Atranes

The UV absorption spectra in the 1800–2400 Å region of 1-alkylsilatranes and 1-alkylgermatranes have been studied, confirming the presence of SiN and GeN bonds, respectively, in these compounds.For part XIX, see [1].     

The structure of organic derivatives of hexacoordinated germanium. (O→Ge) chelated bis-(2-oxo-1-hexahydroazepinylmethyl)difluorogermane and bis-(2-oxo-1-hexahydroazepinylmethyl)fluorogermane tetrafluoroborate

Two fluoro derivatives of hexacoordinated germanium containing chelated 2-oxo-1-hexahydroazepinylmethyl ligands were investigated by X-ray diffraction analysis. The coordination polyhedron of the Ge atom in difluoride1 is a somewhat distorted octahedron with the following bond lengths (Å): Ge-F 1.799(2), GeO 2.185(3), and Ge-C 1.945(4). Tetrafluoroborate 2 has an ionic structure; the valence environment of the Ge atom is a distorted trigonal bipyramid open in the direction of the BF ₄ ^– anion. The bond lengths in 2 are: Ge-F 1.792(8), GeO 2.001(4), and Ge-C 1.937(9) Å; the Ge...F(anion) distances are 3.43(1) and 3.68(1) Å. Analysis of the geometry of1,2, and related structures containing hexa-coordinated germanium shows that the parameters of their hypervalent moieties are related to each other by dependences similar to those observed in compounds of pentacoordinated Si and Ge.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1427–1431, August, 1994.This work was carried out with the financial support of the Russian Foundation for Basic Research (project No 93-03-4855).     

Electronic transitions in mono-olefinic hydrocarbons

Mulliken-Wolfsberg-Helmholz calculations have been performed on ethylene and methyl-substituted ethylenes. The Mulliken assignment (i.e., that the transition between 5–7 eV isR(3s)N in nature) is validated. Spin-orbit coupling calculations indicate that the weakest olefin band at 2700 Å is too intense to be triplet singlet, as is usually assumed. However, behaviour of a predicted low-energyR ^*(3s, 2s)N transition agrees well with the characteristics of these weak bands in the absorption spectra of liquid olefins. That these trends are believable is supported by the accuracy with which the computations predict the experimental changes of ionization potential andVN transition energy caused by increased methylation. In particular, it is predicted that the excitation energy of theVN transition should be strongly dependent on molecular geometry — in agreement with experiment. It is suggested, on the basis of intensity calculations, that theR(3s)N transition gains part of its intensity, at least,via vibronic stealing from theVN transition. Computations on cyclic olefins predict the possibility of several low-lying ^* transitions; the unusual broadening of theVN transition in these molecules may possibly be associated with this complexity. Computations on methylene cycloalkanes and cycloalkylidene-cycloalkanes reveal that-strain can lead to low-lying ^* (valence-shell) transitions. In general, it is found that the 3s atomic orbital can mix appreciably, in both bonding and antibonding combinations, with valence-shell orbitals.

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Zusammenfassung Mulliken-Wolfsberg-Helmholz-Rechnungen werden für Äthylen und eine Reihe methylsubstituierter Äthylene durchgeführt. Die Mullikenzuordnung [d. h. der Übergang zwischen 5 –7 eV entsprichtR(3s)N] wird daraufhin für zutreffend erklärt. Spin-Bahn-Kopplungs-Berechnungen deuten darauf hin, daß das schwächste Olefinband bei 2700 Å zu intensiv ist, um — wie gewöhnlich angenommen —in Triplett-Singulett-Übergang zu sein. Andererseits stimmt das Verhalten eines energetisch tief liegendenR ^*(3s, 2s)N-Übergangs gut mit den Charakteristika dieser schwachen Banden im Absorptionsspektrum der flüssigen Olefine überein. Daß diese Interpretation möglich ist, wird auch durch die Genauigkeit unterstützt, mit der eine Berechnung die experimentell gefundene Änderung von Ionisations- undVN-Übergangsenergie bei zunehmender Methylierung ergibt. Insbesondere wird auch vorhergesagt, daß die Anregungsenergie desVN-Übergangs stark von der molekularen Geometrie abhängt — in Übereinstimmung mit dem Experiment. Es wird deshalb auf Grund einer Intensitätsberechnung vorgeschlagen, daß derR(3s)N-Übergang zumindest einen Teil seiner Intensität durch eine Schwingungs-Anleihe vomVN-Übergang gewinnt. Berechnungen für cyclische Olefine weisen auf verschieden niedrig liegende ^*-Übergänge hin; die ungewöhnliche Verbreitung derVN-Bande bei diesen Molekülen kann möglicherweise damit zusammenhängen. Berechnungen der Methyl-cycloalkane und der Cycloalkylidin-cycloalkane zeigen, daß eine Spannung im-Gerüst zu einem tief liegenden ^*-(Valenz-) Übergang führen kann. Im allgemeinen zeigt sich, daß 3s-Zustände merklich an Valenzzuständen beteiligt sein können, und zwar sowohl bei bindenden als auch bei lockernden Molekülzuständen.

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Résumé Des calculs Mulliken-Wolfsberg-Helmholz ont été effectués sur l'éthylène et sur la série des éthylènes méthyl-substitués. Ces calculs confirment l'assignation de Mulliken: la transition entre 5–7 eV est de natureNR(3s). Des calculs de couplage spin-orbite montrent que la bande oléfinique la plus faible à 2700 Å est trop intense pour être une transition singulet-triplet comme on le suppose généralement. Cependant, le comportement d'une transition théorique de faible énergieNR ^* (3s, 2s) est en accord avec les caractéristiques de ces faibles bandes dans le spectre d'absorption des oléfines liquides. La vraisemblance de ce point de vue est renforcée par la précision avec laquelle les calculs prédisent l'évolution des potentiels d'ionisation, et des énergies des transitionsNV par méthylation croissante. En particulier, il est prévu que l'énergie d'excitationNV dépend fortement de la géométrie moléculaire ce qui est en accord avec l'expérience. On suggère sur la base de calculs d'intensité que la transitionNR (3s) tire une partie de son intensité au moins par transfert vibronique à partir de la transitionNV. Des calculs sur des oléfines cycliques prédisent la possibilité de plusieurs transitions ^* de faible énergie; l'élargissement inhabituel de la transitionN V dans ces molécules pourrait provenir de cette situation. Des calculs sur les méthylène-cycloalkanes et les cycloalkylidène cycloalkanes révèlent la possibilité pour une tension de provoquer l'existence de transitions ^* (couche de valence) de faible énergie. On trouve qu'en général les orbitales atomiques 3s peuvent se mélanger d'une manière appréciable aux orbitales de la couche de valence donnant des combinaisons liantes et antiliantes.

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Supported by The United States Air Force and The United States Atomic Energy Commission-Biology Branchvia Grants to the Louisiana State University.     

Quantum-chemical Investigation of the Hyprevalent Intramolecular Coordination X←N (X = C,Si, Ge) in Quasimonocyclic Models of IVa Group Atranes

The structure and the pentacoordination effect in quasimonocyclic models of IVa group atranes were investigated by ab initio[MP2 (full) /6-311+G **] and the density functional [B3LYP/6-311+G **] quantum chemical calculations. The calculations revealed considerable stabilization of the quasimonocyclic conformations relative to their free-of-strain trans-s-transconformations, which is caused by the formation of secondary (R)XN (X=C, Si, Ge) bonds of the hypervalent type. The strength of the intramolecular (R)XN coordination increases in the order X=C, Si, Ge. The nature of attractive (R)XN coordination is determined by donor-acceptor interaction of the nitrogen lone electron pair and antibonding orbital which primary localize at the X-R bond. Energy of X ··· N (X=Si, Ge) contact is about 3-7 kcal mol^-1.     

Electronic absorption spectra of rhenium(VII) compounds: The effect of the coordination number

Changes in electronic absorption spectra in the following series: MeRe(L₂)O₃ McReO3 ReO4– ReO₆5–, have been studied in terms of the qualitative MO scheme.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1563–1566, June, 1996.     

Effect of the nature of the solvent and the temperature on the frequency and intensity of the stretching vibration of the Ge-H bond in the IR spectra of 1-hydrogermatranes

Conclusions The Ge-H stretching vibration in the IR spectra of 1-hydrogermatranes varies under the influence of the solvent and the temperature as a result of the presence of the transannular Ge N bond. The change in the length of this bond with variation in the polarity of the solvent and the temperature of the solutions is smaller in germatranes than for the Si N bond in the isostructural silatranes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1758–1761, August, 1985.     

Electronic transitions in mono-olefinic hydrocarbons

Investigation of the onset of absorption in the spectra of liquid mono-olefins reveals transitions which seem too intense to be of a triplet singlet nature. Comparison with calculated intensities and excitation energies suggests that an R ^*N(*) assignment migth be appropriate.The R(3s)N transitions in the vapor spectra have been re-investigated and f-numbers have been estimated. Comparison with calculated intensities indicates that this transition might gain part of its intensity via vibronic stealing from the VN transition. This mechanism is shown to offer a possible — but by no means unique — explanation for the vibrational structure of the R(3s)N transition of cyclopentene.Self-pressure dependence of the R(3s)N transition in mono-olefins indicates, as do MO calculations, that the 3s Rydberg orbital is neither as diffuse nor as atomic-like as it is usually assumed to be in these molecules.

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Zusammenfassung Die Untersuchung des Absorptionsbeginns in den Spektren flüssiger Monoolefine zeigt Übergänge, die zu intensiv erscheinen, um vom Triplet-Singlet-Typ zu sein. Der Vergleich mit berechneten Intensitäten und Anregungsenergien läßt vermuten, daß eine Zuordnung R ^*N(^*) richtig sein könnte.Die R(3s)N-Übergänge in der Dampfphase wurden untersucht und die f-Werte abgeschätzt. Der Vergleich mit berechneten Intensitäten zeigt, daß dieser Übergang ein Teil seiner Intensität über vibronische Wehcselwirkung vom VN-Übergang gewinnen könnte. Es wird gezeigt, daß dieser Mechanismus eine mögliche — aber keineswegs eindeutige Erklärung für die Schwingungsstruktur des R(3s)N-Übergangs von Cyclopenten darstellt.Die Abhängigkeit des R(3s)N-Übergangs vom Eigendruck in Monoolefinen zeigt, ebenso wie MO-Rechnungen, daß das 3s-Rydberg-Orbital weder so diffus noch so atomartig ist, wie es normalerweise in diesen Moelkülen angenommen wird.

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Résumé L'étude de l'absorption dans les spectres des mono-oléfines liquides révèle des transitions qui semblent trop intêses pour être du type tripletsingulet. La comparaison avec les intensités et les énergies calculées suggère une identification du type R ^*N(*).Les transitions R(3s)N dans le spectre en phase vapeur ont été réétudiées et l'on a évalué les nombres f. La comparaison avec les intensités calculées indique que cette transition acquiert une partie de son intensité par couplage vibronique à partir de la transition VN. Ce mécanisme offre une explication possible — mais certainement pas unique — pour la structure vibrationnelle de la transition R(3s)N du cyclopentene.La dépendance à la pression propre de la transition R(3s)N dans les mono-oléfines indique, comme d'ailleurs les calculs O.M., que l'orbitale Rydberg 3s n'est ni aussi diffuse ni aussi atomique qu'on le suppose d'habitude dans ces molécules.

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Supported by the United States Air Force and The United States Atomic Energy Commission—Biology Branch via Grants to the Louisiana State University.     

Inclusion complexes of the natural product gossypol. Strong influence of the guest on the host structure in channel-type isostructural inclusion complexes of gossypol

The crystal structures of 1 : 1 inclusion complexes of gossypol with tetrahydrofuran (GPTHF), cyclohexanone (GPCHN) and butanal (GPBTA) have been determined by X-ray structure analysis. The crystals of GPTHF are triclinic, space group P,a = 10.788(2),b = 10.979(3),c = 13,880(2) Å, = 80. 11(2), = 103.87(1), = 77.96(2)°,V = 1517.8(6) ų,Z = 2,R = 0.052 for 2701 observed reflections. The crystals of GPCHN are triclinic, space groups P,a = 10.803(4),b = 11.157(5),c = 15.428(6) Å, = 108.75(3), = 106.93(3), = 103.34(3)°,V = 1573(1) ų,Z = 2,R = 0.071 for 1879 observed reflections. The crystals of GPBTA are triclinic, space group P,a = 10.190(2),b = 11.335(1),c = 14.665(2) Å, = 73.04(1), = 103.74(1), = 81.07(1)°,V = 1529.9(5) ų,Z = 2,R = 0.068 for 2964 observed reflections. Crystal data for another 13 isostructural inclusion complexes are given.[/p]In this isostructural group of complexes guest molecules are accommodated in channels and are hydrogen bonded to the host molecules via an 0(1)-H....O(1) hydrogen bond. The molecular association changes significantly with the shape and size of the guest component. In GPTHF centrosymmetric dimers of gossypol formedvia O(5)-H...O(3) hydrogen bonds are associated in columns via a weak O(4)-H...O(8) hydrogen bond. In GPCHN the latter bond disappears as the distance O(4)-O(8) is increased to 3.73 Å. In GPBTA the O(5)-H...O(3) bond is replaced by three centre hydrogen bonds O(5)-H...O(2) and O(3)-H...O(5), and a centrosymmetric dimer of a new type is formed. These dimers are further connected by two weak hydrogen bonds to form columns. The butanal molecule interacts with the host structure via two hydrogen bonds. This indicates that a guest component can activate or deactivate different functional groups of the host in channel inclusion complexes of gossypol for hydrogen bond formation.     

Atranes

Magnetic susceptibilities and dipole moments of 1-oxovanadatranes are measured, and their IR spectra investigated. The results obtained show these compounds to contain a transannular dative VN bond.For Part VIII see [19].     

The electronic structures of pyridine-N-oxide and related compounds

The electronic structures of pyridinen-oxide, 2- and 4-methoxypyridinen-oxide, their conjugate acids, and 2- and 4-pyridone are calculated using the Pariser-Parr-Pople SCF-CI approximation. The results indicate that the¹ B ₁¹ A ₁ transition of pyridinen-oxide lies in the same energy region as the transition previously assigned as beingn -*. The strong electronic transitions in the 250–280 m region of pyridine-n-oxide, 4-methoxypyridinen-oxide, and 4-pyridone are assigned as being¹ A ₁¹ A ₁.

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Zusammenfassung Die elektronischen Strukturen von Pyridin-N-Oxyd, 2- und 4-Methoxypyridin-N-Oxyd, ihrer Kationen, und von 2- und 4-Pyridon wurden nach der Methode von Pariser-Parr-Popple SCF-CI berechnet. Es ergibt sich, daß der¹ B ₁¹ A ₁ Übergang des Pyridin-N-Oxyds etwa die gleiche Energie besitzt, wie die bisher einemn -* Übergang zugeordnete Bande. Der intensitätsstarke Übergang des Pyridin-N-oxyds, 4-Methoxypyridin-N-oxyds und 4-Pyridons im Bereich von 250–280 m wird einem¹A₁¹ A ₁ Übergang zugeordnet.

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Résumé Les structures électroniques de l'oxyde de pyridine, desn-oxydes de 2- et 4-methoxypyridine, leurs cations, et les 2- et 4-pyridone sont calculés par l'approximation Pariser-Parr-Pople SCF-CI. Les résultats obtenus indiquent que la transition¹ B ₁¹ A ₁ dun-oxyde de pyridine est située dans la même région d'énergie que la transition assignée auparavant comme étantn -*. Les transitions électroniques fortes dans la région de 250–280 m dun-oxyde de pyridine, dun-oxyde de 4-methoxypyridine et du 4-pyridone sont assignées comme étant¹ A ₁¹ A ₁.

     

The designed synthesis and crystallographic characterization of three novel heterotrimetallic linear complexes of [Et4N][(Ph3P)2{M′S2 MS2Fe}Cl2] (M=Mo,M′=Ag;M=W,M′=Cu,Ag)

The complexes [Et₄N][(Ph₃P)₂{MS₂ MS₂Fe}Cl₂] (M=Mo,M=Ag;M=W,M=Cu, Ag) have been obtained by reaction of [Et₄N]₂[S₂ MS₂FeCl₂] (M=Mo, W) with Cu(PPh₃)₃Cl or Ag(PPh₃)₃NO₃ in MeCN/CH₂Cl₂, respectively. Crystal data for [Et₄N][(PPh₃)₂ {AgS₂MoS₂Fe}Cl₂] (I): triclinic, P (No. 2),Z=2,a=13.41(1)Å,b=15.54(1)Å,c=12.30(1)Å, =105.24(6)°, =94.63(7)°, =101.38(6)°, andV=2399(4)ų. The bond lengths of Mo-Fe bond and the Mo-Ag distance are 2.756(2)Å and 3.033(2)Å, respectively. Crystal data for [Et₄N][(PPh₃)₂ {AgS₂WS₂Fe}Cl₂] (II): triclinic, P (No. 2),Z=2,a=13.457(5))Å,b=15.601(6)Å,c=12.338(4)Å, =105.20(3)°, =94.61(4)°, =101.43(4)°, andV=2426(2)ų. The bond length of W-Fe bond and the W-Ag distance are 2.786(2)Å and 3.076(1)Å, respectively. Crystal data for [Et₄N][(PPh₃)₂ {CuS₂WS₂Fe}Cl₂] (III): triclinic, P (No. 2),Z=2,a=13.498(5)Å,b=15.372(4)Å,c=12.340(4)Å, =105.54(2)°, =93.32(3)°, =101.40(3)°, andV=2401(1)ų. The bond lengths of W-Fe bond and the W-Cu bond are 2.800(1)Å and 2.851(1)Å, respectively.     

Crystal and molecular structure of nitraminotetrazole and nitramino-1,2,4-triazole. IV. 5-nitraminotetrazole sodium salt sesquihydrate

The structure of 5-nitraminotetrazole sodium salt sesquihydrate was determined by X-ray diffraction. The crystals are monoclinic, space group P2₁/c;a = 3.551(1) Å, b = 21.834(4) Å, c = 9.075(2) Å; = 110.68(3)°; V = 658.3(2) ų; Z = 4; _calc = 1.807 g/cm³. The anion is planar and has an intramolecular hydrogen bond. The negative charge of the anion is localized on one of the oxygens of the nitro group. The sodium cation (c.n.6) is coordinated by three oxygen atoms of different anions and three oxygens of crystallization water. One of the crystallization water molecules is disordered in the unit cell. The anions are hydrogen-bonded with each other and with crystallization water molecules.Original Russian Text Copyright © 2004 by A. M. Astakhov, A. D. Vasiliev, M. S. Molokeev, L. A. Kruglyakova, A. M. Sirotinin, and R. S. StepanovTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 562–565, May–June 2004.     

Hydrothermal Syntheses and Structural Characterization of Two Novel Arsenic–Vanadium Clusters: [Co(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O and [2,2′-bpy][Ni(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O

Two new arsenic–vanadium clusters, [Co(2,2- bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (1), [2,2-bpy][Ni(2,2-bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (2) (2,2-bpy=2,2-bipyridine), have been hydrothermally synthesized and characterized by IR, elemental analysis, UV–VIS, EPR, TGA, XPS, and single crystal X-ray diffraction analysis. Crystal data: 1, triclinic, P1, a=14.368(3) Å, b=16.753(3) Å, c=24.632(5) Å, =94.15(3)°, =93.16(3)°, =113.05(3)°, Z=2; 2, monoclinic, P2₁/c, a= 30.2150(4) Å, b=14.0690(3) Å, c=26.0536(3) Å, =106.8960(10)°, Z=4. X-ray crystallographic studies showed that crystals 1 and 2 are both composed of discrete cluster anion [As₈V₁₄O₄₂(H₂O)]^4– and transition metal coordination complexes [M(2,2-bpy)₃]²⁺ (M=Co or Ni). Interestingly, compound 2 contains another neutral organic space filler of 2,2-bpy. To the best of our knowledge, compounds 1 and 2 are the first examples of structurally characterized vanadium/2,2-bpy/arsenate polyoxometallates.     

Ab initio Study of H2O–HCl (1:1, 1:2, 2:1) Complexes

This paper reports on an ab initio (6-31G**) study of 1:1, 1:2, and 2:1 (H₂O) _n (HCl) _m complexes. Stable configurations of the 1:2 and 2:1 (H₂O) _n (HCl) _m complexes and their geometrical and energy characteristics were determined. The vibrational analysis of the complexes was carried out. The effect of hydrogen bonding due to S₁S₀ and T₀T₁ electronic excitations is considered.     

Pentacoordination of the silicon atom in phenacetoxymethyltrifluorosilane

Conclusions By means of IR spectroscopy, it was shown that the Si atom in phenacetoxymethyltrifluorosilane is pentacoordinated, apparently by forming both intra-and intermolecular bonds of the type C=O Si. A change in the dielectric permeability of the medium elicits significant shifts of stretching vibration frequencies in C=O, SiF₃, and COC groups of the compound. When phenacetoxymethyltrifluorosilane interacts with pyridine, the coordination number of Si increases to six. It is proposed that two types of complexes are formed in this interaction: (I): 2Py, with the bond groupings N Si N and a free C=O group; and (I): 1 Py, with the fragment N Si O=C.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2712–2715, December, 1986.     

Tetrakis(2-fluorophenylamino)silan und sein erstes Kondensationsprodukt N-(2-fluorophenyl)-Si,Si, Si,Si′, Si′, Si′-hexakis(2-fluorophenylamino)-disilazan. Synthesen und Kristallstrukturen

Zusammenfassung Tetrakis(2-fluorophenylamino)silan (1) wurde als Precursor zur Darstellung poröser, nitridischer Festkörper synthetisiert und mit Hilfe der Einkristallröntgenstrukturanalyse charakterisiert (C2/c;a=16.771(7) Å,b=16.827(5) Å,c=16.753(6) Å, ß=111.00(2)°,z=8). Beim Erhitzen mit Ammoniumcarbamat als Katalysator wurde N-(2-fluorophenyl)-Si, Si, Si, Si, Si, Si, -hexakis(2-fluorophenylamino)disilazan (2) als erstes Kondensationsprodukt isoliert ( ;a=9.331(1) Å,b=13.698(5) Å,c=16.164(4) Å, =90.34(2)°, ß=103.03(2), =103.04(3)°, Z=2).

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Tetrakis(2-fluorophenylamino)silane and its first product of condensation N-(2-fluorophenyl-Si, Si, Si, Si, Si, Si-hexakis(2-fluorophenylamino)disilazane. Syntheses and crystal structures

Summary The synthesis and crystal structure determination of silanetetramine N,N,N,N2-fluorophenyl(C2/c;a=16.771(7) Å,b=16.827(5) Å,c=16.753(6) Å, ß=111.00(2)°, z=8) are reported. In a search for suitable condensation pathways to silicon/nitrogen based porous solids, N-(2-fluorophenyl)-Si,Si,Si,Si,Si,Si-hexakis(2-fluorophenylamino)disilazane (2) has been obtained from the ammonium carbamate catalyzed condensation of the silanetetramine in teflon lined autoclaves. The X-ray crystal structure determination ( ;a=9.331(1) Å,b=13.698(5) Å,c=16.164(4) Å, =90.34(2)°, ß=103.03(2)°, =103.04(3)°, Z=2) shows the disilazane to be a dimer formed by linear condensation from the monomeric silazane.

     

[3]Ferrocenophanes with a tetramethyldisiloxane bridge: Synthesis and molecular structure

Summary 6,6,8,8-Tetramethyl-7-oxa-6,8-disila[3]ferrocenophane2 was obtained from the di(alkoxysilyl) ferrocene (H₄C₅SiMe₂OR)₂Fe (R=CH₂CH₂OCH₂CH₂OCH₂CH₂OMe) by hydrolysis and subsequent intramolecular disiloxane formation. 2,2,3,3,4,4,5,5,6,6,8,8-Dodecamethyl-7-oxa-6,8-disila-[3]ferrocenophane3 was formed by air oxidation of 2,23,3,4,4,5,5,6,6,7,7-dodecamethyl-6,7-disila[2]ferrocenophane. The crystal structures of both compounds were determined by single-crystal X-ray diffraction (2:a=8.5330(10),b=15.610(3),c=18.774(5)Å, =70.68(2), =77.94(2), =75.150(10)°,V=2259.8(8)ų,Z=6, space group P ,R=0.045,R _w =0.044;3:a=12.388(3),b=9.924(3),c=19.136(10)Å, =105.11(3)°,V=2271.2(15)ų,Z=4, space group P2₁/c,R=0.076,R _w =0.060). Owing to the flexibility of the disiloxane bridge,2 and3 are unstrained molecules.

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[3]Ferrocenophane mit Tetramethyldisiloxan-Brücke: Synthese und Molekülstruktur

Zusammenfassung 6,6,8,8-Tetramethyl-7-oxa-6,8-disila[3]-ferrocenophan2 entsteht aus dem Di(alkoxysilyl)ferrocen (H₄C₅SiMe₂OR)₂Fe (R=CH₂CH₂OCH₂CH₂OCH₂CH₂OMe) durch Hydrolyse und anschließende intramolekulare Disiloxan-Bildung. 2,2,3,3,4,4,5,5,6,6,8,8-Dodecamethyl-7-oxa-6,8-disila[3]ferrocenophan3 wurde durch Luftoxidation von 2,2,3,3,4,4,5,5,6,6,7,7-Dodecamethyl-6,7-disila[2]ferrocenophan erhaeten. Die Kristallstrukturen beider Verbindungen wurden durch Einkristall-Röntgenstrukturanalyse bestimmt (2:a=8.5330(10),b=15.610(3),c=18.774(5)Å, =70.68(2), =77.94(2), =75.150(10)°,V=2259.8(8)ų,Z=6, Raumgruppe P ,R=0.045,R _w =0.044;3:a=12.388(3),b=9.924(3),c=19.136(10)Å, =105.11(3)°,V=2271.2(15)ų,Z=4, Raumgruppe P2₁/c,R=0.076,R _w =0.060). Wegen der Flexibilität der Disiloxan-Brücke sind2 und3 ungespannte Moleküle.

     

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.

     

Synthesis and Crystal Structure of a New Copper–PMIDA Compound (H4PMIDA=H2O3PCH2N(CH2CO2H)2)

A new Cu(II)PMIDA compound [Cu(H₂PMIDA)(phen)] 3H₂O (1) (H₄PMIDA = H₂O₃PCH₂N (CH₂CO₂H)₂,phen = 1,10-phenanthroline) has been successfully synthesized and structurally characterized. In complex 1, Cu (II) is six coordinated by chelation in a tetradentate fashion by a PMIDA ligand and by two N atoms of a phen ligand. Every phen–Cu(II)–PMIDA group connects with each other via a hydrogen bond and the edge-to-face -stacking interaction. Complex 1 crystallized in triclinic P-1 with cell dimensions of a = 7.5817(6) Å, b = 10.6980(8) Å, c = 13.1852(10) Å, =82.350(2)°, = 84.151(2)°, =78.4250(2), V= 1035.25(14) ų, Z = 2, Dc = 1.677 Mg/m³.     

Hypervalent Intramolecular X←N (X = C,Si, Ge) Coordination in Atranes: Quantum-Chemical Study

The structure and pentacoordination effect in atranes containig Group IVa element were studied ab initio [MP2(full)/6-31G**] and in terms of the density functional theory [B3LYP/6-311+G**]. Stabiliza- tion of these compounds is determined mainly by the secondary hypervalent (R)XN bond (X = C, Si, Ge), whose strength increases in the series X = C, Si, Ge. Attractive (R)XN interaction originates from donation of unshared electron pair on the nitrogen atom to the antibonding ^* _XR orbital.