On Tetrachlorophosphonium Chlorometallates of Rhenium and Molybdenum: Syntheses,Crystal Structures,and Magnetism of [PCl4]2[Re2Cl10] and [PCl4]3[ReCl6]2, and the Magnetic Properties of [PCl4]2[Mo2Cl10]

MoCl₄, ReCl₄, and ReCl₅ react with PCl₅ in sealed glass ampoules at temperatures between 220° and 320° to [PCl₄]₂[Mo₂Cl₁₀] ( 1 ) [PCl₄]₂[Re₂Cl₁₀] ( 2 ), and [PCl₄]₃[ReCl₆]₂ ( 3 ). 2 crystallizes isotypically to the previously reported 1 and the respective titanium and tin containing analogues. The structure (triclinic, P1, Z = 1, a = 897.3(2), b = 946.0(2), c = 687.13(9) pm, α = 95.59(2)°, β = 95.80(2)°, γ = 101.07(2)°, V = 565.4(2) 10⁶ pm³) is built of tetrahedral [PCl₄]⁺ and edge sharing double octahedral [Re₂Cl₁₀]^2– ions and can be derived from a hexagonal closest packing of Cl^– ions with tetrahedral and octahedral holes partially filled by P(V) and Re(IV), respectively. 3 crystallizes isotypically to [PCl₄]₃[PCl₆][MCl₆] (M = Ti, Sn) (tetragonal, P 4₂/mbc, Z = 4, a = 1496.2(1), c = 1363.2(2) pm). Because no evidence was found for the presence of [PCl₆]^– ions, Re in 3 has to be of mixed valency with Re^IV and Re^V sharing the same crystallographic site. The structure can be derived from a cubic closest packing or alternatively from an only sparsely distorted body centered cubic arrangement of Cl^– ions which is rarely found for anion arrays. The tetrahedral and octahedral holes are partially filled by P^V and M^IV/V, respectively. Magnetic measurements show all three compounds to be paramagnetic and confirm the oxidation state IV for Mo and Re in 1 and 2 and the mixed valence (IV/V) for Re in 3 .     

Preparation and Structure of Rhenium Fluoride Trioxide ReO3F,and the Polymorphism of Rhenium Trifluoride Dioxide,ReO2F3

The methods of preparation of ReO₃F are revised. ReO₃F is an amorphous yellow solid that crystallizes into colorless needles after prolonged heating. Its structure is that of a fluorine and oxygen bridged chain with hexa coordinated rhenium atoms (a = 670.9(2), b = 596.6(2), c = 1030.6(4) pm, β = 90.057(7)°, space group P2/c. In presence of donor solvents ReO₃F·2L (L = (C₂H₅)₂O, (CH₃)₂O, THF) are formed. ReO₂F₃, if crystallized from HF, exists in two crystalline forms, both are fluorine bridged chain polymers. (ReO₂F₃‐I: a = 1539.7(3), b = 999.6(3), c = 924.4(2) pm, β = 95.25(1)°, space group P2₁/c; ReO₂F₃‐II: a = 544.9(1), b = 494.2(1), c = 1253.7(2) pm, β = 98.543(7)°, space group P2₁/c. ReO₂F₃ crystallizes from CFCl₃ or SO₂FCl as fluorine bridged cyclic trimer (a = 881.4(4), c = 822.1(6) pm, γ = 120°, space group P6₃/m, or fluorine bridged cyclic tetramer (a = 1107.8(2), b = 999.4(2), c = 1347.9(3) pm, space group Cmca).     

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.     

The Oxidation of ReCl5 with Oleum: Synthesis and Crystal Structure of Re2O4Cl4(SO4)

The reaction of ReCl₅ and fuming sulfuric acid (25 % SO₃) in a sealed glass tube at 200 °C led to red, needle shaped single crystals of Re₂O₄Cl₄(SO₄) (monoclinic, C2/c, a = 1501.8(2) pm, b = 1545.9(2) pm, c = 945.18(8) pm, β = 98.761(9)°, Z = 8). In the crystal structure the [ReO₂] moieties are linked by [SO₄]^2– tetrahedra to chains along the [101] direction. Each sulfate ion connects four rhenium atoms, additional two chloride ions complete the octahedral coordination sphere of each rhenium atom according to $\rm^1_\infty$ [ReO_2/1Cl_2/1(SO₄)_2/4].     

Rb6LiPr11Cl16[SeO3]12: Ein chloridisch derivatisiertes Rubidium‐Lithium‐Praseodym(III)‐Oxoselenat(IV)

Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂: A Chloride‐Derivatized Rubidium Lithium Praseodymium(III) Oxoselenate(IV) Transparent green square platelets with often truncated edges and corners of Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂ were obtained by the reaction of elemental praseodymium, praseodymium(III,IV) oxide and selenium dioxide with an eutectic LiCl–RbCl flux at 500 °C in evacuated silica ampoules. A single crystal of the moisture and air insensitive compound was characterized by X‐ray diffraction single‐crystal structure analysis. Rb₆LiPr₁₁Cl₁₆[SeO₃]₁₂ crystallizes tetragonally in the space group I4/mcm (no. 140; a = 1590.58(6) pm, c = 2478.97(9) pm, c/a = 1.559; Z = 4). The crystal structure is characterized by two types of layers parallel to the (001) plane following the sequence 121′2′1. Cl^? anions form cubes around the Rb⁺ cations (Rb1 and Rb2; CN = 8; d(Rb⁺?Cl^?) = 331 – 366 pm) within the first layer. One quarter of the possible places for Rb⁺ cations within this CsCl‐type kind of arrangement is not occupied, however the Cl^? anions of these vacancies are connected to Pr³⁺ cations (Pr4) above and below instead, forming square antiprisms of [(Pr4)O₄Cl₄]^9? units (d(Pr4?O) = 247–249 pm; d(Pr4?Cl) = 284–297 pm) that work as links between layer 1 and 2. Central cations of the second layer consist of Li⁺ and Pr³⁺. While the Li⁺ cations are surrounded by eight O^2? anions (d(Li?O5) = 251 pm) in the shape of cubes again, the Pr³⁺ cations are likewisely coordinated by eight O^2? anions as square antiprisms (for Pr1, d(Pr1?O2) = 242 pm) and by ten O^2? anions (for Pr2 and Pr3), respectively. The latter form tetracapped trigonal antiprisms (Pr2, d(Pr2?O) = 251–253 pm and 4 × 262 pm) or bicapped distorted cubes (Pr3, d(Pr3?O) = 245–259 pm and 2 × 279 pm). The non‐binding electron pairs (“lone pairs”) at the two crystallographically different Ψ¹‐tetrahedral [SeO₃]^2? anions (d(Se⁴⁺?O^2?) = 169–173 pm) are directing towards the empty cavities between the layer‐connecting [(Pr4)O₄Cl₄]^9? units.     

Die Kristallstruktur von SCl3[Re2Cl9] und ihre Verwandtschaft zum RuBr3‐Typ

The Crystal Structure of SCl₃[Re₂Cl₉] and its Relation to the RuBr₃ Type SCl₃[Re₂Cl₉] was obtained from the reaction of rhenium and SCl₂ at 400 °C. The X‐ray crystal structure determination revealed a monoclinic structure, a = 834.1 pm, b = 1053.3 pm, c = 866.1 pm, β = 91.90°, space group P2₁/m, R₁ = 0.058. The SCl₃⁺ and Re₂Cl₉^– ions have the known structures; the ReRe bond length in the face‐sharing bioctahedron is 272.2 pm. The crystal packing can be derived from the RuBr₃ structure type, which has infinite columns of face‐sharing octahedra; one quarter of the metal atoms are removed and another quarter are replaced by sulfur atoms. The chlorine atoms form a slightly distorted hexagonal closest‐packing. The symmetry relationships are shown in a family tree of group–subgroup relations.     

Room-Temperature Synthesis of the Bi5[GaCl4]3 Salt From Three Different Classes of Ionic Liquids

Following the development in the synthesis of subvalent cluster compounds, we report on the use of three different classes of room-temperature ionic liquids for the synthesis of the pentabismuth-tris(tetragallate) salt, Bi₅[GaCl₄]₃, characterized by X-ray diffraction. The Bi₅[GaCl₄]₃ salt was prepared by reduction of BiCl₃ using gallium metal in ionic liquid reaction media containing a strong Lewis acid, GaCl₃. The ionic liquids; trihexyltetradecyl phosphonium chloride [Th-Td-P⁺]Cl^?, 1-dodecyl-3-methylimidazolium chloride [Dod-Me-Im⁺]Cl^? and N-butyl-N-methylpyrrolidinium chloride [Bu-Me-Pyrr⁺]Cl^? from three of the main classes of ionic liquids were used in synthesis. Reactions using ionic liquids composed of the trihexyltetradecyl phosphonium cation [Th-Td-P⁺] and the anions; tetrafluoroborate [BF₄ ^?], bis(trifluoro-methyl sulfonyl) imide [(Tf)₂N^?] and hexafluorophosphate [PF₆ ^?] were also investigated.     

S5N5⊕[GaCl4]⊖ und S5N5⊕[Ga2Cl7]⊖. Synthesen,IR-Spektren und Kristallstrukturen

S₅N₅ ^⊕[GaCl₄]^? and S₅N₅ ^⊕[Ga₂Cl₇]^?. Synthesis, IR Spectra, and Crystal Structures . S₅N₅[GaCl₄] was obtained in high yields from gallium and trithiazyl chloride; depending on the solvent, different second products are formed: S₄N₄Cl[GaCl₄] in dichloromethane and S₃N₂Cl[GaCl₄] in carbon tetrachloride. These products can be separated due to their high solubility in CH₂Cl₂, S₅N₅[GaCl₄] being only slightly soluble. S₃N₂Cl[GaCl₄] can be converted to S₅N₅[GaCl₄] with additional (NSCl)₃. By the action of GaCl₃ on S₅N₅[GaCl₄], S₅N₅[Ga₂Cl₇] is formed. The IR spectra of the title compounds are reported; they differ considerably as well in number as in frequencies of the cation bands and show that the S₅N₅^⊕ ion has different structures depending on the anion. The crystal structures of both compounds were determined by X-ray diffraction. Crystal data: S₅N₅[GaCl₄], orthorhombic, a = 943.8, b = 1369.0, c = 2068.8 pm, space group Pnma, Z = 8 (1381 observed reflexions, R = 0.075); S₅N₅[Ga₂Cl₇], monoclinic, a = 847.5, b = 1298.2, c = 1654.0 pm, β = 93.51°, space group P2₁/n, Z = 4 (1359 observed reflexions, R = 0.065). S₅N₅[GaCl₄] is isotypic with S₅N₅[AlCl₄], showing a heartshaped S₅N₅^⊕ ion, but large ellipsoids of vibration suggest the presence of some kind of disorder (statical or dynamical). In S₅N₅[Ga₂Cl₇] the S₅N₅^⊕ has an azulene-like structure. In both cases the cations are planar, all S? N bond lengths being approximately equal.     

Synthese und Struktur von [Re(NH)Cl2(PMe2Ph)3][TaCl6] und [(Me2PhP)3Cl2Re≡N]2VOCl2

Synthesis and Structure of [Re(NH)Cl₂(PMe₂Ph)₃][TaCl₆] and [(Me₂PhP)₃Cl₂Re≡N]₂VOCl₂ The products of the reaction of ReNCl₂(PMe₂Ph)₃ with TaCl₅ are dependent on the solvent. In CH₂Cl₂ the solvent protonates the nitrido ligand to yield [Re(NH)Cl₂(PMe₂Ph)₃][TaCl₆] as air-stable, reddish brown needles with the space group P2₁/n and a = 1213.8(3), b = 1358.0(2), c = 2165.9(4) pm, β = 92.88(1)°, Z = 4. The Re atom of the cation exhibits an octahedral coordination with the phosphine ligands in meridional arrangement. The imido ligand is in trans-position to a Cl atom with a distance Re–N = 170.4(4) pm. When the reaction is carried out in toluene the dinuclear nitrido complex [Re(NTaCl₅)Cl₂(PMe₂Ph)₃] is obtained instead. The reaction of ReNCl₂(PMe₂Ph)₃ with VCl₃(THF)₃ in toluene affords the threenuclear complex [Re₂N₂Cl₄(PMe₂Ph)₅]VCl₃, which upon crystallization at air gives air-stable, reddish-brown crystals of [(Me₂PhP)₃Cl₂ReN]₂VOCl₂. They crystallize in the monoclinic space group P2₁ with a = 1519.2(5), b = 1257.1(1), c = 1564.3(6) pm, β = 102.86(2)°, and Z = 2. The threenuclear complex shows an almost linear arrangement Re≡N–V–N≡Re with distances Re–N 171(2) pm and V–N of 209(2) pm.     

Synthese,Struktur und Eigenschaften der Tetraarsenidometallate(V) M7[TAs4] (M = K,Rb; T = Nb,Ta)

Synthesis, Structure, and Properties of the Tetraarsenidometallates(V) M₇[TAs₄] (M = K, Rb; T = Nb, Ta) The tetraarsenidometallates(V) M₇[TAs₄] (M = K, Rb; T = Nb, Ta) have been prepared from RbAs, KAs, Rb₃As, K₃As, and Nb or Ta in sealed Nb(Ta) ampoules at T = 1100 K. They crystallize in a new structure type oP24 (Pmn2₁, no. 31); K₇[NbAs₄]: a = 1019.2(2) pm, b = 916.2(2) pm, c = 830.6(1) pm; K₇[TaAs₄]: a = 1017.3(2) pm, b = 915.5(2) pm, c = 830.5(2) pm; Rb₇[NbAs₄]: a = 1059.2(4) pm, b = 952.8(4) pm, c = 860.4(4) pm; Z = 2 formula units per unit cell). The compounds form dark red crystals and they are sensitive against air and moisture. They are semiconductors with E_g = 1.80 eV. The thermal decomposition in dynamical vacuum gives evidence for the existance of K₄TAs₃ and K₂TAs₂ (T = Nb, Ta). Main structural units are polar oriented tetrahedra [TAs₄] with d (T – As) = 252.2(1) pm; 251.3(1) pm; 253.0(4) pm, respectively. The As atoms are trigonal prismatically coordinated by M and T atoms. These trigonal prisms form anionic and cationic layers [M₄As₂]^2? and _∞²[M₃TAs₂]²⁺ alternating along the b axis. The structure is comparable with that of Co₂P and can be described as a stuffed shear variant of the Na₆□ZnO₄ type of structure.     

Pertechnetyl Fluorosulfate, [TcO3]+[SO3F]−

A one step synthesis of [TcO₃]⁺[SO₃F]^? is reported. The compound is volatile at room temperature and has according to calculations a tetrahedral coordination around Tc and a monodentate SO₃F group. In the solid state the [SO₃F]^? anion bridges three [TcO₃]⁺ cations, and vice versa. Space group P2₁/c, Z = 4, lattice dimensions at 173 K: a = 695.4(11), b = 808.6(12), c = 893.3(14) pm, β = 97.36(8)°.     

Metallcarbonyl-Synthesen. 23. Kristallstruktur und Reaktionsverhalten von Carbonylmetall-Komplexen des Heptamethylindens

Syntheses of Metal Carbonyls. 23. Crystal Structure and Reactivity of Heptamethylindenyl Carbonyl Metal Complexes Reaction of heptamethylindene (C₉(CH₃)₇, 1 ) with Re₂(CO)₁₀ yields [η⁵-C₉(CH₃)₇]Re(CO)₃ ( 2 ), which reacts with NO⁺BF₄^? to form the cationic complex [{η⁵-C₉(CH₃)₇}Re(CO)₂NO]⁺BF₄^? ( 3 ). Irradiation of 2 with UV light in the presence of triethyl phosphite leads to formation of [η⁵-C₉(CH₃)₇]Re(CO)₂[P(OC₂H₅)₃] ( 4 ). Alkylation of (CH₃)₃SnCl with Ind*Li gives [η¹-C₉(CH₃)₇]Sn(CH₃)₃ ( 5 ). All compounds were characterized by spectroscopic methods. The molecular structures of 3 and 5 were determined by single crystal X-ray diffraction ( 3 : P2₁/n (14), a = 1497.7(4) pm, b = 879.0(2) pm, c = 1609.0(4) pm and β = 110.99(2)°, R₁ = 0.038, wR₂ = 0.080; 5 : P2₁/n (14), a = 726.1(1) pm, b = 2930.7(3) pm, c = 930.0(1) pm and β = 112.834(5)°, R₁ = 0.044, R_w = 0.048). Complexes 2 ? 4 exhibit a piano stool configuration with a η⁵-coordinated permethylindenyl ligand (Ind*). Compound 5 displays a η¹ -coordination of the Ind* ligand. Temperature enhancement causes a hapticity change, as observed by NMR spectroscopy.     

Synthese und Struktur der Komplexe [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2PdCl2], [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 und [(n‐Bu)4N]2[Pd3Cl8]

Synthesis and Crystal Structure of the Complexes [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂PdCl₂], [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ and [(n‐Bu)₄N]₂[Pd₃Cl₈] The threenuclear complex [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂ PdCl₂] ( 1 ) is obtained in THF by the reaction of PdCl₂(NCC₆H₅)₂ with [(n‐Bu)₄N][ReNCl₄] in the molar ration 1:2. It forms orange crystals with the composition 1· THF crystallizing in the monoclinic space group C2/c with a = 2973.3(2); b = 1486.63(7); c = 1662.67(8)pm; β = 120.036(5)° and Z = 4. If the reaction is carried out with PdCl₂ instead of PdCl₂(NCC₆H₅)₂, orange crystals of hitherto unknown [(n‐Bu)₄N]₂[Pd₃Cl₈] ( 3 ) are obtained besides some crystals of 1· THF. 3 crystallizes with the space group P1¯ and a = 1141.50(8), b = 1401.2(1), c = 1665.9(1)pm, α = 67.529(8)°, β = 81.960(9)°, γ = 66.813(8)° and Z = 2. In the centrosymmetric complex anion [{(THF)Cl₄Re≡N}₂PdCl₂]^2— a linear PdCl₂ moiety is connected in trans arrangement with two complex fragments [(THF)Cl₄Re≡N]^— via asymmetric nitrido bridges Re≡N‐Pd. For Pd(II) thereby results a square‐planar coordination PdCl₂N₂. The linear nitrido bridges are characterized by distances Re‐N = 163.8(7)pm and Pd‐N = 194.1(7)pm. The crystal structure of 3 contains two symmetry independent, planar complexes [Pd₃Cl₈]^2— with the symmetry 1¯, in which the Pd atoms are connected by slightly asymmetric chloro bridges. By the reaction of equimolar amounts of [Ph₄P][ReNCl₄] and PdCl₂(NCC₆H₅)₂ in THF brown crystals of the heterometallic complex, [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ ( 2 ) result. 2 crystallizes in the monoclinic space group P2₁/n with a = 979.55(9); b = 2221.5(1); c = 1523.1(2)pm; β = 100.33(1)° and Z = 2. In the central unit ClPd(μ‐Cl)₂PdCl of the centrosymmetric anionic complex [(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂^2— the coordination of the Pd atoms is completed by two nitrido bridges Re≡N‐Pd to nitrido complex fragments [(THF)Cl₄Re≡N]^— forming a square‐planar arrangement for Pd(II). The distances in the linear nitrido bridges are Re‐N = 163.8(9)pm and Pd‐N = 191.5(9)pm.     

离子液体[C2mim][GaCl4]的溶解热研究

在干燥氩气氛下, 用等摩尔的高纯无水GaCl3和[C2mim][Cl](氯化1-甲基-3-乙基咪唑)直接搅拌混合, 制备了淡黄色透明的的离子液体[C2mim][GaCl4] (1-ethyl-3-methylimidazolium chlorogallate) . 在298.15 K下, 利用具有恒温环境的溶解反应热量计, 测定了这种离子液体的不同浓度摩尔溶解焓 . 针对[C2mim][GaCl4]溶解于水后即分解的特点, 在Pitzer电解质溶液理论基础上, 提出了确定这种离子液体标准摩尔溶解焓的新方法, 得到了[C2mim][GaCl4]在水中的标准摩尔溶解焓, ＝－132 kJ•mol－1, 以及Pitzer焓参数组合: ＝－0.1373076和 ＝0.3484209. 借助热力学循环和Glasser离子液体晶格能理论, 用Ga3＋, Cl－和[C2mim]—的离子水化焓数据以及本文得到的[C2mim][GaCl4]标准摩尔溶解焓, 估算了配离子4Cl－(g)解离成Ga3＋(g)和4Cl－(g)的解离焓ΔHdis([GaCl4]-)≈5855 kJ•mol－1. 这个结果揭示了离子液体[C2mim][GaCl4]的标准摩尔溶解焓绝对值并不很大的原因, 即是很大的离子水化焓被很大的[GaCl4]－(g)的解离焓相互抵消了.     

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.     

Synthese und Kristallstrukturen der Seltenerd-Komplexe [LaI2(THF)5]+I3−, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]−, [ErCl3(DME)2] und [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]−

Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI₂(THF)₅]⁺I₃^?, [SmCl₃(THF)₄], [ErCl₂(THF)₅]⁺ [ErCl₄(THF)₂]^?, [ErCl₃(DME)₂], and [Na(18-Crown-6)(THF)₂]⁺[YbBr₄(THF)₂]^? [LaI₂(THF)₅]⁺I₃^? ( 1 ) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at ?83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way. [SmCl₃(THF)₄] ( 2 ) originates as colourless crystals on heating SmCl₃ with excess THF in the presence of Me₃SiNPEt₃. Space group P2₁/c, Z = 8, lattice dimensions at ?50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way. [ErCl₂(THF)₅]⁺[ErCl₄(THF)₂]^? ( 3 ). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at ?50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom. [ErC1₃(DME)₂] ( 4 ) originates as pink single crystals from ₃ with excess boiling 1,2-dimethoxyethane. Space group P2₁/c, Z = 4, lattice dimensions at ?50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions. [Na(18-Krone-6)(THF)₂]⁺ [YbBr₄(THF)₂]^? ( 5 ) is formed as by-product by the reaction of YbBr₃ with NaN(SiMe₃)₂ in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1 , Z = 1, lattice dimensions at ?70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr₄(THF)₂]^?ions, in which the THF molecules are arranged in trans-position.     

(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.     

Constitutional Isomerism of BiW6Cl15: (BiCl)[W6Cl14] and (BiCl2)[W6Cl13]

The compound (BiCl)[W₆Cl₁₄] was previously characterized as a product of the reduction of tungsten hexachloride with elemental bismuth. Another modification of BiW₆Cl₁₅ is now presented as (BiCl₂)[W₆Cl₁₃], based on the results of an X‐ray single crystal structure determination (space group P2₁/c, a = 1354.3(2) pm, b = 1234.4(2) pm, c = 1538.9(2) pm, and β = 118.76(1) °). The structure of (BiCl₂)[W₆Cl₁₃] contains chains of [(W₆Cl₈ⁱ)Cl₄^aCl_2/2^a–a]^– clusters bridged by chlorine atoms. The (BiCl₂)⁺ counterion exhibits two short Bi–Cl distances of 244.1(4) and 245.9(3) pm, respectively.     

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.     

Das Addukt von BiCl3 mit Mo6Cl12: [BiCl]-Hanteln in der Struktur von [BiCl][Mo6Cl14]

The Adduct of BiCl₃ and Mo₆Cl₁₂: [BiCl] Dumbbells in the Structure of [BiCl][Mo₆Cl₁₄] MoCl₃ reacts under decomposition to MoCl₂ and Cl₂ with BiCl₃ in a sealed evacuated glass ampoule at 550 °C to form light red crystals of [BiCl][Mo₆Cl₁₄]. The crystal structure determination (monoclinic, C 2/c, a = 1268.1(4) pm, b = 1304.6(3) pm, c = 2571.9(8) pm, β = 91.79(3)°, Z = 8) shows that the structure is built of [(Mo₆Cl₈)Cl₆] units containing nearly regular octahedral Mo₆ clusters. These units are arranged in the motiv of a cubic closest packing. The octahedral interstices contain [BiCl] dumbbells with a Bi–Cl bond length of 249 pm. The coordination sphere of the Bi atom is completed by six weaker Bi–Cl-contacts of 275 to 308 pm length to a distorted monocapped trigonal prism. Neglecting the secondary Bi–Cl bonds, the title compound can be formulated as [(BiCl)²⁺][(Mo₆Cl₁₄)^2–].