Symmetrieverwandtschaften bei Varianten des ReO3‐Typs

Symmetry Relationships among Derivatives of the ReO₃ Type The relationships among the derivatives of the ReO₃ structure type have been rationalized with a genealogical tree of group‐subgroup relations between the corresponding space groups. The symmetry reductions from the space group Pm3¯m of the ReO₃ type result from tilting or distortions of the coordination octahedra, and also when there is an ordered substitution of the Re position by atoms of several elements. One branch of the genealogical tree contains different modifications of WO₃. Another branch contains skutterudite (CoAs₃) and several hydroxides like In(OH)₃ or CaSn(OH)₆; in these the octahedra tilting is such that square As or (OH^—)₄ units result. Somewhat different tiltings have been found among CuSn(OH)₆ and NaSb(OH)₆. A third branch comprehends cubic and rhombohedral structures like NaSbF₆, VF₃ and LiSbF₆ and their derivatives. The rhombohedral structures have octahedra that have been rotated about a threefold rotation axis; in addition, different distortions occur. The genealogical tree shows between which structure types second order phase transitions may be considered and what kinds of twinned crystals can possibly be expected.     

Die Kristallstrukturen von PPh4[MCl5(NCMe)] · MeCN (M = Ti,Zr), zwei Modifikationen von PPh4[TiCl5(NCMe)] und von cis‐TiCl4(NCMe)2 · MeCN

The Crystal Structures of PPh₄[MCl₅(NCMe)] · MeCN (M = Ti, Zr), two Modifications of PPh₄[TiCl₅(NCMe)] and of cis ‐TiCl₄(NCMe)₂ · MeCN The title compounds were obtained by reactions of TiCl₄ or ZrCl₄, respectively, with PPh₄Cl and acetonitrile in the presence of S₂Cl₂. PPh₄[TiCl₅(NCMe)] · MeCN is unstable and emanates the incorporated acetonitrile. PPh₄[TiCl₅(NCMe)] forms the two modifications aP114 and mP228, the latter being more stable. The crystal structures were determined by X‐ray diffraction. Triclinic PPh₄[TiCl₅(NCMe)]‐(aP114) crystallizes in a distorted variety at the tetragonal AsPh₄[RuNCl₄] type, i. e. with PPh₄⁺ ions that are piled to columns in the c direction; the [TiCl₅(NCMe)]^– ions are tilted vs. this direction and thus cause the symmetry reduction from P4/n to P1. PPh₄[TiCl₅(NCMe)] · MeCN and PPh₄[ZrCl₅(NCMe)] · MeCN also have the same packing principle as in AsPh₄[RuNCl₄] with a symmetry reduction from P4/n to P112₁/n and a doubled c axis. Instead, PPh₄[TiCl₅(NCMe)]‐(mP228) has a packing with (PPh₄⁺)₂ pairs. Orthorhombic TiCl₄(NCMe)₂ · MeCN contains molecules having two acetonitrile ligands attached to the Ti atom in a cis configuration.     

Die Kristallpackung von (PPh4)2[NiCl4] · 2 MeCN und PPh4[CoCl0,6Br2,4(NCMe)]

The Crystal Packings of (PPh₄)₂[NiCl₄] · 2 MeCN and PPh₄[CoCl_0.6Br_2.4(NCMe)] (PPh₄)₂[NiCl₄] · 2 MeCN was obtained from the reaction of PPh₄Cl and NiCl₂ in acetonitrile in the presence of S₂Cl₂, PPh₄[Cl₂H] being a side product. The product of the reaction of CoS₂ with S₂Br₂ (containing rests of S₂Cl₂) at 400 °C was treated with PPh₄Br in acetonitrile yielding PPh₄Br₃ and PPh₄[CoCl_0.6Br_2.4(NCMe)]. The crystal structures of the title compounds were determined by X‐ray diffraction. (PPh₄)₂[NiCl₄] · 2 MeCN (space group I 4, a = 1839.3 pm, c = 1375.3 pm) has a crystal packing derived from the BiPh₄[ClO₄] structure type with a fourfold increased unit cell and one half of the ClO₄^– positions substituted by pairsof acetonitrile molecules. The crystal structure of PPh₄[CoCl_0.6Br_2.4(NCMe)] (space group I4₁/a, a = 1804.7 pm, c = 3198.8 pm) is related to the AsPh₄[RuNCl₄] type with an eightfold increased unit cell. The [CoCl_0.6Br_2.4(NCMe)]^– ions are disordered in two orientations and some halogen positions are randomly occupied by Cl and Br atoms. Family trees of group–subgroup relations show the symmetry relations.     

Synthese und Kristallstruktur der Rhenium(VII)‐Nitridchloride ReNCl4 und ReNCl4·H2O

Syntheses and Crystal Structures of the Rhenium(VII) Nitride Chlorides ReNCl₄ and ReNCl₄·H₂O Rhenium(VII) nitride chloride, ReNCl₄ ( 1 ) is obtained in form of brown needles with metallic luster by the reaction of ReCl₅ with Cl₃VNCl at 140 °C under vacuum in a sealed glass ampoule. It crystallizes in the tetragonal space group I4 with the lattice parameters a = 826.7(4), c = 405.1(2) pm, and Z = 2. The square pyramidal molecules are connected by asymmetric nitrido bridges to form chains along the crystallographic c axis. The shorter Re‐N distance of 163.0(5) pm corresponds to a triple bond, while the pronounced longer distance of 242.0(5) pm can be interpreted with a weak donor bond. The reaction of ReCl₅ with VN at 170 °C under vacuum in a sealed glass ampoule yields red needles of ReNCl₄·H₂O ( 2 ). It crystallizes in the orthorhombic space group Pnma with a = 1075.4(2), b = 1108.5(2), c = 547.7(5) pm and Z = 4. The Re atoms exhibit a distorted octahedral coordination with the aqua ligand in trans position to the nitrido ligand. The Re‐N triple bond has a bond distance of 166.1(11) pm. The complexes are connected by hydrogen bridges O‐H···N to form chains.     

Überschreitungen der konventionellen Zahl von Clusterelektronen in Metallhalogeniden des M6X12‐Typs: W6Cl18, (Me4N)2[W6Cl18] und Cs2[W6Cl18]

Beyond the Conventional Number of Electrons in M₆X₁₂ Type Metal Halide Clusters: W₆Cl₁₈, (Me₄N)₂[W₆Cl₁₈], and Cs₂[W₆Cl₁₈] Black octahedral single crystals of W₆Cl₁₈ were obtained by reducing WCl₄ with graphite in a silica tube at 600 °C. The single crystal structure refinement (space group R 3¯, Z = 3, a = b = 1498.9(1) pm, c = 845.47(5) pm) yielded the W₆Cl₁₈ structure, already reported on the basis of X‐ray powder data. (Me₄N)₂[W₆Cl₁₈] and Cs₂[W₆Cl₁₈] were obtained from methanolic solutions of W₆Cl₁₈ with Me₄NCl and CsCl, respectively. The structure of (Me₄N)₂[W₆Cl₁₈] was refined from X‐ray single crystal data (space group P 3¯m1, Z = 1, a = b = 1079.3(1) pm, c = 857.81(7) pm), and the structure of Cs₂[W₆Cl₁₈] was refined from X‐ray powder data (space group P 3¯, Z = 1, a = b = 932.10(7) pm, c = 853.02(6) pm). The crystal structure of W₆Cl₁₈ contains molecular W₆Cl₁₈ units arranged as in a cubic closest packing. The structures of (Me₄N)₂[W₆Cl₁₈] and Cs₂[W₆Cl₁₈] can be considered as derivatives of the W₆Cl₁₈ structure in which 2/3 of the W₆Cl₁₈ molecules are substituted by Me₄N⁺ ions and Cs⁺ ions, respectively. The conventional number of 16 electrons/cluster is exceeded in these compounds, with 18 electrons for W₆Cl₁₈ and 20 electrons for (Me₄N)₂[W₆Cl₁₈] and Cs₂[W₆Cl₁₈]. Cs₂[W₆Cl₁₈] exhibits temperature independent paramagnetic behaviour.     

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.     

Neue Polyiodide des Caesiums mit Doppel‐ und Tripeldecker‐Kationen, [Cs(Benzo‐18‐Krone‐6)2]Ix und [Cs2(Benzo‐18‐Krone‐6)3](Ix)2 (x = 3, 5)

New Polyiodides of Cesium containing Double and Triple Decker Cations, [Cs(benzo‐18‐crown‐6)₂]I_x and [Cs₂(benzo‐18‐crown‐6)₃](I_x)₂ (x = 3, 5) [Cs(b18c6)₂]I_x (x = 3 (1) , 5 (3) ) and [Cs₂(b18c6)₃](I_x)₂ (x = 3 (2) , 5 (4) ) (b18c6 = benzo‐18‐crown‐6) have been synthesized by the reaction of benzo‐18‐crown‐6 (C₁₆H₂₄O₆), cesium iodide (CsI) and iodine (I₂) in acetonitrile ( 1 ), ethanol/dichloromethane ( 2 , 4 ) and 2‐methoxyethanol ( 3 ). Their crystal structures were determined on the basis of single crystal X‐ray data {( 1 ): monoclinic, C2/c, Z = 4, a = 2048.8(5), b = 1329.5(5), c = 1588.7(5) pm, β = 110.23(1)°; ( 2 ): monoclinic, C2/c, Z = 4, a = 2296.0(1), b = 2092.7(1), c = 1373.6(1) pm, β = 100.21(1)°; ( 3 ): monoclinic, P2₁/n, Z = 4, a = 1586.3(1), b = 1745.5(1), c = 1608.6(1) pm, β = 92.37(1)°; ( 4 ): triclinic, , Z = 2, a = 1241.7(1), b = 1539.8(2), c = 1938.4(2) pm, α = 91.15(1), β = 100.53(1), γ = 95.26(1)°}. As expected, double decker cations centered by Cs atoms, [Cs(b18c6)₂]⁺, are found in the structures of ( 1 ) and ( 3 ). In contrast, the triple decker cation found in ( 2 ) and ( 4 ) is less common. The triiodide anions of ( 1 ) and ( 2 ) can be regarded as normal and the chain‐type pentaiodide anions of ( 3 ) and ( 4 ) fall into the known systematic sequence of these anions. The differences in the connectivity of the crystallographically independent I₅^? anions in ( 4 ) are surprising with respect to the fact that, so far, independent pentaiodide anions do not show variations in their scheme of connectivity within one crystal structure.     

Die Kristallstrukturen der Azido‐Platinate (AsPh4)2[Pt(N3)4] und (AsPh4)2[Pt(N3)6]

Crystal Structures of the Azido Platinates (AsPh₄)₂[Pt(N₃)₄] and (AsPh₄)₂[Pt(N₃)₆] The crystal structures of the two homoleptic azido platinates (AsPh₄)₂[Pt(N₃)₄] ( 1 ) and (AsPh₄)₂[Pt(N₃)₆] ( 2 ) were determined by X‐ray diffraction at single crystals. In 1 the [Pt(N₃)₄]^2– ions are without crystallographic site‐symmetry, and the platinum atoms show a planar surrounding. The [Pt(N₃)₆]^2– ions in 2 are centrosymmetric (C_i) with an octahedral surrounding at the platinum atoms. While 1 is highly explosive, 2 is of significantly greater stability. This behaviour is explained by the packing conditions. 1 : Space group P2₁/n, Z = 6, lattice dimensions at –80 °C: a = 1045.3(1), b = 1620.2(1), c = 4041.0(3) pm; β = 96.70(1)°; R₁ = 0.0654. 2 : Space group P1, Z = 1, lattice dimenstions at –80 °C: a = 1027.6(1), b = 1049.1(2), c = 1249.9(3) pm; α = 88.27(1)°, β = 74.13(1)°, γ = 67.90(1)°; R₁ = 0.0417.     

Li2Sr4Al2Ta2N8O,a Nitridoalumotantalate with BCT‐Zeolite Type Structure

Li₂Sr₄Al₂Ta₂N₈O was synthesized from Li₃AlN₂, Sr(NH₂)₂, LiN₃, and lithium metal as fluxing agent in weld shut tantalum crucibles. Single crystals were obtained as byproduct from reaction with the ampoule material. The crystal structure (P2₁/n (no. 14), a = 9.4081(19), b = 10.012(2), c = 5.9832(12) Å, β = 93.44(3)°, Z = 2) was solved on the basis of single‐crystal X‐ray diffraction data. Li₂Sr₄Al₂Ta₂N₈O is built up of vertex sharing AlN₄ and TaN₄ tetrahedra, forming a BCT‐zeolite type structure with Sr²⁺ ions and molecular Li₂O units incorporated into the voids. Lattice energy calculations (MAPLE) confirmed the electrostatic bonding interactions and the chemical composition.     

Metallkomplexe mit N2O2S2‐Koordinationssphäre. Synthese und Charakterisierung der Cobalt(II)‐, Nickel(II)‐ und Kupfer(II)‐Komplexe eines 15‐ und eines 16‐gliedrigen N,N′‐bis(2‐hydroxyethyl)‐funktionalisierten makrocyclischen Liganden

Metal Complexes with N₂O₂S₂ Donor Set. Synthesis and Characterization of the Cobalt(II), Nickel(II), and Copper(II) Complexes of a 15‐ and a 16‐Membered Bis(2‐hydroxyethyl) Pendant Macrocyclic Ligand The macrocyclic ligands 6, 10‐bis(2‐hydroxyethyl)‐7, 8, 9, 11, 17, 18‐hexahydro‐dibenzo‐[e, n][1, 4, 8, 12]‐dithiadiaza‐cyclopentadecine ( 1 ) (L¹) and 5, 13‐bis(2‐hydroxyethyl)‐7, 8, 9, 10, 16, 17, 18, 19, 20‐nonahydro‐dibenzo‐[g, o][1, 9, 5, 13]‐dithiadiaza‐cyclohexadecine (L⁴) have been prepared. They form the stable complexes [CoL¹(‐H)CoL¹](ClO₄)₃ ( 2 ), [NiL¹](ClO₄)₂·MeOH ( 3 ), Λ‐[CuL¹](ClO₄)₂·MeOH ( 4a ) and rac‐[CuL¹](ClO₄)₂·MeOH ( 4b ), [NiL⁴](ClO₄)₂ ( 5 ), and [CuL⁴](ClO₄)₂ ( 6 ). The compounds 1 to 6 have been characterized by standard methods and single‐crystal X‐ray diffraction. In the complexes 2 to 6 the metal atoms are octahedrally coordinated by the N₂O₂S₂ donor set of the ligands. L¹ and L⁴ are folded herein along the N···M···S‐ and the N···M···N′‐axes, respectively. This results at the metal atom in a all‐cis‐configuration for the complexes of L¹ and a trans‐N₂‐cis‐O₂‐cis‐S₂‐configuration for the complexes of L⁴. The cobalt(II) complex 2 is a dimer, bridged by a rather short hydrogen bridge of 2.402(12)Å length. The copper(II) complexes of L¹ and L⁴ differ with respect to the Jahn‐Teller‐distortion.     

Monomere und polymere Dimethylaminothioquadratato‐Komplexe: Die Kristallstrukturen von Nickel(II)‐, Cobalt(II)‐, Silber(I)‐, Platin(II)‐, Gold(I)‐, Quecksilber(II)‐ und Blei(II)‐Dimethylaminothioquadrataten

Monomeric and Polymeric Dimethylaminothiosquarato Complexes: The Crystal Structures of Nickel(II), Cobalt(II), Silver(I), Platinum(II), Gold(I), Mercury(II) and Lead(II) Dimethylaminothiosquarates The ligand 2‐dimethylamino‐3, 4‐dioxo‐cyclobut‐1‐en‐thiolate, Me₂N‐C₄O₂S⁻ (L) forms neutral and anionic complexes with nickel(II), cobalt(II)‐, silver(I)‐, platinum(II)‐, gold(I)‐, mercury(II)‐ and lead(II). According to the crystal structures of seven complexes the ligand is O, S‐chelating in [Ni(L)₂(H₂O)₂]·2 H₂O, [Co(L)₂(CH₃OH)₂] and (with limitations) in [Pb(L)₂·DMF]. In the remaining compounds the ligand behaves essentially as a thiolate ligand. The platinum, gold and mercury complexes [TMA]₂[Pt(L)₄], [TMA] [Au(L)₂] and [Hg(L)₂] are monomeric. In [TMA][Ag₂(L)₃]·5.5 H₂O a chain‐like structure was found. In the asymmetric unit of this structure eight silver ions, with mutual distances in the range 2.8949(4) to 3.1660(3)Å, are coordinated by twelve thiosquarato ligands. [Pb(L)₂·DMF] has also a polymeric structure. It contains a core of edge‐bridged, irregular PbS₄ polyhedra. TMA[Au(H₂NC₄O₂S)₂] has also been prepared and its structure elucidated.     

Zinkkomplexe des N,N,S‐Liganden 2‐Mercaptobenzyl‐bis‐(2‐pyridylmethyl)amin

Zinc Complexes of the N,N,S‐Ligand 2‐Mercaptobenzyl‐bis‐(2‐pyridylmethyl)amine An improved synthesis of the title ligand MBPA–H has made its complex chemistry accessible. With diethyl zinc it forms the reactive ethyl complex (MBPA)Zn–C₂H₅ ( 1 ) whose reaction with phenol leads to (MBPA)Zn–OC₆H₅ ( 2 ). With zinc nitrate the labile compound (MBPA)Zn–ONO₂ ( 3 ) is formed which in turn is converted with thiophenolate into (MBPA)Zn–SC₆H₅ ( 4 ). Structure determinations of 2 and 3 have confirmed severely deformed trigonal‐bipyramidal coordinations of the zinc atom whose ligation patterns correspond to those in some hydrolytic zinc enzymes.     

Die Kristallstrukturen von trans‐[NiBr2(Pyridin)4] und [Ni(HNPEt3)4]I2

Crystal Structures of trans ‐[NiBr₂(pyridine)₄] and [Ni(HNPEt₃)₄]I₂ Turquoise single crystals of trans‐[NiBr₂(pyridine)₄] have been obtained by the reaction of excess pyridine with nickel(II) bromide/diacetonealcohol. According to the crystal structure determination the nickel atom is octahedrally coordinated by the two bromine atoms in trans‐position and by the nitrogen atoms of the pyridine molecules. Space group Pna2₁, Z = 4, lattice dimensions at 20 °C: a = 1592.9(2), b = 943.8(1), c = 1413.0(2) pm, R₁ = 0.0492. Dark blue single crystals of the phosphoraneimine complex [Ni(HNPEt₃)₄]I₂ have been obtained from NiI₂/H₂O with excess Me₃SiNPEt₃ and subsequent recrystallization from acetonitrile. According to the crystal structure determination the nickel atom is tetrahedrally coordinated by the nitrogen atoms of the HNPEt₃ molecules. The iodide ions are connected via N–H…I contacts with the cation to form an ion triple. Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1934.9(2), b = 1078.3(1), c = 1966.3(2) pm, β = 111.040(8)°; R₁ = 0.043.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalysen der Tetrahalogeno‐bis‐Pyridin‐Osmium(III)‐Komplexe cis‐(n‐Bu4N)[OsCl4Py2] und trans‐(n‐Bu4N)[OsX4Py2], X = Cl,Br

Synthesis, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analyses of the Tetrahalogeno‐bis‐Pyridine‐Osmium(III) Complexes cis ‐( n ‐Bu₄N)[OsCl₄Py₂] and trans ‐( n ‐Bu₄N)[OsX₄Py₂], X = Cl, Br By reaction of (n‐Bu₄N)₂[OsX₆], X = Cl, Br, with pyridine and (n‐Bu₄N)[BH₄] tetrahalogeno‐bis‐pyridine‐osmium(III) complexes are formed and purified by chromatography. X‐ray structure determinations on single crystals have been performed of cis‐(n‐Bu₄N)[OsCl₄Py₂] ( 1 ) (triclinic, space group P1, a = 9.4047(9), b = 10.8424(18), c = 17.007(2) Å, α = 71.833(2), β = 81.249(10), γ = 67.209(12)°, Z = 2), trans‐(n‐Bu₄N)[OsCl₄Py₂] ( 2 ) (orthorhombic, space group P2₁2₁2₁, a = 8.7709(12), b = 20.551(4), c = 17.174(4) Å, Z = 4) and trans‐(n‐Bu₄N)[OsBr₄Py₂] ( 3 ) (triclinic, space group P1, a = 9.132(3), b = 12.053(3), c = 15.398(2) Å, α = 95.551(18), β = 94.12(2), γ = 106.529(19)°, Z = 2). Based on the molecular parameters of the X‐ray structure determinations and assuming C₂ point symmetry for the anion of 1 and D_2h point symmetry for the anions of 2 and 3 the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants of 1 are in the Cl–Os–Cl axis f_d(OsCl) = 1.58, in the asymmetrically coordinated N′–Os–Cl ^· axes f_d(OsCl ^· ) = 1.45, f_d(OsN′) = 2.48, of 2 f_d(OsCl) = 1.62, f_d(OsN) = 2.42 and of 3 f_d(OsBr) = 1.39 and f_d(OsN) = 2.34 mdyn/Å.     

[{(CH3)3Si}3C–Li–C{Si(CH3)3}3][Li · 3(OC4H8)] und {(CH3)3Si}3C–Li · O=C(Si(CH3)3)2, zwei neue Addukte des Lithium‐trisylmethanids

[{(CH₃)₃Si}₃C–Li–C{Si(CH₃)₃}₃][Li · 3(OC₄H₈)] and {(CH₃)₃Si}₃C–Li · O=C(Si(CH₃)₃)₂, two New Adducts of Lithium Trisylmethanide Sublimation of (Tsi–Li) · 2 THF (Tsi = –C(Si(CH₃)₃)₃) at 180 °C and 10^–4 hPa gives (Tsi–Li) · 1.5 THF in very low yield. The X‐ray structure determination shows an almost linear [Tsi–Li–Tsi]^– anion connected by short agostic Li…C contacts with the threefold THF‐coordinated Li‐cation. Base‐free Tsi–Li, solved in toluene is decomposed by oxygen, forming the strawberry‐colored ketone O=C(SiMe₃)₂, which forms an 1 : 1 adduct with undecomposed Tsi–Li. The X‐ray structure elucidation of this compound is also discussed.     

Molybdän‐ und Wolfram‐Komplexe mit MNS‐Sequenzen. Die Kristallstrukturen von [MoCl3(N3S2)(1,4‐Dioxan)2] und [Mo2Cl2(μ‐NSN)2(μ‐O)(NCMe3)(OCMe3)2]2

Molybdenum and Tungsten Complexes with MNS Sequences. Crystal Structures of [MoCl₃(N₃S₂)(1,4‐dioxane)₂] and [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ The cyclo‐thiazeno complexes [Cl₃MNSNSN]₂ of molybdenum and tungsten react with 1,4‐dioxane in dichloromethane suspension to give the binuclear donor‐acceptor complexes [μ‐(1,4‐dioxane){MCl₃(N₃S₂)}₂] which are characterized by IR spectroscopy. With excess 1,4‐dioxane the molybdenum compound forms the complex [MoCl₃(N₃S₂)(1,4‐dioxane)₂] in which, according to the crystal structure determination, one of the dioxane molecules coordinates at the molybdenum atom, the other one at one of the sulfur atoms of the cyclo‐thiazeno ring. The μ‐(NSN^2–) complex [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ has been obtained by the reaction of [MoN(OCMe₃)₃] with trithiazyle chloride in carbontetrachloride solution. According to the crystal structure determination this compound forms centrosymmetric dimeric molecules via two of the nitrogen atoms of two of the μ‐(NSN) groups to give a Mo₂N₂ fourmembered ring. [MoCl₃(N₃S₂)(1,4‐dioxane)₂]: Space group P2₁/c, Z = 4, lattice dimensions at –70 °C: a = 1522.9(2); b = 990.3(1); c = 1161.7(1) pm; β = 106.31(1)°, R₁ = 0.0317. [Mo₂Cl₂(μ‐NSN)₂(μ‐O)(NCMe₃)(OCMe₃)₂]₂ · 4 CCl₄: Space group P2₁/c, Z = 2, lattice dimensions at –83 °C: a = 1216.7(1); b = 2193.1(2); c = 1321.8(1) pm; β = 98.23(1)°; R₁ = 0.0507.     

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.     

Bildung und Strukturen von Nickelacyclen des Typs (LL′) NiCH2CH2C(O)O

Synthesis and Structures of Nickelacyclic Compounds of the Type (LL′) NiCH₂CH₂C(O)O In the title indicated type of nickelacyclic compounds could be prepared with bipy or Ph₂P(O)CH₂PPh₂ as stabilizing ligands. The complexes were characterized by means of crystal structure analyses. Additionally, both the synthesis of the methanol adduct of a nickelacyclic carboxylate and cis-(bipy)₂NiCl₂ · 2 DMF was successful as well as their structure analyses. Using the structure data including the data of formerly described nickelcycles, bond lengths and angels within the planar group (LL′)Ni(O)(C) and the mutual trans-influence of the ligands are discussed. The structure of (bipy)₂NiCl₂ · 2 DMF is discussed with respect to other compounds of the type cis-(bipy)₂M^IICl₂. In the case of the corresponding trans-isomeres, steric hindrances between the bipy-ligands are to be expected which can be equalized by a small distortion of the coordination polyhedron.     

Die Kristallstrukturen von Hexachalcogeno‐Hypodiphosphaten des Magnesiums und Zinks

Crystal Structures of Hexachalcogeno‐Hypodiphosphates of Magnesium and Zinc Five chalcogeno‐hypodiphosphates were synthesized and investigated by single crystal X‐ray methods. Mg₂P₂S₆ (C2/m; a = 6.085(1), b = 10.560(2), c = 6.835(1)Å, β = 106.97(3)°; Z = 2) crystallizes with the Fe₂P₂S₆ type structure, whereas Mg₂P₂Se₆ (a = 6.404(1), c = 20.194(4)Å) and Zn₂P₂Se₆ (a = 6.290(3), c = 19.93(2)Å) build up the Fe₂P₂Se₆ type (R3; Z = 3). The structures are characterized by closest packings of sulfur (selenium) with Mg²⁺ (Zn²⁺) ions and P₂ pairs in half the octahedra — analogous to the CdCl₂ and CdI₂ type, respectively. In Mg₂P₂S₆ half the Mg²⁺ ions can be substituted by Ag⁺ ions resulting in Ag₂MgP₂S₆ (C2/n; a = 6.364(1), b = 10.975(2), c = 13.999(3)Å, β = 108.29(3)°; Z = 4). In this compound the Ag⁺ ions are disordered and located in the octahedra originally occupied by Mg²⁺ ions. In Mg₂P₂Se₆ an analogous substitution by K⁺ ions leads to the compound K₂MgP₂Se₆ (P2₁/n; a = 6.546(1), b = 12.724(3), c = 7.599(2)Å, β = 103.02(3)°; Z = 2) with K₂FeP₂S₆ type structure. The structure is characterized by columns of alternating face‐sharing Se octahedra (centered by Mg) and trigonal antiprisms (centered by P₂ pairs) along [100]. The columns are interconnected by inserted K⁺ ions.     

Koordinationspolymere 1, 2‐Dithiooxalato‐ und 1, 2‐Dithioquadratato‐Komplexe. Synthese und Strukturen von [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H2O und [H3O][H5O2][Cu(cyclam)]3[Cu2(1, 2‐dtsq)3]2

Coordination Polymeric 1, 2‐Dithiooxalato and 1, 2‐Dithiosquarato Complexes. Syntheses and Structures of [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H2₂, and [H₃O][H₅O₂][Cu(cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ 1, 2‐Dithioxalate and 1, 2‐dithiosquarate ions have a pair of soft and hard donor centers and thus are suited for the formation of coordination polymeric complexes containing soft and hard metal ions. The structures of four compounds with building blocks containing these ligands are reported: In [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂] Barium ions and pairs of Cr(bipy)(1, 2‐dtox)₂ complexes form linear chains by the bisbidentate coordination of the dithiooxalate ligands towards Ba²⁺ and Cr³⁺. In [Ni(cyclam)(1, 2‐dtsq)]·2DMF short NÖH···O hydrogen bonds link the NiS₂N₄‐octahedra with C_2v‐symmetry to an infinite chain. In [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H₂O the 1, 2‐dithiosquarato ligand shows a rare example of S‐coordination towards manganese(II). The sulfur atoms of cis‐MnO₂S₄‐polyedra are weakly coordinated towards the axial sites of square‐planar NiN₄‐centers, thus forming a zig‐zag‐chain of Mn···Ni···Mn···Ni polyhedra. [H₃O][H₅O₂][Cu (cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ contains square planar [Cu^II(cyclam)]²⁺ ions and dinuclear [Cu^I₂(1, 2‐dtsq)₃]^4— ions. Here each copper atom is trigonally planar coordinated by S‐donor atoms of the ligands. The Cu…Cu distance is 2.861(4)Å.