₂O (at 130 K: P6₁; a = 9.0984(14) Å, c = 49.926(13) Å; V = 3579.2(12) ų; Z = 6) and K₄P₂O₈ (P2₁/c; a = 5.9041(15) Å, b = 10.254(2) Å, c = 7.356(2) Å, β = 99.05(3)°; V = 439.79(18) ų; Z = 2) have been determined by X‐ray diffraction. In the Li salt the cations are tetrahedrally coordinated by one water molecule and three oxygen atoms of the anions, whereas the Na salt is characterized by binuclear [Na₂(H₂O)₉]²⁺ complexes. At low temperatures, the latter undergoes a phase transition from a structure with disordered anions to a completely ordered phase. K₄P₂O₈ is solvent‐free and exhibits irregular cation coordination. The structure of the peroxodiphosphate anion is very similar in all compounds; the mean O–O distance is 1.49(1) Å. In addition, the structure determination of K₄(HPO₄)₂·3H₂O₂ (P2₁/n; a = 6.076(1) Å, b = 6.579(1) Å, c = 17.215(2) Å, β = 99.73(1)°; V = 678.26(17) ų; Z = 2), which can be mistaken for K₄P₂O₈, is presented.     

Dithiolylium‐Chlorooxomolybdate(V): Synthese und Kristallstruktur von (C3Cl3S2)[MoOCl4] und (C3Cl3S2)[Mo2O2Cl7]

Dithiolylium Chlorooxomolybdates(V): Synthesis and Crystal Structure of (C₃Cl₃S₂)[MoOCl₄] and (C₃Cl₃S₂)[Mo₂O₂Cl₇] The reaction of 3, 4, 5‐Trichlor‐1, 2‐dithiolylium chloride with MoOCl₃ in dichlormethane under solvothermal conditions at 65 °C simultaneously yields the green tetrachlorooxomolybdate(V) (C₃Cl₃S₂)[MoOCl₄] and the yellow‐brown heptachlorodioxodimolybdate(V) (C₃Cl₃S₂)[Mo₂O₂Cl₇]. The crystal structures of both compounds contain nearly planar (C₃Cl₃S₂)⁺ ions with a S—S bond length of 203 pm. The discrete [MoOCl₄]^— ion in the structure of (C₃Cl₃S₂)[MoOCl₄] has the shape of a square pyramid with the oxygen atom at the apex. The molybdenum atom is displaced by 58 pm from the basal plane towards the oxygen atom. The [Mo₂O₂Cl₇]^— ion in the structure of (C₃Cl₃S₂)[Mo₂O₂Cl₇] has the form of a face‐sharing double octahedron. It is formally composed of a [MoOCl₄]^— ion and a MoOCl₃ molecule connected by one symmetrical and two unsymmetrical chloro bridges. The molybdenum atoms placed in the centers of such connected octahedra are 357 pm apart, indicating no Mo—Mo bond.     

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.     

Hydroxo‐bridged Tetranuclear CuII Complexes: {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O and {[Cu(phen)(OH)]4(H2O)2}]Cl4 · 4 H2O

The blue tetranuclear Cu^II complexes {[Cu(bpy)(OH)]₄Cl₂}Cl₂ · 6 H₂O ( 1 ) and {[Cu(phen)(OH)]₄(H₂O)₂}Cl₄ · 4 H₂O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) ų, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) ų, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]₄Cl₂}²⁺ and {[Cu(phen)(OH)]₄(H₂O)₂}⁴⁺ complex cations formed by condensation of four elongated square pyramids CuN₂(OH)₂L^ap with the apical ligands L^ap = Cl, H₂O, OH. The resulting [Cu₄(μ₂‐OH)₂(μ₃‐OH)₂] core has the shape of a zigzag band of three Cu₂(OH)₂ squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl^– anions and H₂O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Cl^ap = 2.563; Cu–O^ap(OH) = 2.334–2.369 Å; Cu–O^ap(H₂O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χ_m(T‐θ) = 0.933 cm³ · mol^–1 · K with θ = –0.7 K).     

Halogenide der Seltenerdmetalle Ln4X5Z. Teil 3: Das Chlorid La4Cl5B4 – Präparation,Struktur und Verwandtschaft zu La4Br5B4, La4I5B4

Rare Earth Halides Ln₄X₅Z. Part 3: The Chloride La₄Cl₅B₄ – Preparation, Structure, and Relation to La₄Br₅B₄, La₄I₅B₄ La₄Cl₅B₄ is synthesized by reaction of LaCl₃, La metal and boron in sealed Ta containers at 1050 °C < T < 1350 °C. It crystallizes in the monoclinic space group C2/m with a = 16.484(3) Å, b = 4.263(1) Å, c = 9.276(2) Å and β = 120.06(3)°. Ce₄Cl₅B₄ is isotypic, a = 16.391(3) Å, b = 4.251(1) Å, c = 9.180(2) Å and β = 120.20(3)°. The La atoms form strings of trans-edge shared La octahedra, and the B atoms inside the strings form B₄-rhomboids, which are condensed to chains via opposite corners. The Cl atoms interconnect the channels according to La₂La_4/2Clⁱ⁻ⁱ_6/2Cl^i−a_2/2Cl^a−i_2/2. The crystal structures of the bromide and the iodide are comparabel, however, the interconnection of the strings is different in the three structure types, as 14 Cl, 13 Br and 12 I atoms surround the La₆ octahedra.     

Polymere,bandförmige Tellurkationen in den Strukturen des Chloroberyllats Te7[Be2Cl6] und des Chlorobismutats (Te4)(Te10)[Bi4Cl16]

Polymeric, Band Shaped Tellurium Cations in the Structures of the Chloroberyllate Te₇[Be₂Cl₆] and the Chlorobismutate (Te₄)(Te₁₀)[Bi₄Cl₁₆] Te₇[Be₂Cl₆] is obtained at 250 °C in an eutectic Na₂[BeCl₄] / BeCl₂ melt from Te, TeCl₄ und BeCl₂ in form of black crystals, which are sensitive towards hydrolysis in moist air. (Te₄) (Te₁₀)[Bi₄Cl₁₆] is prepared from Te, TeCl₄ und BiCl₃ by chemical vapour transport in sealed evacuated glass ampoules in a temperature gradient 150 ° → 90 °Cin form of needle shaped crystals with a silver lustre. The structures of both compounds were determined based on single crystal X‐ray diffraction data (Te₇[Be₂Cl₆]: orthorhombic, Pnnm, Z = 2, a = 541.60(3), b = 974.79(6), c = 1664.4(1) pm; (Te₄)(Te₁₀)[Bi₄Cl₁₆]: triclinic, P1¯, Z = 2, a = 547.2(3), b = 1321.1(7), c = 1490(1) pm, α = 102.09(5)°, β = 95.05(5)°, γ = 96.69(4)°). The structure of Te₇[Be₂Cl₆] consists of one‐dimensional polymeric cations (Te₇²⁺)_n which form folded bands and of discrete [Be₂Cl₆]^2— anions which form double tetrahedraconnected by a common edge. By a different way of folding compared with the cations present in the structures of Te₇[MOX₄]X (M = Nb, W; X = Cl, Br) the (Te₇²⁺)_n cation in Te₇[Be₂Cl₆]represents a new, isomeric form. The structure of (Te₄)(Te₁₀)[Bi₄Cl₁₆] contains two different polymeric cations. (Te₁₀²⁺)_n consists of planar Te₁₀ groups in the form of three corner‐sharing Te₄ rings connected to folded bands. (Te₄²⁺)_n forms in contrast to the so far notoriously observed discrete, square‐planar E₄²⁺ ions a chain of rectangular planar Te₄ rings (Te—Te 274 and 281 pm) connected by Te‐Te bonds of 297 pm. [Bi₄Cl₁₆]^4— has a complex one‐dimensional structure of edge‐ and corner‐sharing BiCl₇ units.     

Ortho‐Chalcogenotetrelate Anions as Chelating Ligands: Syntheses and Characterization of [K6(MeOH)9][Sn2Se6][Cr(en)2(SnSe4)]2, [Na(H2O)4][Cr(en)3]2[GeS3OH]2[Cr(en)2(GeS4)], and [Ba(H2O)10][{Cr(en)}2(GeSe4)2]

Reactions of K₄[SnSe₄], Na₄[GeS₄] or Ba₂[GeSe₄] with different 1,2‐diaminoethane (= en) coordinated complexes of CrCl₃ ([Cr(en)₂Cl₂]Cl or [Cr(en)₃]Cl₃) in MeOH or aqueous solution yielded three novel compounds that contain complexes of Cr³⁺ with ortho‐chalcogenotetrelate anions [E′E₄]^4? (E′ = Ge, Sn; E = S; Se): the crystal structures of [K₆(MeOH)₉][Sn₂Se₆][Cr(en)₂(SnSe₄)]₂ ( 1 ), [Na(H₂O)₄][Cr(en)₃]₂[GeS₃OH]₂[Cr(en)₂(GeS₄)] ( 2 ), and [Ba(H₂O)₁₀][{Cr(en)}₂(GeSe₄)₂] ( 4 ) have been determined by means of single crystal X‐ray diffraction ( 1 : triclinic space group ; lattice dimensions at 203 K: a = 1175.7(2), b = 1315.3(3), c = 1326.7(3) pm, α = 61.99(3)°, β = 64.05(3)°, γ = 83.57(3)°, V = 1617.4(6)·10⁶ pm³; R₁ [I > 2σ(I)] = 0.0788; wR₂ = 0.1306; 2 : monoclinic space group C2/c; lattice dimensions at 203 K: a = 2445.3(5), b = 1442.5(3), c = 1579.3(3) pm, β = 94.61(3)°, V = 5552.9(19)·10⁶ pm³; R₁ [I > 2σ(I)] = 0.0801; wR₂ = 0.2046; 4 : triclinic space group ; lattice dimension at 203 K: a = 1198.4(2), b = 1236.8(3), c = 1297.5(3) pm, α = 65.69(3)°, β = 63.35(3)°, γ = 81.21(3)°, V = 1565.2(5)·10⁶ pm³; R₁ [I > 2σ(I)] = 0.0732; wR₂ = 0.1855). 1 and 2 show the yet unprecedented complexation of transition metal ions by non‐bridging, single chalcogenotetrelate ligands to produce dinuclear, heterobimetallic complexes. Compound 2 contains the first structurally characterized complex with an ortho‐thiogermanate ligand. The formation of these compounds, and of a by‐product of 2 , [Cr(en)₃][GeS₃OH]·6H₂O ( 3 : monoclinic space group C2/c; lattice dimensions at 203 K: a = 2396.8(5), b = 1463.4(3), c = 1740.1(4) pm, β = 132.99(3)°, V = 4463.8(15)·10⁶ pm³; R₁ [I > 2σ(I)] = 0.0462; wR₂ = 0.1058), provides some insight in fundamental differences between the reaction behavior of [SnE₄]^4? anions one the one hand and [GeE₄]^4? anions on the other hand. The crucial role of the counterion charge becomes evident when comparing the structure motifs of the ternary anions in 1 and 2 with that observed in the Ba²⁺ compound 4 .     

Adducts of Cyclodiphosph(V)azenes: Synthesis and Structure

The reaction of Ph₂PCl and PhPCl₂ with bis(trimethylsilyl)sulfur diimide in the presence of GaCl₃ and AlCl₃ yields diadducts of the corresponding cyclodiphosph(V)azene: [Ph₂PN]₂·(GaCl₃)₂ ( 1 ), [Ph₂PN]₂·(AlCl₃)₂ ( 2 ), and [Ph(Cl)PN]₂·(AlCl₃)₂ ( 3 ). This reaction is triggered by Lewis acids, which catalyse the (CH₃)₃Si‐Cl and S₈ elimination. The structures of 1· 2 CH₂Cl₂, 2· 2 CH₂Cl₂ and 3 were determined by single crystal X‐ray studies ( 1 : triclinic, , a = 9.679(2) Å, b = 9.863(2) Å, c = 11.366(2) Å, α = 113.55(3)°; β = 99.59(3)°; γ = 106.67(3)°; V = 902.8(3) ų, Z = 1; 2 : triclinic, , a = 9.639(2) Å, b = 9.804(2) Å, c = 11.321(2) Å, α = 113.71(3)°; β = 99.44(3)°; γ = 106.70(3)°; V = 889.3(3) ų, Z = 1; 3 : orthorhombic, Pbca, a = 14.853(3) Å, b = 9.261(2) Å, c = 16.631(3) Å, V = 2287.7(8) ų, Z = 4.