Die Reaktion von SeCl4 mit Übergangsmetalltetrachloriden. Synthese und Kristallstrukturen von (SeCl3)2MCl6 mit M = Zr,Hf, Mo,Re

The Reaction of SeCl₄ with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl₃)₂MCl₆ with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl₄, HfCl₄ and MoCl₄ react with SeCl₄ in closed ampoules at temperatures of 140°C to (SeCl₃)₂MCl₆ (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl₃)₂ReCl₆ structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl^? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se⁴⁺ and M⁴⁺ in an ordered way. The MCl₆ octahedra are regular, the SeCl₆ octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl₃⁺ and MCl₆^2? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly.     

1‐Oxa‐nido‐dodecaborate [OB11H12]− from the Controlled Oxidation of the closo‐Borates [B11H11]2− and [B12H12]2−

The closo‐dodecaborate [B₁₂H₁₂]^2? is degraded at room temperature by oxygen in an acidic aqueous solution in the course of several weeks to give B(OH)₃. The degradation is induced by Ag²⁺ ions, generated from Ag⁺ by the action of H₂S₂O₈. Oxa‐nido‐dodecaborate(1?) is an intermediate anion, that can be separated from the reaction mixture as [NBzlEt₃][OB₁₁H₁₂] after five days in a yield of 18 %. The action of FeCl₃ on the closo‐undecaborate [B₁₁H₁₁]^2? in an aqueous solution gives either [B₂₂H₂₂]^2? (by fusion) or nido‐B₁₁H₁₃(OH)^? (by protonation and hydration), depending on the concentration of FeCl₃. In acetonitrile, however, [B₁₁H₁₁]^2? is transformed into [OB₁₁H₁₂]^? by Fe³⁺ and oxygen. The radical anions [B₁₂H₁₂] ^{˙ ?} and [B₁₁H₁₁] ^{˙ ?} are assumed to be the primary products of the oxidation with the one‐electron oxidants Ag²⁺ and Fe³⁺, respectively. These radical anions are subsequently transformed into [OB₁₁H₁₂]^? by oxygen. The crystal structure analysis shows that the structure of [OB₁₁H₁₂]^? is derived from the hypothetical closo‐oxaborane OB₁₂H₁₂ by removal of the B3 vertex, leaving a non‐planar pentagonal aperture with a three‐coordinate O vertex, as predicted by NMR spectra and theory.     

Sind die ‚Lehrbuch-Anionen’︁ O2−, [CO3]2− und [SO4]2− Fiktionen?

Are the ‘Textbook Anions’ O^2?, [CO₃]^2?, and [SO₄]^2? Fictitious? Experimental second electron affinities are still unknown for the title anions. It will be shown by means of quantum chemical ab initio calculations that these dianions are unstable with respect to spontaneous ionization. They all must be designated as non-existent.     

AlCl3 · 2NH3 – eine Verbindung mit der Kristallstruktur eines Tetraammindichloroaluminium-tetrachloroaluminats – [AlCl2(NH3)4]+[AlCl4]−

ACl₃ · 2NH₃ – a Compound with the Crystal Structure of a Tetraammine Dichloroaluminiumtetrachloroaluminate – [AlCl₂(NH₃)₄]⁺[AlCl₄]^? Ammoniates of aluminiumchloride AlCl₃ · xNH₃ are in discussion as starting materials for the synthesis of aluminiumnitride. Therefore the reactions of melts of monoamminealuminiumchloride with ammonia were investigated. They react at 150°C within 10 min with one mole of ammonia to the diammoniate, [AlCl₂(NH₃)₄]⁺[AlCl₄]^?. The pure compound can be obtained by sublimation at 200°C in vacuumline apparatus. X-ray structure determination on [AlCl₂(NH₃)₄]⁺[AlCl₄]^? was carried out: see “Inhaltsübersicht”.     

Darstellung und spektroskopische Eigenschaften von Di(phthalocyaninato(1−))-lanthanidpolybromid; Kristallstruktur von α-Di(phthalocyaninato)samariumpolybromid, α-[Sm(Pc)2]Br1,45 und α-Di(phthalocyaninato)samariumperchlorat, α-[Sm(Pc)2](ClO4)0,63

Synthesis and Spectroscopical Properties of Di(phthalocyaninato(1?))lanthanidepolybromide; Crystal Structure of α-Di(phthalocyaninato)samariumpolybromide, α-[Sm(Pc)₂]Br_1.45 and α-Di(phthalocyaninato)samariumperchlorate, α-[Sm(Pc)₂](ClO₄)_0.63 Bronze-coloured di(phthalocyaninato)lanthanidepolybromide, [Ln(Pc^?)₂]Br_y (Ln = La…(? Ce, Pm)…Lu; y > 1.5) is prepared by oxidation of (ⁿBu₄N)[Ln(Pc^2?)₂] with bromine in excess. The UV-VIS-NIR spectra show the typical B and Q₁ bands of the Pc^? ligand at ～ 14 kK and ～ 20 kK. For the [Ln(Pc^?)₂]⁺ cation a NIR(D) band between 9,14 kK (La) and 11,50 kK (Lu) is characteristic for dimeric cofacial Pc^? radicals. Within the row La…Lu, there is a linear relationship of the hypsochromic shift of the strong bands and the Ln^III radius. In the case of La? Nd the D band shifts successively with longer time of bromination to ～ 3 kK as a result of increasing electron delocalisation. Characteristic vibrational bands are at ～ 1350/1450 cm^?1 (IR) and ～ 560/1120/1170/1600 cm^?1 (RR). In the FT-Raman spectra the totally symmetric Ln? N stretching vibration between 141 cm^?1 (La) and 172 cm^?1 (Lu) is selectively enhanced. As shown by α-[Sm(Pc)₂]Br_1,45 and α-[Sm(Pc)₂](ClO₄)_0,63 only partially ringoxidized complexes are obtained by the anodic oxidation. Both crystallize in the tetragonal space group P4/nnc. The [Sm(Pc)₂] molecular building block contains two nearly planar staggered (～41°) Pc rings packed in columns parallel along [001] leading to the quasi-one-dimensional structure. There is a statistical disorder of the Sm^III and the ClO₄^? resp. Br^?/Br₃^? ions over two incompletely filled crystallographic positions for the cation resp. anion. This results in a partial oxidation of the Pc ligand, which in the picture of localized valence states for α-[Sm(Pc)₂](ClO₄)_0,63 corresponds to [SmPc^?Pc^2?] · 2[Sm(Pc^?)₂](ClO₄). Accepting the same valence state for [Sm(Pc)₂]Br_1,45 five positive charges are compensated by two Br^? and three Br₃^?. The spectroscopic differences of the partially and fully oxidized complexes are discussed.     

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.     

Zwei Vertreter des α-LiFeO2 Typs: LilnO2 und α-LiYbO2 [1, 2]

Two Representatives of the α-LiFeO₂ Type: LiInO₂ and α-LiYbO₂ Single crystals of LiInO₂ (well ground mixtures of ‘In₂O’: KO₂: Li₂O = 1:1.8:1, Ag-tube, 22d, 520°C); and α-LiYbO₂ (Yb₂O₃:Li₂O = 1:1.1, Ni-tube, 30d, 1150°C) were prepared for the first time from mixtures of the binary oxides. The determination of the structure confirmed the α-LiFeO₂ type. Both oxides crystallize in the space group I 4₁/amd (Z = 4); LiInO₂: a = 431.2(1) pm c = 934.2(2) pm; c/a = 2.167; 123 I_o(hkl), R = 3.6%, R_w = 2.9%. α-LiYbO₂:a = 438.7(1) pm c = 1006.7(2) pm; c/a = 2.295, 130 I_o(hkl), R = 4.4%, R_w = 3.6%. The Madelung part of lattice energy, MAPLE and characteristics of this kind of structure are discussed.     

(PPh4)[(ReO2S2)CuI] und (NEt4)2[(ReOS3)Cu3Cl4]: Fixierung der bisher nicht isolierten Ionen [ReO2S2]− und [ReOS3]− durch Ausnutzung der Stabilität der CuS2(Re)- und Cu3S3(Re)-Fragmente

(PPh₄)[(ReO₂S₂)CuI] and (NEt₄)₂[ReOS₃)Cu₃Cl₄]: Fixation of the up to now not Isolated Ions [ReO₂S₂]^? and [ReOS₃]^? Utilizing the Stability of the CuS₂(Re) and Cu₃S₃(Re) Fragments (PPh₄)[(ReO₂S₂)CuI] ( 1 ) and (NEt₄)₂[ReOS₃)Cu₃Cl₄] ( 2 ) containing the up to now not isolated oxothioperrhenate ions [ReO₂S₂]^? and [ReOS₃]^? as ligands, have been prepared by the reaction of (NEt₄)[ReS₄] with PPh₃ and CuI in acetone in the presence of (PPh₄)I (( 1 )) or with CuCl in CH₂Cl₂ in the presence of (NEt₄)Cl (( 2 )), respectively. 1 and 2 have been characterized by X-ray structure analysis, elemental analysis and spectroscopic studies (IR, UV/Vis). The electronic spectra show bands which can approximately be assigned to interesting low-energy charge-transfer-transitions of the type d(Cu) → d(Re). For crystal data see Inhaltsübersicht.     

Neue Phosphido-verbrückte Mehrkernkomplexe des Ag,Cd und Zn Die Kristallstrukturen von [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] und [M4Cl4(PPh2)4(PnPr3)2] (M = Zn,Cd)

New Phosphido-bridged Multinuclear Complexes of Ag, Cd and Zn. The Crystal Structures of [Ag₄(PPh₂)₄(PMe₃)₄], [Ag₆(PPh₂)₆(P^tBu₃)₂] and [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn, Cd) AgCl reacts with Ph₂PSiMe₃ in the presence of a tertiary Phosphine PMe₃ or P^tBu₃ to form the multinuclear complexes [Ag₄(PPh₂)₄(PMe₃)₄] ( 1 ) and [Ag₆(PPh₂)₆(P^tBu₃)₂] ( 2 ). In analogy to that MCl₂ reacts with Ph₂PSiMe₃ in the presence of PⁿPr₃ to form the two multinuclear complexes [M₄Cl₄(PPh₂)₄(PⁿPr₃)₂] (M = Zn ( 3 ), Cd ( 4 )). The structures were characterized by X-ray single crystal structure analysis ( 1 : space group Pna2₁ (Nr. 33), Z = 4, a = 1 313.8(11) pm, b = 1 511.1(6) pm, c = 4 126.0(18) pm, 2 : space group P–1 (Nr. 2), Z = 2, a = 1 559.0(4) pm, b = 1 885.9(7) pm, c = 2 112.4(8) pm, α = 104.93(3)°, β = 94.48(3)°, γ = 104.41(3)°; 3 : space group C2/c (Nr. 15), Z = 4, a = 2 228.6(6) pm, b = 1 847.6(6) pm, c = 1 827.3(6) pm, β = 110.86(2); 4 : space group C2/c (Nr. 15), Z = 4, a = 1 894.2(9) pm, b = 1 867.9(7) pm, c = 2 264.8(6) pm, β = 111.77(3)°). 3 and 4 may be considered as intermediates on the route towards polymeric [M(PPh₂)₂]_n (M = Zn, Cd).     

Synthese und Kristallstrukturen von (Ph4P)4[Bi8I28], (nBu4N)[Bi2I7] und (Et3PhN)2[Bi3I11] – Iodobismutate mit isolierten bzw. polymeren Anionen

Synthesis and Crystal Structures of (Ph₄P)₄[Bi₈I₂₈], (ⁿBu₄N)[Bi₂I₇], and (Et₃PhN)₂[Bi₃I₁₁] – Bismuth Iodo Complexes with Isolated and Polymeric Anions Solutions of BiI₃ in methanol react with NaI and (ⁿBu₄N)(PF₆) or (Et₃NPh)(PF₆) to form anionic bismuth iodo complexes (ⁿBu₄N)[Bi₂I₇] 1 and (Et₃PhN)₂[Bi₃I₁₁] 2 . In 1 Bi₄I₁₆ units, and in 2 Bi₆I₂₄ units are linked by common I-atoms to onedimensional infinite chains. Reaction of BiI₃ with (Ph₄P)(PF₆) in methanol yields (Ph₄P)₄[Bi₈I₂₈] 3 . The anions of 1–3 consist of edge-sharing BiI₆ octahedra. (ⁿBu₄N)[Bi₂I₇] 1 : Space group I2/m (No. 13), a = 1 082.3(5), b = 2 597.1(13), c = 1 206.1(6) pm, β = 93.17(2)°, V = 3 385(3) · 10⁶ pm³; (Et₃PhN)₂[Bi₃I₁₁] 2 : Space group P1 (No. 2), a = 1 283.5(6), b = 1 345.9(7), c = 1 546.3(8) pm, α = 83.87(2), β = 74.24(2), γ = 68.26(2)°, V = 2 388(2) · 10⁶ pm³; (Ph₄P)₄[Bi₈I₂₈] 3 : Space group P1 (No. 2), a = 1 329.3(4), b = 1 337.0(4), c = 2 193.1(5) pm, α = 104.20(2), β = 99.73(2), γ = 100.44(2)°, V = 3 622(2) · 10⁶ pm³.     

Kristallstruktur von Tetraphenylphosphonium-Monothiocyanatohydro-closo-Decaborat, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN

Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN The X-ray structure determination of [P(C₆H₅)₄]₂[2-(SCN)B₁₀H₉] · CH₃CN (monoclinic, space group P2₁/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°).     

Synthesis,Characterization, and Crystal Structures of [N(CH3)4]2[B12H12] and [N(CH3)4]2[B12H12] · CH3CN

Bis(tetramethylammonium) dodecahydrododecaborate, [(CH₃)₄N]₂[B₁₂H₁₂], and bis(tetramethylammonium) dodecahydrododecaborate acetonitrile, [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN, were synthesized and characterized via Infrared, ¹H and ¹¹B NMR spectroscopy. [(CH₃)₄N]₂[B₁₂H₁₂] crystallizes isopunctual to the alkali metal dodecaborates. The crystal structure of [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN was determined from single crystal data and refined in the orthorhombic crystal system (Pcmn, no. 62, a = 898.68(8), b = 1312.85(9) c = 1994.5(1) pm, R(|F| , 4σ) = 5.9%, wR(F²) = 18.3%). Here, the geometry of the dodecaborate anion is that of an almost ideal icosahedron, less distorted than most other dodecaborates known. By low‐temperature Guinier‐Simon diffractometry phase transitions were detected for [(CH₃)₄N]₂[B₁₂H₁₂] and [(CH₃)₄N]₂[B₁₂H₁₂] · CH₃CN at –70 and –15 °C, respectively.     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Bi53+‐Polykationen in geordneten und plastischen Kristallen von Bi5[AlI4]3 und Bi5[AlBr4]3

Bi₅³⁺ Polycations in Ordered and Plastic Crystals of Bi₅[AlI₄]₃ and Bi₅[AlBr₄]₃ Dark‐red air‐sensitive crystals of pentabismuth‐tris(tetrabromoaluminate) Bi₅[AlBr₄]₃ and black crystals of Bi₅[AlI₄]₃ have been crystallized from melts of Bi, BiX₃ and AlX₃ (X = Br, I). X‐ray diffraction on a single crystal of Bi₅[AlI₄]₃ (T = 293(2) K; space group Pnma; a = 2143.6(3) pm, b = 1889.1(1) pm, c = 811.74(5) pm) revealed an ordered packing of Bi₅³⁺ trigonal bipyramids and [AlI₄]^? tetrahedra that corresponds to the PuBr₃ structure type. Contrary to the so far known Bi₅³⁺ polycations with accurate D_3h symmetry, the bismuth cluster found in Bi₅[AlI₄]₃ holds only C_s symmetry. The room temperature structure of the tetrabromoaluminate Bi₅[AlBr₄]₃, which is related to the AuCu₃ type, shows a dynamic disorder of the Bi₅³⁺ polycations (T = 293(2) K; space group ; a = 1766.2(3) pm). Slight cooling induces the transition into an ordered rhombohedral phase isostructural to Bi₅[AlCl₄]₃ (T = 260(2) K; space group a = 1241.5(8) pm, c = 3041(2) pm).     

Reaktionen von [B12H12–n(OH)n]2–, n = 1, 2 mit Säuredichloriden und Kristallstruktur von Cs2[1,2-B12H10(ox)] · CH3OH

Reactions of [B₁₂H_12–n(OH)_n]^2–, n = 1, 2 with Acid Dichlorides and Crystal Structure of Cs₂[1,2-B₁₂H₁₀(ox)] · CH₃OH By treatment of [B₁₂H₁₁(OH)]^2– with organic and inorganic acid dichlorides in acetonitrile the bridged dicluster compounds [B₁₂H₁₁(ox)B₁₂H₁₁)]^4– ( 1 ), [B₁₂H₁₁(p-OOCC₆H₄COO)B₁₂H₁₁]^4– ( 2 ), [B₁₂H₁₁(m-OOCC₆H₄COO)B₁₂H₁₁]^4– ( 3 ), [B₁₂H₁₁(SO₃)B₁₂H₁₁]^4– ( 4 ), [B₁₂H₁₁(SO₄)B₁₂H₁₁]^4– ( 5 ) are obtained in good yields. The dihydroxododecaborates [1,2-B₁₂H₁₀(OH)₂]^2– and [1,7-B₁₂H₁₀(OH)₂]^2– afford clusters with an anellated ring: [1,2-B₁₂H₁₀(ox)]^2– ( 6 ), [1,2-B₁₂H₁₀(SO₄)]^2– ( 7 ) and [1,7-B₁₂H₁₀(OOC(CH₂)₈COO)]^2– ( 8 ). Isomerically pure [1,7-B₁₂H₁₀(OH)₂]^2– ( 9 ) is formed by reaction of (H₃O)₂[B₁₂H₁₂] with ethylene glycol. All new compounds are characterized by vibrational, ¹¹B, ¹³C and ¹H NMR spectra. The crystal structure of Cs₂[1,2-B₁₂H₁₀(ox)] · CH₃OH (monoclinic, space group P 2₁/c, a = 9.616(2), b = 10.817(1), c = 15.875(6) Å, β = 95.84(8)°, Z = 4) reveals a distortion of the B₁₂ icosahedron caused by the anellated six-membered heteroring.     

AlCl3 · 3NH3 — eine Verbindung mit der Kristallstruktur eines Tetraammindichloroaluminium-diammintetrachloroaluminats: [AlCl2(NH3)4]+[AlCl4(NH3)2]−

AlCl₃ · 3NH₃ — a Compound with the Crystal Structure of a Tetraammine Dichloro Aluminium-Diammine Tetrachloro Aluminate: [AlCl₂(NH₃)₄]⁺[AlCl₄(NH₃)₂]^? . AlCl₃ · 3 NH₃ ? [AlCl₂(NH₃)₄]⁺ [AlCl₄(NH₃)₂]^? forms during the reaction of two mole NH₃ with AlCl₃(NH₃) at T ≥ 200°C. Repeated heating and cooling within 48 h between 200°C and 250°C gives a homogeneous product with total uptake of the necessary amount of NH₃. Slow sublimation in a vacuum line apparatus at 200°C gives crystals of the triammoniate sufficient for a X-ray structure determination: The compound contains elongated [AlCl₂(NH₃)₄]⁺ octahedra and compressed [AlCl₄(NH₃)₂]^? octahedra. Besides ionic bonding hydrogen bridge bonds with 3.369 Å ? d(N—H … Cl) ? 3.589 Å stabilize the atomic arrangement.     

Tellur-Polykationen stabilisiert durch Nioboxidhalogenide: Synthese und Kristallstrukturen von Te7NbOBr5 und Te7NbOCl5

Tellurium Cations stabilized by Niobium Oxytrihalides: Synthesis and Crystal Structure of Te₇NbOBr₅ and Te₇NbOCl₅ The reaction of Te₂Br with NbOBr₃ in a sealed evacuated glass ampoule at 225°C yields Te₇NbOBr₅ in form of bright black needles. Te₇NbOCl₅ is obtained from tellurium, TeCl₄ and NbOCl₃ at 220°C. Both compounds crystallize orthorhombic in the space group Pcca (Te₇NbOBr₅: a = 2 651,9(4) pm, b = 836.6(1) pm, c = 794.6(1) pm; Te₇NbOCl₅: a = 2 597.7(5) pm, b = 805.1(1) pm, c = 791.2(1) pm). The crystal structure determinations show that Te₇NbOBr₅ and Te₇NbOCl₅ are built of one-dimensional polymeric tellurium cations, one-dimensional associated pyramidal NbOX₄ groups (X = Cl, Br) and isolated halide anions. Magnetic properties of Te₇NbOX₅ were determined and confirm the expected diamagnetism. Te₇NbOX₅ can thus be formulated as [Te₇²⁺] [NbOX₄^?] (X^?). The charge distribution in the structure type Te₇MOX₅ (M = W, Nb; X = Cl, Br) became clear by synthesis and characterisation of the two niobium containing compounds.     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

Synthese,Struktur und Phasenumwandlung von Se4(MoOCl4)2

Synthesis, Crystal Structure, and Phase Transition of Se₄(MoOCl₄)₂ Dark green, very air sensitive crystals of Se₄(MoOCl₄)₂ are formed from selenium and MoOCl₄ at 190°C in a sealed, evacuated glass ampoule in quantitative yield. The structure is built of nearly square planar Se₄²⁺ ions and centrosymmetric dimeric MoOCl₄^? ions which are linked by bridging Cl atoms. At ?21°C Se₄(MoOCl₄)₂ undergoes a reversible solid state phase transition of first order. Structure determinations at ?70°C and 23°C show that during the phase transition the structures of the ions remain unchanged, while the orientations of the ions with respect to each other change in such a way that in the low temperature form the Se₄²⁺ ions obtain a higher coordination number by Cl and O atoms of neighboring MoOCl₄^? ions.     

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.