19F-NMR-spektroskopischer Nachweis und statistische Untersuchung zur Bildung der gemischten Clusteranionen [(Mo6ICl)F]2−, n = 0–7, und Darstellung von (TBA)2[(Mo6I)F]

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆I Cl )F ]^2?, n = 0–7, and Preparation of (TBA)₂[(Mo₆I )F ] The octa-μ₃-iodo-hexafluoro-hexamolybdate(2?)ion [(Mo₆I)F]^2? is prepared for the first time. The system of the 21 innersphere mixed clusters (Mo₆ICl)⁴⁺, n = 0–7 is formed by exchange of innersphere bound Clⁱ against outersphere bound I^a on tempering solid [(Mo₆Cl)I] at 400°C. Prolonged tempering leads to increasing average n values of the mixture, which is converted into the tetrabutylammonium salt (TBA)₂[(Mo₆ICl)F]. Using increments of chemical shifts and integral peak intensities the 54 ¹⁹F-nmr signals of the 21 species (compound n = 8 is absent) are assigned and confirmed by the 2 D-¹⁹F/¹⁹F-COSY spectrum. From the measured intensities the distribution of the different compounds is determined and proves significant deviation from statistical occupation, revealing the preference of isomers with iodine atoms occupying edges of the innersphere cube and discrimination of those sharing diagonals of the faces. Moreover all compounds with n = 3 and 4 are present overaverage in comparison to the others.     

Struktur und Eigenschaften von Gd3I3C

Structure and Properties of Gd₃I₃C . The compound Gd₃I₃C is prepared by reaction of Gd, GdI₃ and C (2:1:1 mole) at 1 250 K in sealed Ta tubes. It is obtained as bronze-coloured needles which are air and moisture sensitive. The structure of Gd₃I₃C contains twin chains of C centered Gd₆ octahedra surrounded by I atoms capping all free edges like in the M₆X₁₂ cluster. The one-dimensional units are oriented along [010] and linked according to (GdGd_1/3Gd_2/2Gd_2/3C)₂IIII. Gd₃I₃C is metallic in the temperature range 300 K ≥ T ≥ 120 K, between 120 and 15 K the electrical resistance increases by 6 orders of magnitude. At high temperatures the susceptibility follows the Curie-Weiß law with a paramagnetic Curie temperature θ ≈ - 340 K. Two local maxima in the susceptibility at 100 K and 25 K indicate successive formation of antiferromagnetically ordered structures.     

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.     

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).     

Cs4[Sc6C]Cl13 und Cs4[Pr6(C2)]I13 — zwei Beispiele für das fehlende Bindeglied bei der Verknüpfung der Baueinheiten [M6Z]XX

Cs₄[Sc₆C]Cl₁₃ and Cs₄[Pr₆(C₂)]I₁₃ — Two Examples for the Missing Link in the Connectivity of [M₆Z]X X Building Units Cs₄[Sc₆C]Cl₁₃ (tetragonal, I4₁/amd, a = 1 540.5(4), c = 1 017.9(7) pm, c/a = 0.661, Z = 4, R = 0.038, R_w = 0.026) and Cs₄[Pr₆(C₂)]I₁₃ (a = 1 804.9(3), c = 1 259.5(3) pm, c/a = 0.698, R = 0.106, R_w = 0.068) are obtained as green-black and blue-black single crystals with brass-like metallic lustre through metallothermic reduction of ScCl₃ and PrI₃, respectively, with cesium in the presence of carbon in sealed tantalum containers. The, overall, isotypic compounds contain isolated [Sc₆C] and [Pr₆(C₂)] clusters, respectively, that are surrounded by 18 halide (X) ligands (12 Xⁱ and 6 X^a; X = Cl or I). The connection is carried out via the motif [M₆Z]XXXX (M = Sc and Pr; Z = C and C₂, respectively) and is thereby the missing link of the motifs of connection for the composition A_x[M₆Z]X₁₃. Analogous interconnection of [TiO₆] octahedra is found in the anatase-type of structure of TiO₂.     

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.     

Über das Auftreten von Monoselenan- und Monotelluran-disulfandiphosphonat bei der Umsetzung von SPO mit Seleno- und Telluropolythionaten

On the Formation of Monoselenane and Monotellurane Disulphane-diphosphonate by the Reaction of SPO with Seleno and Telluropolythionates In the reaction of seleno- and telluropolythionates with SPO, SeS₂P₂O and TeS₂P₂O are formed and are described for the first time. Polysulfphane-diphosphonates, -disulphonates and -phosphonsulphonates occur as side and consecutive products. By evaluation of radiochemical double labelling with the nuclide pairs ³⁵S? ³²P and ³⁵S? ⁷⁵Se, it is possible to identify the products formed and obtain information about the reaction mechanism.     

Dibrommethylsulfoniumsalze – Darstellung und Kristallstruktur [1]

Dibromomethylsulfoniumsalts — Preparation and Crystal Structure The salts CH₃SBrA^? (A^? = SbCl, AsF) were prepared by various routes and characterized by their Ramanspectra. CH₃SBrAsF crystallized in the monoclinic space group P2₁/c with a = 770,5(4) pm, b = 942,4(12) pm, c = 1329,3(14) pm, β = 100,28(6)°, Z = 4. Distances and bond angles in the cation are as expected.     

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.     

Thermisches Verhalten und Kristallstruktur von YAl3Cl12

Thermal Behaviour and Crystal Structure of YAl₃Cl₁₂ We determined the thermodynamic data of YAl₃Cl₁₂ ΔH = ?739.9 ± 3 kcal/mol and S = 136.1 ± 4 cal/K · mol by total pressure measurements and ΔH = ?739.1 ± 1.6 kcal/mol by solution calorimetry. Using DTA-investigations we established the phase diagram in the system AlCl₃–YCl₃. The crystal structure was refined on the basis of single crystal data (P3₁ 12; Z = 3; a = 1 046.8(2); c = 1 562.3(3) pm).     

K3Au5Pb: eine Schichtstruktur mit [AuAu3/2]-Gold-Tetraedern und [Pb2/2]-Blei-Ketten

K₃Au₅Pb: Layers of [AuAu_3/2] Gold Tetrahedra and [Pb_2/2] Lead Chains Silver coloured, brittle single crystals of K₃Au₅Pb were synthesized by reaction of potassium azide with gold sponge and lead powder at T = 920 K. The structure of the compound (space group Imma, Z = 4, a = 5.646(1) Å, b = 19.500(4) Å, c = 8.412(1) Å) was determined from X-ray single-crystal diffractometry data. The gold lead partial structure consists of layers of [AuAu_3/2] tetrahedra and [Pb_2/2] zigzag chains with four-bonded lead atoms which are connected to a framework structure via Au–Pb contacts. The potassium atoms occupy channels within the gold lead partial structure.     

Über geordnete Perowskite mit Kationenfehlstellen. XI. Verbindungen vom Typ ABB□1/4WVIO6 ≙ ABIIB□WO24 mit AII,BII = Ba,Sr

On Ordered Perovskites with Cationic Vacancies. XI. Compounds of Type A B B □_1/4W^VIO₆ ? A B^IIB □W O₂₄ with A^II, B^II = Ba, Sr Depending on the ionic radii of the two and three valent cations in the perovskites of type ABB □_1/4W^VIO₆ ?; AB^IIB □WO₂₄ order disorder phenomena are present. The results of the x-ray and vibrational spectroscopic investigations as well as the diffuse reflectance spectra and the visible photoluminescence are reported.     

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).     

Übergangsmetallchalkogenverbindungen. Darstellung,IR- und Raman-Spektren sowie röntgenographische Untersuchungen von Verbindungen des Typs A3(MeOS3)Cl und A2MeOS3 (A = K,Rb; Me = Mo W)

Transition Metal Chalkogen Compounds. Preparation, I.R. spectra, Raman Spectra, and X-Ray Investigations on Compounds of the Type A₃(MeOS₃)CI and A₂ MeOS₃(A = K, Rb; Me = Mo, W) The preparation, vibrational spectra, and x-ray data of compounds of the type A₃(MeOS₃)Cl and A₂MeOS₃ (A = K, Rb; Me = Mo, W) are reported. K₃(MoOS₃)Cl, K₃(WOS₃)Cl, and Rb₃(WOS₃)Cl are novel salts which can be prepared by passing H₂S through strong alcaline aqueous MoO and WO solutions containing KCl or RbCl. The salts crystallize in space group Pca2₁? C (No. 29) (Z = 4) with discrete MeOS tetrahedrons. The compounds A₂MeOS₃ (A = K, Rb; Ne = Mo, W) which are in part precipitable only by addition of organic solvents crystallize in space group Pnma? D (No. 62) with four formula units per unit cell.     

Neutral and Cationic Hexanuclear Rhenium Phosphine Clusters with μ3‐(Phosphido‐Chalcogenido), μ3‐(Arsenido‐Chalcogenido), and μ3‐(Imido or Oxo‐Chalcogenido) Hetero Ligand Shells

Reactions of dry THF/MeCN solutions of Ca[Re₆SCl(Cl^a)₆] with silylated derivatives E(SiMe₃)₂ (E = PhAs, PSiMe₃, HN, O, S) and addition of trialkylphosphine PPr₃ afford in high yields and at room temperature either the neutral clusters [Re₆SX(PPr₃)] ( 1 : X = As, 2 : X = P) or the ionic compounds [Re₆SX(PPr₃)]²⁺ · [Re₆S₆Cl₈]^2– ( 3 : X = NH, 4 : X = O, 5 : X = S). The compounds 1 – 5 were characterised by X‐ray crystal structure analysis. A di‐substitution reaction occurs on the {Re₆SCl}⁴⁺ cluster core, where the two inner μ₃‐chloro ligands Clⁱ are substituted by X (X = As, P, NH, O, S) and all six terminal chloro ligands Cl^a are exchanged by terminal PPr₃‐ligands.     

Über Perowskite Ba2BBTeVIO6

On Perovskites Ba₂B B Te^VIO₆ Compounds of composition Ba₂BBTe^VIO₆ with B^I = Li, Na; B^III = La, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Yb, Y, In, Sc crystallize in a cubic 1:1 ordered perovskite structure. The vibrational spectroscopic investigations show, that more species of TeO₆ octahedra are present in the lattice.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [OsBr(acac)(PPh3)] und [OsBr(acac)(AsPh3)]

Synthesis, Crystal Structures, and Vibrational Spectra of [OsBr(acac)(PPh₃)] and [OsBr(acac)(AsPh₃)] By reaction of tetrabromoacetylacetonatoosmate(IV) with PPh₃ or AsPh₃ in ethanol the complexes [OsBr(acac)(PPh₃)] ( 1 ) and [OsBr(acac)(AsPh₃)] ( 2 ) are formed, which are purified by chromatography on silica gel. X-ray structure determinations of single crystals of ( 1 ) (monoclinic, space group P 2₁/n, a = 13.035(2), b = 18.2640(14), c = 16.636(3) Å, β = 112.776(14)°, Z = 4) and ( 2 ) (monoclinic, space group P 2₁/c, a = 13.23(5), b = 18.35(2), c = 16.65(2) Å, β = 112.9(5)°, Z = 4) result in mean bond distances Os–P = 2.413, Os–As = 2.483, Os–Br = 2.488 and Os–O = 2.037 Å. The vibrational spectra (10 K) exhibit the inner ligand vibrations of the acac, PPh₃ and AsPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 499–522, of OsAs at 330–339, of OsBr at 213–214 and of OsO in the range 460–694 cm^–1.     

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.     

Röntgenographische Untersuchungen und Strukturchemie von Chalkogenomolybdaten und -wolframaten

X-Ray Investigations and Structure Chemistry of Chalkogenomolybdates and - tungstates. I. Crystallographic data of compounds of the type A₂MeX₄, A₂MeOX₃, and A₂MeO₂X₂ (A = K, NH, Rb, Cs; (Me = Mo, W; X = S, Se) are discussed and general trends are illustrated. The molybdates and tungstates A₂MeX₄ and A₂MeOX₃ (A = K, NH, Rb, Cs; X = S, Se) crystallize in the rhombic space group D? Pnma. The compounds (NH₄)₂MeO₂X₂ (Me = Mo, W; X = S, Se) crystallize in the monoclinic space group C? C2/c.     

Die Kristall- und MolekülStruktur von (S4N3)2SbCI5

The structure of (S₄N₃)₂SbCI₅ has been determined by X-ray methods using least-squares′ refinement. The compound crystallises monoclinic; C–P2₁/c, a = 9.24 Å, b = 17.77 Å, c = 11.29 Å, β = 110.06°, Z = 4. The antimony atom has a fivefold coordination the geometry being derived from a deformed octahedron, the S₄N-rings retained their planar shape.