Zur Kenntnis der Oxocobaltate(II) Na4[CoO3], ein Nesocobaltat(II)

On the Knowledge of Oxocobaltates(II). Na₄[CoO₃], the First Nesocobaltate(II) Newly prepared transparent, blood red single crystals of Na₄[CoO₃] (Na₂O/?CoO’? Na:Co = 4.4:1, cobalt tube, 550°C, 20d, dry argon), crystallize triclinically, P1, a = 8.14₄, b = 6.22₀, c = 5.75₈ Å; α = 117.5, β = 89.9, γ = 111.2 (diffractometer data), Z = 2. There are carbonate-like, isolated [CoO₃] groups, respectively parameters and distances see text. 2358 symmetry independent reflections (automatical four cycle diffractometer PW 1100, Mo–Kα, graphite monochromator, 4° ? Θ ? 36°), R = 0.0597. The Madelung Part of the Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN and Mean Fictive Ionic Radii, MEFIR are calculated and discussed.     

The crystal structure of tris (ethylenediamine), cobalt(III) hexacyanoferrate(III)dihydrate,Co(C2H8N2)3[Fe(CN)6] · 2H2O

The crystal structure of the title compound has been determined from three dimensional x-ray data obtained by the multiple film method. The space group is P2_l/n and the cell dimensions are: a = 14.90, b = 16.84, c = 8.38 Å; β = 93.5° Z = 4. The structure is formed by discrete Co (en) and Fe(CN) ions, both of which have an octahedral configuration. The Fe(CN) ions are approximately octahedrally surrounded by the Co (en) ions while arrangement of Fe (CN) ions around the Co(en) ions completely differs from an octahedron. The mean Fe? C and Co? C dustances are 1.91 and 2.01 Å, respectively. The water molecules do not play an important role in the structure and all distances between oxygen and other atoms indicate the presence of very weak hydrogen bonds. The salts M (en)₃ Q(CN)₆ · H₂O, where M = Co and Cr and Q = Cr, Mn, Fe and Co, are all isomorphous.     

Interactions Magnetiques dans quelques Ferrites Oxyfluores a Structure Spinelle de Formule ZnxMFe2−xO4–xFx (M ? Fe,Co, Ni)

Magnetic interactions in some oxyfluoroferrites of spinel structure with the formula Zn_xMe_2?xO_4?xFx (M = Fe, Co, Ni) Whereas the ferromagnetic spin arrangement of the B-cations is not modified by the Zn²⁺?Fe³⁺ substitution in the ZnFe[Fe₂₊Fe³⁺]O_4?xF_x (0 ≤ x ≤ 0,50) spinel, this same substitution leads to a spin canting in the ZnFe[Co₂₊Fe³⁺]O_4?xF_x and ZnFe[Ni₂₊Fe³⁺]O_4?xF_x (0 ≤ x ≤ 0,80) simples. The difference in the magnetic behaviors with regard to the AB and BB interactions can be explained on the basis of the magnetic exchange theory.     

Subgroup 4 (Ti,Zr, Hf) derivatives of Cobalt Carbonyls

Bimetallic and trimetallic compounds containing unsupported bonds of subgroup 4 metals (M = Ti, Zr, Hf) and Co were prepared by hydride elimination (A) from RM derivatives (R¹ = PhCH₂; RN; R² = Me, Et)) and by salt elimination (B) from RMX (X = Cl, Br; R.¹ = PhCH₂, RN and R³O; R³= i-Pr, n-Bu)) by reaction with HCo(CO)₄ and Na[Co(CO)₄], respectively. Compounds RMCo(CO)₄ with R¹ = PhCH₂, RM[Co(CO)₄]₂ R.¹ = PhCH₂, were prepared both by methods A and B, while (R³O)₄-n Ti[Co(Co)₄]n (n = 1, 2) compounds were obtained by reaction B. Several tertiary phosphine and phosphite derivatives of the former two types were obtained by substitution of a carbonyl group by PR ligand or by A type reaction of HCo(CO)³(PR with RM compounds.     

Synthese und Struktur des ersten ternären Blei(II)-Oxocuprats(I): PbCu2O2

Synthesis and Structure of the First Ternary Lead(II) Copper(I) Oxide: PbCu₂O₂ PbCu₂O₂ can be prepared by solid state reaction or by precipitation from a basic aqueous solution. Single crystals of the new compound were prepared by recrystallisation from a molten mixture (PbO? Cu₂O) and investigated by X-ray diffractometer technique. PbCu₂O₂ crystallizes isotypically with the homologue silver compound PbAg₂O₂ (monoclinic with a = 8.22₃ Å, b = 8.28₉ Å, c = 6.01₅ Å, β = 132.6₂°, Z = 4, space group C? C 1 2/c 1). The crystallographic data from the X-ray investigation are reported. The structure is built by endless [PbO_4/4]- and [CuO_2/4]-chains. Pb²⁺ has a one-sided asymmetric coordination with four next oxygen neighbours and Cu⁺ forms a stretched dumbbell with two oxygen atoms.     

Synthesis and Structure of [Sn4Se11]6–, [Sn2Se52–], and [Sn3Se72–] – Model Anions for the Solventothermal Reaction Pathway to Lamellar Selenidostannates(IV)

Reaction of A₂CO₃ (A = K, Rb) with Sn and Se in an H₂O/CH₃OH mixture at 115–130°C affords the isotypic selenidostannates(IV) A₆Sn₄Se₁₁ _. xH₂O (A = K, x = 8) 1 and 2 whose discrete [Sn₄Se₁₁]^6– anions each contain two corner‐bridged ditetrahedral [Sn₂Se₆]^4– species. Similar reaction conditions with A = Cs afford Cs₂Sn₂Se₅ _. H₂O ( 3a ) and Cs₂Sn₂Se₅ ( 3b ) in which such [Sn₂Se₆]^4– building blocks are connected through common Se atoms into infinite [Sn₂Se₅^2–] chains. The [Sn₃Se₇^2–] ribbons of (Et₄N)₂Sn₃Se₇ ( 4 ), formed by treating (Et₄N)I with Sn and Se in methanol at 130°C, can be regarded as resulting from the condensation of [Sn₂Se₅^2–] chains with molecular [SnSe₄]^4– anions. The anions [Sn₄Se₁₁]^6–, [Sn₂Se₅^2–], and [Sn₃Se₇^2–] represent the products of individual reaction steps on the potential condensation pathway of [Sn₂Se₆]^4– to the lamellar selenidostannates(IV) [Sn₄Se₉^2–] or [Sn₃Se₇^2–].     

Schwingungsspektren und Kraftkonstanten der Übergangsreihe O2PF—S2PF— S2P(CH3)

Vibration spectra and force constants of the series O₂PF — S₂PF — S₂P(CH₃). The vibrational spectra of OSPF, S₂PF, S₂PF(CH₃) and S₂P(CN) are reported and discussed with O₂PF and S₂P(CH₃). On the basis of a simplified valence-force-field the force constants are calculated and the bonding relations are discussed. In the ions, f PF is lower than in corresponding molecules. The ionic charge is distributed over nearly all atoms of the ions.     

Thallium(I)-thiometallate(II,IV) vom Typ TI2MeMeIVS6

Thallium(I) Thiometallates(II, IV), Tl₂MeMe^IVS₆ The preparation and some properties of the compounds Tl₂MeMe^IVS₆ are reported, where Me^II = Pt, Pd, Ni; Me^IV = Pt, Zr, Sn, Ta. Their structure is discussed in relation to the structure of the alkali compounds A₂MeMe^IVS₆.     

One‐ to Three‐Dimensional CuI and CuCN Based Coordination Polymers containing the Alkali Cation Ligating Thiacrown Ether 1, 10‐Dithia‐18‐Crown‐6

Treatment of an acetonitrile solution of CuI with 1, 10‐dithia‐18‐crown‐6 (1, 10DT18C6) in the presence of Rb₂CO₃ leads to formation of the lamellar coordination polymer [Rb{Cu₄I₅(1, 10DT18C6)₂}] ( 1 ).The anionic network of 1 is composed of parallel [(Cu₄I₅)^—] chains linked by bridging thiacrown ether ligands, pairs of which coordinate the Rb⁺ counter cations. [Cs{Cu₅I₆(1, 10DT18C6)₂}] ( 2 ) can be prepared under similar conditions but contains separated helical anionic chains. In this case 1, 10DT18C6 ligands bridge copper atoms of individual chains in an intrastrand manner. In contrast the coordination networks in [(CuCN)₂(1, 10DT18C6)] ( 3 ) and [K₂{Cu₁₂(CN)₁₄(1, 10DT18C6)₃} · CH₃CN] ( 4 ) are both three‐dimensional and based on CuCN‐containing sheets bridged by 1, 10DT18C6 ligands. In the latter compound pairs of K⁺ cations are coordinated by groups of three thiacrown ether molecules. The neutral network of 3 can imbibe up to 31 % KNO₃ per 1, 10DT18C6 pair without loss of lattice integrity.     

19F-NMR-spektroskopischer Nachweis und Berechnung der statistischen Bildung der gemischten Clusteranionen [(Mo6BrCl)F]2−, n = 0 – 8

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆Br Cl )F ]^2?, n = 0 – 8 The complete system of the innersphere mixed clusters (Mo₆BrCl)⁴⁺ is formed by exchange of innersphere bound Clⁱ against outersphere bound Br^a on tempering the solid [(Mo₆Cl)Br] at 500°C for 16 h. After conversion with conc. HCl into (H₃O)₂[(Mo₆BrCl)Cl] and precipitation of the outer Cl^a with AgBF₄ in ethanol, treatment with tetrabutylammonium(TBA)fluoride yields (TBA)₂ [(Mo₆BrCl)F], a mixture of 22 different species. According to the sets of chemical equivalent fluorine atoms in total 55 ¹⁹F nmr signals are expected, which are really observed in the high resolution 1D-¹⁹F-nmr spectrum. Using increments of chemical shifts, peak intensities and multiplet structures as well as the 2D-¹⁹F/¹⁹F-COSY spectrum the complete and unambiguous assignment of all resonances is achieved. From the measured integral intensities the distribution of the different compounds is determined, revealing statistical formation of the geometrical isomers.     

Complexes of Silver(l) with arsenic and phosphorus donor ligands. Co-ordination number 4

Some tetracoordinated complexes having the formulae, [AgL₄]X (L = Triphenyl-arsine; X = NO, ClO and BrO) and [AgL₃X] (L = Triphenyl-arsine/phosphine; X = SCN^? and NCO^?) have been prepared and characterised by analyses, conductance, magnetic susceptibility and infra-red spectroscopy.     

Low Valence States of Metal Chelates. V. Tris(1,10-phenanthroline)cobalt(II) and bis(2,9-dimethyl-1,10-phenanthroline)cobalt(II) perchlorates

D. C. polarography and cyclic voltammetry were used for investigating the reduction processes of the tris(1,10-phenanthroline)cobalt(II) and bis(2,9-dimethyl-1, 10-phenanthroline)-cobalt(II) perchlorates in 0.1 M solutions of tetraethylammonium perchlorate in acetonitrile. The first complex gave a four-step reduction wave; the first two steps were found to be diffusion controlled and reversible reductions from Co(phen)⁺ to Co(phen)₃⁺ to Co(phen) to Co(phen;) occured. The second complex gave a six-step reduction wave; the first three steps were found to be diffusion controlled and were to be considered as successive reversible reductions from Co(2, 9dm-phen)⁺ to Co(2, 9dmphen), from Co(2, 9dmphen) to Co(2, 9dmphen)₂ and from Co(2, 9dmphen)₂ to Co(2, 9dmphen).     

Dicyanmethanido- und Cyanamido-oxoanionen. Untersuchungen zum sauerstoffanalogen Charakter der C(CN)2- und NCN-Gruppen

The equivalence of the C(CN)₂- and the NCN-groups with oxygen in the series of homologous ions C(CN), N(CN), OCN^? and NOC(CN), NO causes us to postulate a more general value of this relation. Arguments for the formulation of a pseudochalkogen series C(CN)₂? NCN? O are discussed. Synthesis, structure and reactivity of some dicyanmethanido- and cyanamido-oxoanions RCOY^?, CO₂Y^2?, COY, NOY^?, NO₂Y^?, PO₃Y^3?, PO₂Y and SO₂Y^2? are described. (Y ? C(CN)₂, NCN.) The preparation of some triorganoleadacyles is reported.     

Cs5[Na{W4N10}]: The first framework nitridotungstate(VI)

Cs₅[Na{W₄N₁₀}] was prepared from a mixture of NaNH₂, CsNH₂ and tungsten powder (molar ration 1 : 10 : 4) at 700°C in autoclaves. After the reaction is finished the nitride is embedded in an alkali metal matrix. Dark red crystals were isolated by washing out the alkali metal with liquid ammonia at room temperature. The structure of Cs₅[Na{W₄N₁₀}] was solved by X-ray single crystal data: I4₁ (No. 80), Z = 4, a = 13.926(3) Å, c = 8.723(3) Å, Z(F) ≥ 3σ(F) = 1535, Z(Variables) = 63, R/R_w = 0.040/0.052. The compound is highly sensitive against moisture giving oxotungstates and ammonia. It contains a framework of tetrahedra [WNN_3/2^1.5?]. Sodium shares four terminal nitrogen ligands. Including sodium a distorted, β-cristobalite type arrangement [Na{W₄N₁₀}^5?] results. It contains caesium in all interstices formed by twelve nitrogen ligands in so-called Friauf polyhedra.     

Darstellung,Schwingungsspektrum und Kristallstruktur von (n‐Bu4N)2[(W6Cl)F] · 2 CH2Cl2 und 19F‐NMR‐spektroskopischer Nachweis der gemischten Clusteranionen [(W6Cl)FCl]2–, n = 1–6

Synthesis, Vibrational Spectra, and Crystal Structure of ( n ‐Bu₄N)₂[(W₆Cl )F ] · 2 CH₂Cl₂ and ¹⁹F NMR Spectroscopic Evidence of the Mixed Cluster Anions [(W₆Cl )F Cl ]^2–, n = 1–6 The reaction of (n‐Bu₄N)₂[(W₆Cl)Cl] with CF₃COOH in dichloromethane gives intermediately a mixture of the cluster anions [(W₆Cl)(CF₃COO)Cl]^2–, n = 1–6. By treatment with NH₄F the outer sphere coordinated trifluoracetato ligands are easily substituted and the components of the series [(W₆Cl)FCl], n = 1–6 are formed and characterized by their distinct ¹⁹F NMR chemical shifts. An X‐ray structure determination has been performed on a single crystal of (n‐Bu₄N)₂[(W₆Cl)F] · 2 CH₂Cl₂ (orthorhombic, space group Pbca, a = 15.628(4), b = 17.656(3), c = 20.687(4) Å, Z = 4). The low temperatur IR (60 K) and Raman (20 K) spectra are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are f_d(WW) = 1.89, f_d(WF) = 2.43 and f_d(WCl) = 0.93 mdyn/Å.     

Zur Kristallstruktur von OMF (M = Sb,Ru, Pt,Au)

On the Crystal Structure of O MF (M = Sb, Ru, Pt, Au) OMF (M = Sb, Ru, Pt, Au) were obtained again, but for the first time investigated by X-ray methods. Colourless OSbF and the rubyred compounds ORuF and OPtF crystallize isostructural in space group Ia3 -T_h⁷ (Nr. 206) with a = 1016(1) pm (Sb), a = 1002.6(9) pm (Ru) and a = 1003.6(9) pm (Pt), Z = 8. Yellow OAuF crystallizes trigonal-rhombohedric in space group R3 -D₃₂⁶ (Nr. 148) with a = 775.9(3) pm, c = 711.7(4) pm, Z = 3.     

Assembly of Chiral Two- and Three-dimensional Copper(I) Pseudohalide Based Coordination Polymers with Asymmetrically Substituted Pyrazine and Pyrimidine Ligands

The coordination polymers [(CuCN)₂(μ-2 Mepyz)], [CuCN(μ-2 Mepyz)] and [CuCN(μ-4 Mepym)] ( 1 – 3 ) (2 Mepyz = 2-methylpyrazine; 4 Mepym = 4-methylpyrimidine) may be prepared by self-assembly in acetonitrile solution at 100 °C ( 1 , 3 ) or without solvent at 20 °C ( 2 ). All three contain [CuCN] chains that are bridged by the bidentate aromatic ligands into sheets in 1 and 3 D frameworks in 2 and 3 . Reaction of CuSCN with these heterocyclic diazines at 100 °C leads to formation of the lamellar coordination polymers [(CuSCN)(μ-2 Mepyz)] ( 4 ) and [CuSCN · (4 Mepym-κN1)] ( 5 ), which contain respectively [CuSCN] chains and trans-trans fused [CuSCN] sheets as substructures. The presence of an asymmetric substitution pattern in 2 Mepyz and 4 Mepym induces the adoption of a chiral structure by 2 and 5 (space groups P2₁2₁2₁ and P1).     

Darstellung und Struktur der Tetrafluoroaurate(III) MI[AuF4] mit MI = Li,Rb

Synthesis and Structure of Tetrafluoroaurates(III) M^I[AuF₄] with M^I = Li, Rb Single crystal investigations on Rb[AuF₄], light yellow, confirm the tetragonal unit cell (K[BrF₄]-type) with a = 618.2(1) and c = 1191(1) pm, Z = 4, space group I 4/mcm-D (No. 140). Li[AuF₄], light yellow too, crystallizes monoclinic with a = 485.32(7), b = 634.29(8), c = 1004.43(13) pm, β = 92.759(12), Z = 4; space group P 2/c-C (No. 13). The structure of Li[AuF₄] is related to the Rb[AuF₄]-type of structure.     

Darstellung,Kristallstruktur und Schwingungsspektren von (n-Bu4N)2[(Mo6I)(NCS)]

Synthesis, Crystal Structure, and Vibrational Spectra of (n-Bu₄N)₂[(Mo₆I)(NCS)] By treatment of [(Mo₆I)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(Mo₆I)(NCS)]^2– is formed. The X-ray structure determination of (n-Bu₄N)₂[(Mo₆I)(NCS)] · 2 Me₂CO (monoclinic, space group P2₁/c, a = 13.168(5), b = 11.964(5), c = 24.636(5) Å, β = 104.960(5)°, Z = 2) shows, that the thiocyanate groups are coordinated exclusively via N atoms with Mo–N bond lengths of 2.141–2.150 Å, Mo–N–C angles of 166–178° and N–C–S-angles of 174–180°. The vibrational spectra exhibit characteristic innerligand vibrations at 2073–2054 (ν_CN), 846–844 (ν_CS) and 480–462 cm^–1 (δ_NCS).     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.