Metall-Schwefelstickstoff-Verbindungen. 13. Die Reaktion von [Ni(HN2S2)2] mit Basen Salze mit den Anionen [Ni(HN2S2)(N2S2)]− und [Ni(N2S2)2]2−

Metal Sulfur Nitrogen Compounds. 13. Reaction of [Ni(HN₂S₂)₂] with Bases. Salts with the Anions [Ni(HN₂S₂)(N₂S₂)]^? and [Ni(N₂S₂)₂]^2? Whereas the complex [Ni(HN₂S₂)₂] reacts with alcoholic solutions of alkaline hydroxides by double deprotonation to the anion [Ni(N₂S₂)₂]^2?, only one proton is removed by the reaction with strong organic bases like tetraalkylammonium, tetraphenylphosphonium, and tetrphenylarsonium hydroxides. The corresponding salts with the anion [Ni(HN₂S₂)(N₂S₂)]^? are formed. The salts containing the tetramethylammonium, tetraethylammonium, tetra-n-butylammonium and tetraphenylarsonium cations were isolated as rather stable, crystalline solids. The structure of the tetraphenylarsonium salt [Ph₄As][Ni(HN₂S₂)(N₂S₂)] was determined by X-ray structure analysis.     

Synthesis and spectroscopic characterization of bis(N-alkyldithiocarbamato)nickel(II) complexes: crystal structures of [Ni(S2CNH(n-Pr))2] and [Ni(S2CNH(i-Pr))2]

Bis(N-alkyldithiocarbamato)nickel(II) complexes (1–5) [Ni(S₂CNHR)₂] (where R?=?Me, Et, n-Pr, i-Pr, n-Bu) were synthesized by the reaction of NiCl₂?·?6H₂O and the corresponding sodium salt of N-alkyldithiocarbamate in 1?:?2 molar ratio in aqueous medium. These bis(N-alkyldithiocarbamato)nickel(II) complexes (1–5) were characterized by elemental analysis, UV-Visible, IR, and ¹H/¹³C-NMR spectroscopy. The crystallographic investigation of [Ni(S₂CNH(n-Pr))₂] (3) and [Ni(S₂CNH(i-Pr))₂] (4) revealed distorted square-planar geometry around nickel(II). The dithiocarbamates have anisobidentate coordination with nickel and the dithiocarbamates are trans.     

Crystallographic report: Diazido[bis(2‐pyridyl)amine]zinc(II) hydrate, [Zn(C10H9N3)2(N3)2]·H2O

In mononuclear [Zn(C₁₀H₉N₃)₂(N₃)₂]·H₂O, the zinc atom has an approximate octahedral geometry, coordinated with four pyridyl nitrogen atoms derived from two bis(2‐pyridyl)amine molecules and two terminal nitrogen donors of the azide anions. Hydrogen‐bonding interactions extend this structure to form a double‐layer architecture. Copyright © 2004 John Wiley & Sons, Ltd.     

Bis(1,10‐phenanthroline‐N,N′)(thiosulfato‐O,S)­nickel(II)–water–methanol (1/0.92/1.4) and bis(2,2′‐bi­pyridyl‐N,N′)(thiosulfato‐O,S)nickel(II)–water–methanol (1/2/0.55)

The title compounds, [Ni(S₂O₃)­(C₁₂H₈N₂)₂]·­0.92H₂O·­1.4CH₄O and [Ni(S₂O₃)­(C₁₀H₈N₂)₂]·­2H₂O·­0.55CH₄O, are monomeric, containing nickel(II) in a distorted octahedral coordination environment provided by the four N atoms of two bidentate bipy or phen groups and one S and one O atom from a chelating thio­sulfate anion. The crystals are highly unstable outside their mother liquors and are stabilized in solution by a not fully determined number of water and methanol solvate mol­ecules. The phenanthroline structure includes two independent moieties related by a non‐crystallographic inversion center. The thio­sulfate anions display the usual S—O lengthening found when the anion acts in a bidentate mode.     

Neue Koordinations-Motive bei Cyclothiazeno-Komplexen von Molybdän und Wolfram. Die Kristallstrukturen von [{Mo(N3S2)(Cl)(OtBu)2}{Mo(O)(N3S2)(OtBu)}]2 und [W(N3S2)2(LiCl){N≡W(NPPh3)3}2]

New Coordination Motives at Cyclothiazeno Complexes of Molybdenum and Tungsten. Crystal Structures of [{Mo(N₃S₂)(Cl)(O^tBu)₂}{Mo(O)(N₃S₂)(O^tBu)}]₂ and [W(N₃S₂)₂(LiCl){N≡W(NPPh₃)₃}₂] The metalla cyclothiazeno complexes (Cyclo-1λ⁶-metalla-3,5-dithia-2,4,6-triazino complexes) [{Mo(N₃S₂)(Cl) · (O^tBu)₂}{Mo(O)(N₃S₂)(O^tBu)}]₂ ( 1 ) and [W(N₃S₂)₂(LiCl) · {N≡W(NPPh₃)₃}₂] ( 2 ) are formed from [MoCl₃(N₃S₂)]₂ and LiO^tBu in toluene, and from [WCl₃(N₃S₂)]₂ and LiNPPh₃ in THF, respectively. The complexes form moisture sensitive, black ( 1 ) or brown ( 2 ) crystals, which we characterized by crystal structure analyses. 1 · Toluene: Space group P 1, Z = 1, lattice dimensions at –83 °C: a = 934.2(1), b = 964.4(1), c = 1700.3(1) pm; α = 83.54(1)°, β = 78.35(1)°, γ = 71.56(1)°, R₁ = 0.0339. 2 · 1.625 Toluene · 0.75 THF: Space group P 1, Z = 4, lattice dimensions at –80 °C: a = 1313.8(1), b = 2896.8(2), c = 3384.9(3) pm; α = 82.42(1)°, β = 88.71(1)°, γ = 77.28(1)°, R₁ = 0.0603.     

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.     

Synthesen und Kristallstrukturen der chalkogenidoverbrückten Nickelclusterverbindungen [Ni5Se4Cl2(PPhEt2)6], [Ni12Se12(PnPr3)6] und [Ni18S18(PiPr3)6]

Syntheses and Crystal Structures of Chalcogenido‐bridged Nickel Cluster Compounds [Ni₅Se₄Cl₂(PPhEt₂)₆], [Ni₁₂Se₁₂(PⁿPr₃)₆], and [Ni₁₈S₁₈(PⁱPr₃)₆] The reaction of (R)ESiMe₃ (R = SiMe₃, Mes = C₉H₁₁; E = S, Se) with [NiCl₂(PPhEt₂)₂] and [NiCl₂(PR₃)₂] (R = ⁿPr, ⁱPr) gives new chalcogenido‐bridged nickel cluster compounds [Ni₅Se₄Cl₂(PPhEt₂)₆]·2THF ( 1 ), [Ni₁₂Se₁₂(PⁿPr₃)₆]·2THF ( 2 ), and [Ni₁₈S₁₈(PⁱPr₃)₆]·2THF ( 3 ). The structures of these compounds were determined by single crystal X‐ray structural analyses.     

Darstellung und Strukturaufklärung von Ammonium‐tetraamminlithium‐amidotrithiophosphat‐Ammoniak(1/1) (NH4) [Li(NH3)4] [P(NH2)S3] · NH3

Synthesis and Crystal Structure of Ammonium Tetraamminelithium Amidotrithiophosphate‐Ammonia(1/1)(NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ Colourless crystals of (NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ were prepared by the reduction of P₄S₁₀ with a solution of lithium in liquid ammonia. The X‐ray structure determination shows them to contain the pseudo‐tetrahedral amidotrithiophosphate anion [P(NH₂)S₃]²⁻ (point group C_S), which is the hitherto unknown final member of a series of previously characterized amidothiophosphates. The ammonium ion and the ammonia molecule of solvation form an diamminehydrogen(1+)‐ion N₂H₇⁺ with a short, nearly linear hydrogen bond of 2.864(3) Å.     

Syntheses,Crystal Structures and Non‐linear Optical Properties of Cluster Compounds [MoAu2S4(PPh2Py)2] and [WAu2S4(PPh2Py)2]

The cluster compounds, [MoAu₂S₄(PPh₂Py)₂] ( 1 ) and [WAu₂S₄(PPh₂Py)₂] ( 2 ), were synthesized by the reaction of (NH₄)₂MS₄ (M = Mo, W), H[AuCl₄]·4H₂O and diphenyl‐2‐pyridyl‐phosphine (PPh₂Py) in CH₂Cl₂ solution. [MoAu₂S₄(PPh₂Py)₂] crystallizes in the monoclinic space group P2₁/c with a = 18.385(2), b =12.304(1), c = 16.904(2) Å, β =110.722(2)°, and Z = 4. [WAu₂S₄(PPh₂Py)₂] crystallizes in the triclinic space group P‐1 with a = 9.333 (3), b = 10.628(3), c = 19.566(6) Å, α = 89.26(1), β = 80.87(1), γ = 68.85(1)°, and Z = 2. Single crystal X‐ray analysis showed that these two compounds are isostructural, but belong to different space groups. The Mo (W) atom has a slightly distorted tetrahedral coordination, and the two Au atoms are distorted from trigonal planar, the P—Au—M—Au—P chain is nearly linear. Measurement of the nonlinear optical (NLO) properties using the Z‐scan technique with an 8‐ns pulsed laser at 532 nm showed that 1 and 2 possess NLO absorption and effective self‐focusing effect. The effective α₂ and n₂ values of cluster 1 are 5.89 × 10^—12 m · W^—1 and 6.45 × 10^—18 m² · W^—1; the effective α₂ and n₂ values of compound 2 are 4.35 × 10^—11 m · W^—1 and 3.73 × 10^—17 m² · W^—1.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

S4N4 und seine Derivate: [Cu(CH3CN)Cl2]2S2N2, ein Übergangsmetallkomplex mit dem S2N2-Ligand

S₄N₄ and its Derivatives: [Cu(CH₃CN)CL₂]₂S₂N₂, a Transition Metal Complex with the S₂N₂ Ligand S₄N₄ reacts with CuCl₂ · 2H₂O in acetonitrile to give among other products the polymer copper(II) complex [Cu(CH₃CN)Cl₂]₂S₂N₂, This complex crystallizes in the space group P2₁/c with a = 9.635(4), b = 7.270(4), c = 10.009(6) Å, β = 93.16(6)°, and Z = 2. An X-ray structure analysis (R = 0,065) shows the crystal to.contain parallel chains with copper atoms bridged by Cl and S₂N₂ bridges. The coordination of the Cu atom is square pyramidal. The S₂N₂ ring is planar. The SN bond distances are 1.633 and 1.641 Å.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

Reaktionen von Oxiden der Elemente der V. Hauptgruppe mit Trithiazylchlorid Kristallstruktur von (S5N5)4[As8Cl28] · 2 S4N4

Reactions of Element Oxides of the Fifth Main Group with Trithiazyl Chloride. Crystal Structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ Whereas P₄O₁₀ does not react with (NSCl)₃, the oxides As₂O₃, Sb₂O₃, and Bi₂O₃ react under formation of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄, S₅N₅[SbCl₆] and a mixture of S₄N₅[BiCl₄] and S₄N₄Cl[BiCl₄], respectively. The products were characterized by their IR spectra. The crystal structure of (S₅N₅)₄[As₈Cl₂₈] · 2 S₄N₄ was determined by means of X-ray diffraction (1168 independent observed reflexions, R = 0.059). Crystal data: tetragonal, space group P4 2₁c, Z = 2, a = 1596.6, c = 1520.1 pm. The compound consists of planar S₅N₅^⊕ cations, octameric anions [As₈Cl₂₈]^4? and S₄N₄ molecules. The S₅N₅^⊕ ions and the S₄N₄ molecules show positional disorder, which very probably is of dynamical type for the S₅N₅^⊕ ion. The [As₈Cl₂₈]^4? ions can be described as a (so far unknown) [As₄Cl₁₆]^4? ion with cubane-like structure (As? Cl bridging distances between 286 and 305 pm) to which four AsCl₃ molecules are attached via chloro bridges with As? Cl bond lengths between 314 and 328 pm.     

Polysulfonylamine. CLXV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 14 [1] Cs3Ag[(MeSO2)2N]4 und CsAg[(MeSO2)2N]2: Ein dreidimensionales und ein schichtförmiges Koordinationspolymer mit Bis(dimesylamido‐N)argentat‐Baugruppen

Polysulfonylamines. CLXV. Crystal Structures of Metal Di(methanesulfonyl)amides. 14. Cs₃Ag[(MeSO₂)₂N]₄ and CsAg[(MeSO₂)₂N]₂: A Three‐Dimensional and a Layered Coordination Polymer Containing Bis(dimesylamido‐N)argentate Building Blocks Serendipitous formation pathways and low‐temperature X‐ray structures are reported for the coordination compounds Cs₃A₂[AgA₂] ( 1 ) and Cs[AgA₂] ( 2 ), where A^— represents the pentadentate dimesylamide ligand (MeSO₂)₂N^—. Both phases (monoclinic, space group C2/c, Z′ = 1/2) contain inversion‐symmetric bis(dimesylamido‐N)argentate units displaying exactly linear N—Ag—N cores and short, predominantly covalent Ag—N bonds [ 1 : 213.5(2), 2 : 213.35(12) pm]; in each case, the coordination number of the silver ion is extended to 2 + 6 by four internal and two external Ag···O secondary interactions. The three‐dimensional coordination polymer 1 is built up from alternating layer substructures [{Cs(1)}{A}_4/2]^— with Cs(1) lying on twofold rotation axes and [{Cs(2)}₂{AgA₂}_4/4]⁺ with Cs(2) occupying general positions. Within the substructural layers, both types of cesium cation have approximately planar O₄ environments, whereas the final coordination spheres including interlayer bonds are extended to O₆ for Cs(1) and to O₈N for Cs(2). Compound 2 , in contrast, forms a genuine layer structure. The layers are constructed from Cs⁺ chains located on twofold rotation axes, alternating with [AgA₂]^— stacks reinforced by Ag···O secondary interactions and weak C—H···O hydrogen bonds; Cs⁺ is embedded in an O₈ environment. Both structures are pervaded by a three‐dimensional C—H···O network.     

Synthese,Kristallstruktur und Eigenschaften der käfigartigen,sechsbasigen Säure P12S12N8(NH)6 · 14 H2O sowie ihrer Salze Li6[P12S12N14] · 26 H2O, (NH4)6[P12S12N14] · 10 H2O und K6[P12S12N14] · 8 H2O

Syntheses, Crystal Structure, and Properties of the Cage‐like, Hexaacidic P₁₂S₁₂N₈(NH)₆ · 14 H₂O and its Salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O, (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O, and K₆[P₁₂S₁₂N₁₄] · 8 H₂O The cage‐like acid P₁₂S₁₂N₈(NH)₆ · 14 H₂O was obtained by the reaction of KSCN with P₄S₁₀ via the formation of K₆[P₁₂S₁₂N₁₄] · 8 H₂O and subsequent ion exchange reactions in aqueous solution. Starting from the acid the salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O and (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O were synthesized. According to X‐ray single‐crystal structure analyses the compounds are built up by isosteric P–N cages [P₁₂S₁₂N^[3]₈N^[2]₆]^6–. Each of them is made up of twelve P₃N₃ rings, which exclusively exhibit the boat conformation. The cages have the idealized symmetry 2/m3; P₁₂S₁₂N₈(NH)₆ · 14 H₂O: P1, a = 1119.11(7), b = 1123.61(7), c = 1125.80(6) pm, α = 80.186(4), β = 60.391(4), γ = 60.605(4)°, Z = 1; Li₆[P₁₂S₁₂N₁₄] · 26 H₂O: Fm3, a = 1797.4(1) pm, Z = 4; (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O: P6₃, a = 1153.2(1), c = 2035.6(2) pm, Z = 2; K₆[P₁₂S₁₂N₁₄] · 8 H₂O: R3c, a = 1142.37(5), c = 6009.6(3) pm, Z = 6. In the crystal the cages of the acid are crosslinked via hydrate molecules by hydrogen bonds. The cations in the salts show a high‐mobility and are located between the cages.     

Temperature Influence on the Formation of Selenidoantimonates: Solvothermal Syntheses,Crystal Structures and Thermal Properties of [Ni(dien)2]2Sb2Se6, [Mn(dien)2]2(SbSe4)(Cl), [Co(dien)2]2(SbSe4)(Br), and [Co(dien)2]3(SbSe4)2

New selenidoantimonats [Ni(dien)₂]₂Sb₂Se₆ ( 1 ), [Mn(dien)₂]₂(SbSe₄)(Cl) ( 2 ), [Co(dien)₂]₂(SbSe₄)(Br) ( 3 ), and [Co(dien)₂]₃(SbSe₄)₂ ( 4 ) (dien = diethylenetriamine) were solvothermally synthesized in dien solvent at 180 °C. The crystal structure of 1 consists of two octahedral [Ni(dien)₂]²⁺ cations and a mixed‐valent [Sb₂Se₆]^4? anion. The isolated [Sb₂Se₆]^4? anion is formed by a Sb^IIISe₃ trigonal pyramid and a Sb^VSe₄ tetrahedron sharing a common corner. 2 and 3 are composed of octahedral [M(dien)₂]²⁺ cations, tetrahedral [SbSe₄]^3? anions and halide ions forming an extended network through hydrogen‐bonding interactions. In 4 the [Co(1)(dien)₂]²⁺, [Co(2)(dien)₂]²⁺ and [SbSe₄]^3? ions form layered structures via N–H···Se hydrogen bonds. The [Co(3)(dien)₂]²⁺ ion is located between the layers, and interacts with the layers by N–H···Se bonds. The synthesis and solid state structural studies on the title compounds show that the higher reaction temperature is helpful for the formation of selenidoantimonate(V) compounds in the synthesis of selenidoantimonate from the M²⁺/Sb/Se/dien system. 1 – 4 start to decompose at temperature about 210 °C in N₂ atmosphere. They lose dien ligands at a wide temperature range of 210–450 °C with multisteps for 1 – 3 and a single step for 4 .     

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.     

Bimetallic assemblies, [Ni(en)2]3[M(CN)6]2·3H2O (en = H2NCH2CH2NH2; M = Fe,Co)

The reaction between tris(ethyl­enedi­amine)­nickel(II) cations and hexa­cyanometallate(III) anions (M = Fe, Co) yields ordered bimetallic assemblies, catena‐poly­[[tris­(ethyl­enedi­amine)­nickel‐bis(μ‐hexa­cyano­iron‐N,N′)] trihydrate] and catena‐poly­[[tris­(ethyl­enedi­amine)­nickel‐bis(μ‐hexa­cyano­cobalt‐N,N′)] trihydrate], [{Ni(C₂H₈N₂)₂}₃{M(CN)₆}₂]·3H₂O, in which both cis and trans [Ni(en)₂] and [M(CN)₆] moieties are linked to give S‐shaped Ni–NC–M–CN–Ni–NC–M–CN–Ni units which are cross­linked to give ribbons parallel to the b axis. The two compounds are isomorphous with mean metal–ligand distances Fe—C = 1.940 (3), Co—C = 1.844 (3) and Ni—N = 2.102 (2) Å for the iron, and 2.105 (3) Å for the cobalt compound. These compounds appear to be identical with those formulated as [Ni(en)₂]₃[M(CN)₆]₂·2H₂O [Ohba, Maruona, Okawa, Enoki & Latour (1994). J. Am. Chem. Soc. 116 , 11566–11567; Ohba, Fukita & Okawa (1997). J. Chem. Soc. Dalton Trans. pp. 1733–1737] which were indexed on a smaller unit cell and described as disordered.     

FeIII in a low‐spin state in caesium bis[3‐ethoxysalicylaldehyde 4‐methylthiosemicarbazonato(2–)‐κ3O2,N1,S]ferrate(III) methanol monosolvate

The synthesis and crystal structure (at 100 K) of the title compound, Cs[Fe(C₁₁H₁₃N₃O₂S₂)₂]·CH₃OH, is reported. The asymmetric unit consists of an octahedral [Fe^III(L)₂]⁻ fragment, where L²⁻ is 3‐ethoxysalicylaldehyde 4‐methylthiosemicarbazonate(2−) {systematic name: [2‐(3‐ethoxy‐2‐oxidobenzylidene)hydrazin‐1‐ylidene](methylamino)methanethiolate}, a caesium cation and a methanol solvent molecule. Each L²⁻ ligand binds through the thiolate S, the imine N and the phenolate O atoms as donors, resulting in an Fe^IIIS₂N₂O₂ chromophore. The O,N,S‐coordinating ligands are orientated in two perpendicular planes, with the O and S atoms in cis positions and the N atoms in trans positions. The Fe^III cation is in the low‐spin state at 100 K.     

The Binary Group 4 Azides [PPh4]2[Zr(N3)6] and [PPh4]2[Hf(N3)6]

The binary zirconium and hafnium polyazides [PPh₄]₂[M(N₃)₆] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF₄ by fluoride–azide exchange reactions with Me₃SiN₃ in the presence of two equivalents of [PPh₄][N₃]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N₃)₄], [M(N₃)₅]^? and [M(N₃)₆]^2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.