On the crystal chemistry of three copper(II)-arsenates: Cu3(AsO4)2-III,Na4Cu(AsO4)2, and KCu4(AsO4)3

The three copper(II)-arsenates were synthesized under hydrothermal conditions; their crystal structures were determined by single-crystal X-ray diffraction methods:Cu₃(AsO₄)₂-III:a=5.046(2) Å,b=5.417(2) Å,c=6.354(2) Å, =70.61(2)°, =86.52(2)°, =68.43(2)°,Z=1, space group ,R=0.035 for 1674 reflections with sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a=4.882(2) Å,b=5.870(2) Å,c=6.958(3) Å, =98.51(2)°, =90.76(2)°, =105.97(2)°,Z=1, space group ,R=0.028 for 2157 reflections with sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a=12.234(5) Å,b=12.438(5) Å,c=7.307(3) Å, =118.17(2)°,Z=4, space group C2/c,R=0.029 for 1896 reflections with sin / 0.80 Å^–1.Within these three compounds the Cu atoms are square planar [4], tetragonal pyramidal [4+1], and tetragonal bipyramidal [4+2] coordinated by O atoms; an exception is the Cu(2)^[4+1] atom in Cu₃(AsO₄)₂-III: the coordination polyhedron is a representative for the transition from a tetragonal pyramid towards a trigonal bipyramid. In KCu₄(AsO₄)₃ the Cu(1)^[4]O₄ square and the As(1)O₄ tetrahedron share a common O—O edge of 2.428(5) Å, resulting in distortions of both the CuO₄ square and the AsO₄ tetrahedron. The two Na atoms in Na₄Cu(AsO₄)₂ are [6] coordinated, the K atom in KCu₄(AsO₄)₃ is [8] coordinated by O atoms.Die drei Kupfer(II)-Arsenate wurden unter Hydrothermalbedingungen gezüchtet und ihre Kristallstrukturen mittels Einkristall-Röntgenbeugungsmethoden ermittelt:Cu₃(AsO₄)₂-III:a = 5.046(2) Å,b = 5.417(2) Å,c = 6.354(2) Å, = 70.61 (2)°, = 86.52(2)°, = 68.43(2)°,Z = 1, Raumgruppe ,R = 0.035 für 1674 Reflexe mit sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a = 4.882(2) Å,b = 5.870(2) Å,c = 6.958(3) Å, = 98.51(2)°, = 90.76(2)°, = 105.97(2)°,Z = 1, Raumgruppe ,R = 0.028 für 2157 Reflexe mit sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a = 12.234(5) Å,b = 12.438(5) Å,c = 7.307(3) Å, = 118.17(2)°,Z = 4, Raumgruppe C2/c,R = 0.029 für 1896 Reflexe mit sin / 0.80 Å^–1.Die Cu-Atome in diesen drei Verbindungen sind durch O-Atome quadratisch planar [4], tetragonal pyramidal [4 + 1] und tetragonal dipyramidal [4 + 2]-koordiniert; eine Ausnahme ist das Cu(2)^{[4 + 1]}-Atom in Cu₃(AsO₄)₂-III: Das Koordinationspolyeder stellt einen Vertreter des Übergangs von einer tetragonalen Pyramide zu einer trigonalen Dipyramide dar. In KCu₄(AsO₄)₃ haben das Cu(1)^[4]O₄-Quadrat und das As(1)O₄-Tetraeder eine gemeinsame O—O-Kante von 2.428(5) Å, was eine Verzerrung der beiden Koordinationsfiguren CuO₄-Quadrat und AsO₄-Tetraeder bedingt. Die zwei Na-Atome in Na₄Cu(AsO₄)₃ sind durch O-Atome [6]-koordiniert, das K-Atom in KCu₄(AsO₄)₃ ist [8]-koordiniert.

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Zur Kristallchemie dreier Kupfer (II)-Arsenate: Cu₃(AsO₄)₂-III, Na₄Cu(AsO₄)₂ und KCu₄(AsO₄)₃

     

An extension of the CNDO/2 formalism for the study of transition metal complexes

A previously described extended CNDO/2 method is used for investigating the energy level distribution and electronic structure of trifluorophosphine metal complexes: Cr(PF₃)₆, Fe(PF₃)₅, Ni(PF₃)₄. The results are compared with the few experimental data which are known for these complexes. The metal-phosphorus bonds show large (P M) and (M P) charge transfers but small total charge transfers (M P) which induce on the metal in any case a small positive charge.Such ( + ) coordination bonds seem to be generally characterized by small bond overlap populations (or small Wiberg indices).     

Phase equilibria in the Ag4SSe-SnTe system

The phase diagram of the system Ag₄SSe-SnTe is studied by means of X-ray diffraction, differential thermal and metallographic analyses and measurements of the microhardness and the density of the material. This diagram is divided into two eutectic-type subdiagrams by the composition Ag₄SSe·2SnTe. The unit-cell parameters of the intermediate phases 3Ag₄SSe·SnTe (phase A) and -Ag₄SSe·2SnTe (phase B) are determined as follows: for phase A: a=0.7851 nm, b=0.7196 nm, c=0.6296 nm, =101.32°, =85.90°, =111.36°; for phase B: a=0.3662 nm, b=0.3303 nm, c=0.3343 nm, =90.74°, =108.94°, =91.91°. The phase Ag4SSe·2SnTe melts congruently at 615°C and a polymorphic transition of the phase takes place at T _- =110°C.This revised version was published online in November 2005 with corrections to the Cover Date.     

Ein neuer Typ quaternärer Oxometallate: K3Na2[InO4]

With K₃Na₂[InO₄] the first example of new kind of oxides of the type A₃A₂[MO₄] with R(A)>R(A) was prepared in form of colourless single crystals by oxidation of the intermetallic compound KNaIn₂. Intimate mixtures of the educts (K₂O₂: K_0.5Na_0.5In=1.2:1) were heated in sealed Ag-tubes (380 °C, 2 d, then 480 °C, 5 d). K₃Na₂[InO₄] crystallizes monoclinic (P2₁/n) witha=1012.6 pm,b=969.9 pm,c=725.4 pm, =91.02°;Z=4. The crystal structure was elucidated by four-circle diffractometer (PW 1100, Ag-K, 6047I _o(hkl),R=7.3%,R _w=4.4%). The new typ forms a very complicated 3-dimensional network ³ {Na₂InO₄} stuffed by 3 K⁺. The Madelung part of lattice energy, MAPLE, is calculated and discussed.

Professor Edwin Hengge zum 60. Geburtstag am 21. Juli 1990 gewidmet     

Photoluminescence Spectra and Crystallization of θ-Al2O3 and α-Al2O3 from AlOOH-Fe(NO3)3 Gels

Diphasic boehmite derived unseeded and seeded (by either -Al₂O₃, -Fe₂O₃, or Fe(NO₃)₃) alumina gel planar monoliths were examined by DTA, XRD and photoluminescence spectroscopy. Luminescence spectra enable sensitive monitoring of the - and -Al₂O₃ crystallization in heat-treated gels due to Cr³⁺ impurity traces. Fe(NO₃)₃ unlike other seeds effectively influences crystallization of both - and -Al₂O₃. The present results are interpreted as prevailing solution or Fe³⁺ ion effect on the crystallization process.     

The ground state of MoCr(O2CH)4 at theab initio SCF and CI levels. A symmetry adapted RHF energy functional with an artificial double minimum

Ab initio restricted Hartree-Fock (RHF) calculations carried out on the ground state of MoCr(O₂CH)₄ lead to two distinct energy minima according to the initial guess made for the set of trial vectors. It is shown that these two symmetry-adapted wavefunctions can be correlated with a twofold degenerate broken-symmetry solution previously characterized for the related system of higher symmetry Cr₂(O₂CH)₄. Complete CI expansions have been carried out from either RHF polarized wavefunction using as a basis the set of eight frontier MO's with high metal character. These expansions yield poorly resymmetrized wavefunctions. A similar CI expansion has finally been carried out from a wavefunction resymmetrized at the SCF level and corresponding to a saddle point of the RHF energy hypersurface. The total energy associated with this latter expansion is the lowest obtained in the present work. The natural orbital analysis corresponds to ()^1.86()^3.58()^1.54()^0.46()^0.42 (^*)^0.14 and shows that this resymmetrized CI expansion is in many respects similar to the correlated wavefunctions obtained for the homobinuclear parent systems.     

A comparison of quantitative theoretical results of the bonding in Ni(CO)4 and Ni(N2)4

Using non-empirical calculations the details of bonding in Ni(CO)₄ and in the analogous Ni(N₂)₄ are investigated.For Ni(CO)₄ some previous results are confirmed. In the calculation on Ni(N₂)₄ the close resemblance with Ni(CO)₄ is quite remarkable. The main difference is contained in the fact that carbon has a lower -electron density than nitrogen and that therefore the *-orbital in CO is lower in energy and geometrically more favourable for back donation.From the calculations we find a difference in metal-ligand bond energy between the carbonyl complex and the dinitrogen complex of approximately 18 kcal/mol.     

Crystal structure of Li2Cu3(SeO3)2(SeO4)2

Summary Single crystal X-ray data of the hydrothermally grown new phase Li₂Cu₃(SeO₃)₂(SeO₄)₂ were measured with a four-circle diffractometer up to sin /=0.81 Å^–1 [I2/a,Z=4,V=1175.5 ų,a=16.293(6),b=5.007(2),c=14.448(6) Å, = 94.21(1)°]. The structure was determined by direct and Fourier methods and refined toR=0.034,R _w =0.027 for 2 086 independent reflections.Cu(1)^[4+1]O₅ forms a tetragonal pyramid, Cu(2)^{[4 + 2]}O₆ is a strongly elongated octahedron. The Li atom is surrounded by four O atoms forming a distorted tetrahedron. Se(IV)O₃ and Se(VI)O₄ groups are in accordance to literature, mean Se-O bond lengths are 1.714 and 1.644 Å.

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Die Kristallstruktur von Li₂Cu₃(SeO₃)₂(SeO₄)₂

Zusammenfassung Einkristall-Röntgendaten der hydrothermal gezüchteten neuen Phase Li₂Cu₃(SeO₃)₂(SeO₄)₂ wurden mit einem Vierkreisdiffraktometer im Bereich bis zu sin /=0.81 Å^–1 gemessen [I2/a,Z=4,V=1175.5 ų,a=16.293(6),b=5.007(2),c=14.448(6) Å, =94.21(1)°]. Die Kristallstruktur wurde mittels direkter und Fourier-Methoden bestimmt und für 2 086 unabhängige Reflexe zuR=0.034,R _w =0.027 verfeinert.Cu(1)^[4+1]O₅ bildet eine tetragonale Pyramide, Cu(2)^[4+2]O₆ ist ein stark verlängertes Oktaeder. Das Li-Atom ist von vier O-Atomen in Gestalt eines verzerrten Tetraeders umgeben. Die Se(IV)O₃-und Se(VI)O₄-Gruppen entsprechen der Literatur, die mittleren Se-O-Abstände betragen 1.714 und 1.644 Å.

     

Complex polarizability as used to analyze dielectric relaxation measurements

The effect of representing dielectric properties in terms of the complex polarizability ^c = – i is examined. Loss curves ( and tan ) are shifted towards higher frequencies, revealing the existence of new relaxations and allowing the clarifications of ones already known. We have calculated the shift ratios (at maximum or tan )/ (at maximum or tan ) from the more conventional empirical equations representing the dielectric behavior. Some examples are given.     

Steroids,LIII: New routes to aminosteroids

Summary Steroid ketoximes were reduced with sodium tetrahydroborate in the presence of nickel chloride or molybdenum trioxide. These processes yielded 17- and 20-aminosteroids (1c–5c) in higher yields than common reduction methods.

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Steroide, 53. Mitt.: Neue Wege zu Aminosteroiden

Zusammenfassung Oxime von Ketosteroiden wurden mit NaBH₄ in Gegenwart von NiCl₂ und MoO₃ reduziert. Dieses Verfahren lieferte 17- und 20-Aminosteroide(1c–5c) in größeren Ausbeuten als übliche Methoden.

     

The thermal decomposition of (NH4)[VO(O2)2(NH3)]

The compound, (NH₄)[VO(O₂)₂(NH₃)], thermally decomposes to ammonium metavanadate, which then decomposes to vanadium pentoxide. Using a heating rate of 5 deg·min^–1, the first decomposition step occurs between 74° and 102°C. The transformation degree dependence of the activation energy (-E) is shown to follow a decreasing convex form, indicating that the first decomposition step is a complex reaction with a change in the limiting stage of the reaction. Infrared spectra indicated that the decomposition proceeds via the gradual reduction of the ratio of the (NH₄)₂O to V₂O₅ units from the original 11 ratio in ammonium metavanadate, which may be written as (NH₄)₂O·V₂O₅, to V₂O₅.The assistance of Professor A. M. Heyns (University of Pretoria) and Professor K. L. Range (University of Regensburg) is gratefully acknowledged as well as the financial assistance of the University of Pretoria and the FRD.     

Mono and dinuclear cationic rhodium(I) and iridium(I) complexes with sulphur donor and group Vb ligands

Summary Rhodium(I) and iridium(I) mixed complexes of the formulae [M(diolefin)LL]ClO₄, [M(diolefin)L₂L]ClO₄, [(diolefin)LIr(-L)₂IrL(diolefin)](ClO₄)₂, [(diolefin)LM(-L-L)ML'(diolefin)](ClO₄)₂, [(diolefin)Rh{-(L-L)}₂Rh(PPh₃)₂](ClO₄)₂ and [(diolefin)LIr{-(L-L)}₂IrL (diolefin)](C1O₄)₂, (L=monodentate sulphur ligand, L-L=bidentate sulphur ligand, L=group Vb ligand; M=Rh, diolefin=1,5-cyclooctadiene (COD) or 2,5-norbornadiene (NBD); M=Ir, diolefin=COD) are described.Author to whom all correspondence should be directed.     

Die Kristallstrukturen der Kupfer(II)-oxo-selenite Cu2O(SeO3) (kubisch und monoklin) und Cu4O(SeO3)3 (monoklin und triklin)

Syntheses within the system CuO-SeO₂-H₂O revealed four copper(II)-oxo-selenites. The crystal structures of these compounds were determined by single crystal X-ray techniques. Chemical formulae, lattice parameters and space groups are: Cu₂O(SeO₃)-I [a=8.925 (1) Å, P2₁3], Cu₂O(SeO₃)-II [a=6.987 (5) Å,b=5.953 (4) Å,c=8.429 (6) Å, =92.17 (3)°, P2₁/n], Cu₄O(SeO₃)₃-I [a=15.990 (8) Å,b=13.518 (8) Å,c=17.745 (12) Å, =90.49 (5)°, P2₁/a], and Cu₄O(SeO₃)₃-II [a=7.992 (6) Å,b=8.141 (6) Å,c=8.391 (6) Å, =77.34 (3)°, =65.56 (3)°, =81.36 (3)°, ].All the Cu atoms are-with one exception-[4], [4+1], and [4+2] coordinated by O atoms. The four nearest O atoms are more or less distorted square planar arranged. Within the CuO₄ squares the Cu-O bond lengths are significantly shorter for the [4] coordinated O atoms as compared with those of the [4+1] and [4+2] coordinated Cu atoms. The exception in the coordination of the Cu atoms is the Cu(1) atom in Cu₂O(SeO₃)-I with the site symmetry 3, which is trigonal dipyramidal [5] coordinated. A common feature of these four crystal structures is, that O atoms outside the SeO₃ groups are tetrahedrally coordinated by four Cu(II) atoms. The Se atoms are as usual [3] coordinated, building up SeO₃ pyramids. In all these four compounds the copper-oxygen polyhedra are combined to a three-dimensional network.

     

New chiral acyclic analogs of 2′-deoxynucleosides

Convenient methods for the synthesis of chiral 2,3-seco-2-deoxynucleosides were developed. An isopropylidene protective group was used to block the 3,5-hydroxy groups in 2,3-seco-uridine. Conversion of the hydroxymethyl group to a methyl group was accomplished by chlorination with a mixture of CCl₄ and Ph₃P with subsequent reduction with n-Bu₃SnH. 2,3-seco-2-Deoxyuridine was obtained after deacetonation. The (S) enantiomer was similarly synthesized starting from 1-(-D-arabinofuranosyl)uracil. 3-O-tert-Butyldimethylsilyl-5-O-(p-monomethoxytrityl)-2,3-seco-2-deoxyuridine, which has optically active centers at C₍₁₎ and C₍₄₎, was also synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 822–826, June, 1988.The authors thank Professor M. Ya. Karpeiskii for his constant interest in this research.     

Untersuchungen der Hydroxylammonium-Fluorozirconate(IV)

Summary Hydroxylammonium fluorozirconates have been investigated. Two new microcristalline phases have been isolated from aqueous solutions: (NH₃OH)₂ZrF₆ (1) and (NH₃OH)₃ZrF₇ (2). The crystals were prepared by slow evaporation of the solution of NH₂OH, Zr, and HF. Different compositions of the crystals were achieved by varying the molar ratios of the components. They were characterized by thermal analysis, vibrational spectroscopy, and structure (single crystal x-ray methods). (NH₃OH)₂ZrF₆ (1) crystallizes triclinic, P (No.: 2),a=7.400(2),b=7.609(2),c=7.887(2) Å, =57.29(3)°, =62.16(3)°, =67.83(2)°. (NH₃OH)₃ZrF₇ (2) crystallizes triclinic, P (No.: 2),a=7.128(1),b=7.989(1),c=8.888(1) Å, =109.72(1)°, =91.01(1)°, =104.27(1)°.

     

The electronic structure of molecules by a many-body approach

The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C₃H₆ the ordering of the ionization potentials is 2e(), 1e(), 2a₁(), 1a₂(), 1e(). The assignment of the 2a₁ and the 1a₂ ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C₂H₄O the ordering of the ionization potentials is 2b ₁(), 4a ₁, 1a ₂(), 2b ₂,3a ₁, 1b ₁(), 1b ₂, 2a ₁ and for C₂H₅N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory.     

The crystal structure of Fe(SeO2OH)(SeO4)·H2O

Summary The crystal structure of the hydrothermally synthesized compound Fe(SeO₂OH) (SeO₄) · H₂O was determined by single crystal diffraction methods:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, space group P2₁/c,R=0.029,R _w=0.027 for 2430 independent reflections (sin /0.76 Å^–1). Isolated FeO₅(H₂O)-octahedra share five corners with [SeO₂OH] and [SeO₄] groups to form sheets parallel to (100). These sheets are interconnected via hydrogen bonds only.

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Die Kristallstruktur von Fe(SeO₂OH)(SeO₄)·H₂O

Zusammenfassung Die Kristallstruktur der hydrothermal dargestellten Verbindung Fe(SeO₂OH) (SeO₄)·H₂O wurde mittels Einkristallbeugungsmethoden bestimmt:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, Raumgruppe P2₁/c,R=0.029,R _w=0.027 für 2 430 unabhängige Reflexe (sin / 0.76 Å^–1). Isolierte FeO₅(H₂O)-Oktaeder teilen fünf Ecken mit [SeO₂OH]- und [SeO₄]-Gruppen, wobei sie Schichten parallel (100) bilden. Diese Schichten sind nur über Wasserstoffbrücken miteinander verbunden.

     

Mixed-ligand and binuclear complexes of oxovanadium(IV)

Summary Mixed ligand complexes of the type [VOLA]ClO₄ where L=5-bromosalicylaldehyde (L) or 5-nitrosalicylaldehyde (L) and A=2, 2-dipyridyl (A) or 1, 10-phenanthroline (A) have been prepared. Treatment of the mononuclear complexes, [VOLA]ClO₄, withp-phenylenediamine (ppd) orm-phenylenediamine (mpd) yielded homobinuclear [VOLA-NC₆H₄N-LAVO](ClO₄)₂, complexes, which were characterised by elemental analyses, spectra, magnetic susceptibility and molar conductance measurements.     

Sorption of C6 Alkanes in Aluminophosphate Molecular Sieve, AlPO4-5

Sorption of C₆ alkanes viz.,n-hexane, 2-methylpentane, 2,2-dimethyl butane, 2,3-dimethyl butane, cyclohexane and methyl cyclopentane in AlPO₄-5 is studied and sorption capacity and thermodynamic parameters (H⁰, H, G, S and S_a) at various sorption coverage for these sorbates have been estimated. The initial heat of sorption (H⁰) is found to increase with the degree of branching in the alkane chain. The sorbate-sorbate interactions are found to be more prominent during the sorption of doubly branched alkanes and cyclic alkanes and a higher sorption capacity has been observed for cyclic alkanes. Based on the results obtained, a packing model has been proposed for various C₆ alkanes inside the AlPO₄-5 channel.     

A structural study of the naringin-β-cyclodextrin complex

The structure of the inclusion complex formed between naringin (naringenin-7-O--neohesperidoside) and-cyclodextrin (BCD) was studied in detail by UV and NMR spectroscopic techniques and potentiometry. A binding constant value of 1016±150M^–1 was arrived at from UV studies. Potentiometric studies showed that pK values of 4-OH and 5-OH were affected by and-cyclodextrins. One-dimensional difference NOE and spin-lattice relaxation time (T ₁) measurements indicated that the aglycone protion was affected more than the neohesperidoside portion. TheT ₁ values analysed for local motions indicated that _c values of complexed naringin was higher than that of free naringin. The internal rotation calculated for different groups showed _i values for the phenolic and dihydrobenzopyran portion decrease by a factor of 2. Also a value of 0.12–0.17 observed for the aglycone portion indicated that the coupling between guest and host is weak. All the studies have shown that the disposition in which the phenol group at 2 is inside the BCD cavity with 4-keto and 5-OH hydrogen bonded to the secondary hydroxyl groups at the rim of the wider end of the BCD cavity is the most probable one.