Crystal and Molecular Structure of {1,2-Bis[2-(o-hydroxyphenoxy)ethoxy]ethane}bis(isothiocyanato)calcium

The crystal, molecular structure of {1'2-bis[2-(o-hydroxyphenoxy)ethoxy]ethane}bis(iso-thiocyanato)calcium was studied by single crystal X-ray diffraction. The compound is a host-guest complex.In the molecule of this complex, the podand is wrapped around the Ca^{2 +} cation (CN 8), which is coordi- nated with all the six oxygen atoms of the podand and with two nitrogen atoms of two SCN^- ligands. The geometric parameters and crystal packing of the complex were determined. The molecules in the crystal are linked by O-H···S hydrogen bonds to form three-dimensional layers.     

Crystal Structure of Diaqua(1,2-bis(2-(o-hydroxy-phenoxy)ethyloxy)ethane)(isothiocyanato)strontium Thiocyanate

The aqua complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with strontium thiocyanate of the composition [Sr(NCS)L(H₂O)₂]⁺ · SCN^– (I), was synthesized and studied by X-ray diffraction analysis: space group P 2₁/c, a = 17.730 Å, b = 8.558 Å, c = 18.169 Å, = 116.15°, Z = 4. The structure was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.039 for 4333 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains complex cation [Sr(NCS)L(H₂O)₂]⁺ of the host–guest type. The coordination polyhedron of Sr²⁺ cation (coordination number 9) is a distorted pentagonal bipyramid with four oxygen atoms at the benzene rings of the L podand and the oxygen atom of one water molecule in its base, the N atom of the SCN^– ligand at its single vertex, and with the remaining two O atoms of the L podand and O atom of another water molecule at a triple vertex. In a crystal, the complex cations and SCN^– anions are joined through the hydrogen bonds to form bulky layers parallel to the xy plane.     

Bis[(1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane)-(isothiocyanato)potassium] [K2(NCS)2(C18H22O6)2]: Crystal and Molecular Structure

Complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with potassium thiocyanate, [K₂(NCS)₂L₂] (I) was synthesized and studied using X-ray diffraction analysis: space group P , a = 7.771 Å, b = 11.711 Å, c = 11.965 Å, = 72.22°, = 79.21°, = 89.07°, Z = 1. Structure I was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.040 for all 4370 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains [K(NCS)L] monomers of the host–guest type united into centrosymmetrical [K₂(NCS)₂L₂] dimers via two bridging OH groups (one group from two L podands). In the monomer, the L podand appears as though to envelope the octacoordinated K⁺ cation, whose the coordination polyhedron is a strongly distorted hexagonal bipyramid with all six oxygen atoms of the L podand in its base and the N atom of the SCN^– ligand and the O atom of one of OH group of the neighboring (in dimer) L podand at its axial vertices. Molecules of I in crystal are joined through the O–H···N hydrogen bonds to form broad infinite chains along the x-axis.     

Copper(I) π-Complexes with Alkyne Ligands: Synthesis and Crystal Structure of M[CuCl2(HOCH2C≡CCH2OH)] (M = K+, NH+ 4)

Crystals of anionic complexes of the composition M[CuCl₂(HOCH₂CCCH₂OH)], where M = NH₄ ⁺ (I), K⁺ (II), were isolated from concentrated aqueous solutions of CuCl and MCl (M = NH₄ ⁺, K⁺) in the presence of 2-butyne-1,4-diol. Their structures were studied by X-ray diffraction analysis. Isostructural crystals I and II are orthorhombic; Z = 8, space group Ibam; a = 6.735(1) and 6.666(2) Å, b = 17.206(3) and 16.874(6) Å, c = 15.172(3) and 15.032(4) Å, V = 1758(1) and 1691(1) ų, respectively. The compounds are built of individual [CuCl₂(HOCH₂CCCH₂OH)] anions; the NH₄ ⁺ (I) or K⁺ (II) cations are arranged in the voids between the anions. The -coordinated Cu(I) atoms have trigonal-planar environment of two chlorine atoms and CC bond of the 2-butyne-1,4-diol molecule. The Cu–(CC) distances in the -core are 1.892(4) and 1.887(6) Å, CC are 1.233(5) and 1.228(5) Å in I and II, respectively. In complex I, additional hydrogen bonds Cl···H–NH₃ (Cl···H 2.43(4) Å) and O···H–NH₃ (O···H 1.97(3) Å) stabilize the structure.     

Arrangement and Diffusive Mobility of Extraframework Species in the Hydrated Ammonium Forms of Zeolites Clinoptilolite and Chabazite

The location and diffusive mobility of ammonium ions and water molecules in the channels of the NH₄substituted forms of the natural zeolites clinoptilolite (NH₄)_6.5[Al_6.5Si_29.5O₇₂] · 12.6H₂O and chabazite (NH₄)_9.6Ca_0.6Na_0.3[Al_11.1Si_24.9O₇₂] · 25.8H₂O were studied by Xray diffraction analysis and ¹H NMR spectroscopy. The arrangement of the extraframework subsystem was shown to be largely determined by hydrogen bonds N—H...O(H₂O) of length 2.7–2.9 . The diffusive mobility of the ions was found to correspond to abnormally low energy barriers, similar to those for H₂O diffusion. The activation parameters for the diffusion jumps of the ions and molecules are E(NH₄) = E(H₂O) = 31(2) kJ/mole, ₀(NH₄) = 2 · 10¹¹ sec^-1, ₀(H₂O) = 4 · 10¹² sec^-1 in NH₄chabazite and E(NH₄) = E(H₂O) = 25(1) kJ/mole, ₀(NH₄) = 2 · 10¹⁰ sec^-1, ₀(H₂O) = 3 · 10¹¹ sec^-1 in NH₄clinoptilolite. It is suggested that the development of ion and molecular diffusion is caused by the same defects, whose formation with temperature rise is controlled by Hbond rearrangement.     

Goldbestimmung mit Hilfe von Reinecke-Salz

Zusammenfassung Es wird ein Verfahren zur Goldbestimmung beschrieben, das auf der quantitativen FÄllung des Goldes mit Reinecke-Salz beruht. Der Niederschlag hat nach dem Trocknen bei 105 C die Zusammensetzung Au[Cr(NH₃)₂(SCN)₄] · H₂O, nach dem Trocknen bei 170 C die Zusammensetzung Au[Cr(NH₃)₂(SCN)₄]. Er kann in beiden Formen gewogen werden oder man kann volumetrisch arbeiten, indem man den Niederschlag alkalisch hydrolysiert und in der erhaltenen Lösung die Rhodanidionen nach Volhard titriert. Alle drei Arbeitsweisen geben befriedigende Werte.     

Thiocyanate bond mode determination on solid manganese(II) mixed ligand coordination compounds

Synthesized and in solid state characterized compounds correspond to the following types [Mn(NCS)₂L_mL'_n] · x D, [Mn(NCS)₂L_y]_z, and [MnX₂(CH₃SCN)(CH₃OH)] · x D (L=CH₃OH or O-donors; L=CH₃SCN or N-donors; D=solvent molecules; x=0, 1 or 2; m=0, 1 or 2; n=1, 2 or 3; y=0, 1, 2, 3 or 4; z2; X=Cl or Br). Derivatographic investigations confirm the formation of intermediates, especially for L=H₂O the existence of thermic stable partially dehydrated (hydrate poor) species (y=1/2 or 1/3) and -NCS-bonding with different ligating atoms. Solid state FT-IR analysis were carried out for band shapes, measurements of the integrated intensity, and correlations between located absorption maxima for v(CN), v(CS), (NCS), v(MnN), and v(MnS) and the thiocyanate bond mode.     

Polymorphism of Crystalline Inclusion Complexes and Unsolvated Hosts. Part 8

Crystallization of cyclotriveratrylene (CTV) from solutions in acetone at 40°C gave a new 4:1 host-guest complex instead of the conventional 2:1 clathrate (-phase) whose X-ray crystal structure was determined. Data for 2(C₂₇H₃₀O₆) · 0.5(CO(CH₃)₂): monoclinic, P2₁/c, a = 18.942(4), b = 24.697(5), c = 10.508(2) Å, = 91.10(2)°, V = 4915(2) ų, Z = 8, D _x = 1.257 g/cm³, T = 293 K, R = 0.077 (for 2694 reflections). One of the two crystallographically independent CTV molecules (molecule A) is stacked into columns characteristic of the CTV - or -phase complexes. Molecules B face each other enclathrating inside around the inversion center disordered acetone molecules giving rise to the molecular capsule. The acetone molecule is H-bonded simultaneously to both host molecules by C(H₂)--H ··· O type bonds forming centrosymmetric dimers. Dimers are incorporated together with two A molecules into centrosymmetric units also by C(H₂)--H ··· O type H-bonds. Packing of these units gives rise to the crystal structure of the clathrate.     

Oxidation of isomeric η6- and η5-fluorenylchromiumtricarbonyl anions

The oxidation of the carbon-centered [(⁶-C₁₃H₉)Cr(CO)₃]^– anion (1 ^–) results in formation of (-⁶:⁶-9,9-bifluorenyl)bis-chromiumtricarbonyl (3) due to coupling of the intermediate carbon-centered radical (1^.). The oxidation of the metal-centered anion [(⁵-C₁₃H₉)Cr(CO)₃]^– (2 ^–), which is isomeric to the 1^– anion, gives an equilibrium mixture of the chromium-centered radical {(⁵-C₁₃H₉)Cr(CO)₃}^. (2 ^.) and its dimer [(⁵-C₁₃H₉)Cr(CO)₃]₂ (6). Radical2 ^. readily reacts with MeI and the solvent (THF); the resulting derivatives, (⁵-C₁₃H₉)Cr(CO)₃R (R=Me (10); R=H (7)), undergo fast ricochet inter-ring ⁵⁶ rearrangements into (⁶-9R-C₁₃H₉)Cr(CO)₃ (R=CH₃ (9); R=H (4)).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1354–1358, July, 1995.The authors are grateful to D. V. Zagorevskii who recorded the mass spectra. This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-05209) and the International Science Foundation (Grant Nos. MQ 4000 and REV 000).     

Ein Ger?t zur h?chstempfindlichen Differentialspektrophotometrie mit dem Rapidspektroskop

Zusammenfassung Eine Methode zur Differentialspektrophotometrie durch Modulation eines Monochromators wird beschrieben. Der Monochromator oscilliert mit variabler Bandbreite zwischen ₁ und ( ₁+). Wenn ( ₁+) die Wellenlänge des Absorptionsmaximums ist, erscheint am Photo multiplierausgang einer Sinuswelle, deren Amplitude der Extinktions differenz zwischen ¹ und ( ₁+) proportional ist. Die Schaltung zur ultralinearen Messung dieser Amplitude ist angegeben und ihre Anwendung mit dem Zweistrahlphotometer Rapidspektroskop gezeigt. Die Empfindlichkeit wird durch die Kombination um den Faktor 10 bis 100 gesteigert. Der Rauschpegel ist bei der Monochromator-Modulationstechnik etwa 10^–4 E.Das Differentialspektrum stellt die erste Ableitung eines Spektrums dar und gestattet die genauere Lokalisation von Schultern in steilen Flanken eines Spektrums. Die Kombination der beschriebenen Methode mit der Technik des Rapidspektroskops erlaubt es, dasselbe mit gleichem Erfolg wie ein Dual-Wavelength-Gerät einzusetzen.

---

Summary A method for differential spectrophotometry by modulation of a single monochromator is described. A single monochromator oscillates with variable bandwidth between ₁ and ( ₁+ ). If ( ₁ + ) is the wavelength at maximal optical density, the photomultiplier output gives a sinus-wave, the amplitude of which is proportional to the optical density difference between ₁ and ( ₁+). The circuit for ultralinear measurement of this amplitude is described and details of its application with the split-beam spectrophotometer Rapidspektroskop are given. The sensitivity of the entire assembly is increased by a factor of between ten and one hundred. The noise level of the monochromator-modulated technique is about 10^–4 optical density units. The differential spectrum represents the first derivative of a spectrum and allows one to determine more exactly the location of shoulders in the slope of a spectrum.The combination of the described method with the techniques of the Rapid spektroskop thus provides facilities which equal those of a dual-wavelength apparatus.

     

f-Element/crown ether complexes, 11. Preparation and structural characterization of [UO2(OH2)5] [ClO4]2·3(15-crown-5)·CH3CN and [UO2(OH2)5] [ClO4]2·2(18-crown-6)·2 CH3CN·H2O

The reaction of UO₂(ClO₄)·nH₂O with 15-crown-5 and 18-crown-6 in acetonitrile yielded the title complexes. [UO₂(OH₂)₅] [ClO₄]₂·3(15-crown-5)·CH₃CN crystallizes in the triclinic space groupPT with (at–150°C)a=8.288(6),b=12.874(7),c=24.678(7) Å, =82.62(4), =76.06(5), =81.06(5)°, andD _calc=1.67 g cm^–3 forZ=2 formula units. Least-squares refinement using 6248 independent observed reflections [F _o5(F _o)] led toR=0.111. [UO₂(OH₂)₅] [ClO₄]₂·2(18-crown-6)·2CH₃CN·H₂O is orthorhombicP2₁2₁2₁ with (at–150 °C)a=12.280(2),b=17.311(7),c=22.056(3) Å,D _calc=1.68 g cm^–3,Z=4, andR=0.032 (3777 observed reflections). In each complex the crown ether molecules are hydrogen bonded to the water molecules of the pentagonal bipyramidal [UO₂(OH₂)₅]²⁺ ions, each crown ether having exclusive use of two hydrogen atoms from one water molecule and one hydrogen from another water molecule. In the 15-crown-5 complex the remaining hydrogen bonding interaction is between one of the water molecules and one of the perchlorate anions. The solvent molecule has a close contact between the methyl group and a perchlorate anion suggesting a weak interaction. There are a total of three U-OH...OClO₃ hydrogen bonds to the two perchlorate anions in [UO₂(OH₂)₅] [ClO₄]₂·(18-crown-6)·2CH₃CN ·H₂O. The remaining coordinated water hydrogen bond is to the uncoordinated 2H₂O molecule, which in turn is hydrogen bonded to a perchlorate oxygen atom and an acetonitrile nitrogen atom. One solvent methyl group interacts with an anion, the other with one of the 18-crown-6 molecules. Unlike the 15-crown-5 structure, the hydrogen bonding in this complex results in a polymeric network with formula units joined by hydrogen bonds from one of the solvent molecules and the uncoordinated water molecule. Supplementary data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82051 (37 pages).For Part 10, see reference [1].     

Crystal Structure of Tetrafluoro(1,10-phenanthroline-N,N')silicon Acetonitrile Semisolvate

The crystal structure of tetrafluoro(1,10-phenanthroline-N,N')silicon acetonitrile semisolvate, [SiF₄(phen)]·1/2CH₃CN (I), was studied by X-ray diffraction analysis. The structure of I is tetragonal (space group I4₁/a; a=9.184(1), c=29.700(5) , Z=8); direct methods, full-matrix least-squares refinement in an anisotropic approximation; R=0.039 for all 1820 independent reflections collected (CAD-4 automatic diffractometer, MoK). The geometrical parameters of the [SiF₄(phen)] molecule (bond lengths and angles, etc.) were determined with a high accuracy.     

Synthesis,structure and the e.s.r. spectrum of the mixed-valence molybdovandate Na2(NH4)4[(VIVVV8Mo)O28] · 10H2O

The mixed-valence molybdovanadate compound Na₂(NH₄)₄[V^IVV^V ₈Mo)O₂₈] · 10H₂O [Vanadata(6-)tetradeca--oxotetra-₃-oxodi-₆-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH₂OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO₆ octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4.     

The phenomenon of conglomerate crystallization. XVIII. Clavic dissymmetry in coordination compounds. XVI

The x-ray crystal structure of {[Co(NH₃)₄(CO₃)]NO₃}₂ · H₂O has been determined as part of a study of the intra- and interionic interactions present in crystals of several transition-metal-amine complexes chosen to examine the occurrence and causes of conglomerate crystallization. {[Co(NH₃)₄(CO₃)]NO₃}₂ · H₂O crystallizes in the monoclinic space group P2₁/n with cell constantsa=7.4960(9)Å,b=22.673(6),c=10.513(1), and=91.41(1)°;V=1786.12 ų, andd(calc;Z=4)=1.915 g cm^–3. In all, 5333 data were collected over the range of 4° 2 60°; of these, 3395 [independent and with /3(1)] were used in the structural analysis. Data were corrected for absorption (=19.361 cm^–1) and the relative transmission coefficients ranged from 0.9987 to 0.8013. The data were of a quality such that both ammonia and water hydrogens were found in difference Fourier maps. The finalR(F) andR _w(F) residuals were, respectively, 0.0333 and 0.0332. A trans effect is observed for both cations of {[Co(NH₃ (CO₃)]NO₃}₂ · H₂O. The equatorial nitrogens, trans to the carbonato oxygens, have shorter Co-N distances than the axial nitrogens, trans to one another. The carbonato ligands are not symmetrically bonded to their respective metal centers. The Co-O distances for cation 1 are 1.913(1) and 1.903(1) Å and those for cation 2 are 1.916(1) and 1.896(1) Å. The structure reveals the existence of an intricate array of hydrogen bonds, involving both the chelating and nonchelating oxygens of the carbonato ligands as hydrogen bond acceptors of the amine hydrogens. The amine hydrogens are also involved in significant hydrogen-bonding interactions with the nitrate oxygens and water of crystallization, although they are generally weaker than those of the carbonato oxygens.     

Preparation and disordered crystal structure of (18-crown-6)ammonium isothiocyanate hemihydrate

A crystalline complex salt, (18-crown-6)ammonium isothiocyanate hemihydrate [NH ₄ ⁺ (18C6)]·SCN^?·0.5H₂O, was prepared and studied by single-crystal X-ray diffraction. The crystal structure of this salt is highly disordered: Almost all the constituents (except the water molecule) are disordered over two different orientations: major and less occupied or weakly occupied. The geometric parameters (bond lengths, bond angles, etc.) of the molecular and ionic constituents of the salt were determined with reasonable accuracy, and the crystal packing was elucidated. The sale forms in the crystal a complex tetrahedral supramolecular hydrogen-bonded structure consisting of one water molecule, two complex cations [NH ₄ ⁺ (18C6)], and two SCN^? anions.     

Crystallographic studies on sterically affected chemical species

The crystal and molecular structure of 2-carboxy-2-methoxybiphenyl has been determined to R=0.035. Crystals are tetragonal, of space group I4₁cd, witha=b=15.181(2)c=19.874(2) Å. Mean esd values for bond lengths and bond angles are 0.005 Å and 0.3°, respectively. The angle between phenyl rings is 54.5(1)°. The C(1) (carboxy) and O (methoxy) distance is 3.02 Å. Dimers of the title compound are hydrogen bonded with O·O distances of 2.68 Å and 2.58 Å. Due to the symmetry of the space group, the hydrogen atoms are necessarily located in the center of the O·O distance. Parameters of repulsive deformations for bond angles have been defined. Due to overcrowding in the region ofo,o-substitution, significant deformations of exocyclic bond angles have been observed. The magnitudes of these deformations depend roughly on the spatial requirements of the sterically interacting substituents, expressed by Charton's [1] parameter.     

Crystal Structure of Diaqua(1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane)(perchlorato-O)strontium Perchlorate Hydrate

The aqua complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with strontium perchlorate of the composition [Sr(ClO₄)L(H₂O)₂]⁺ · ClO₄ ^– · H₂O (I) was synthesized and studied using X-ray diffraction analysis: space group P2₁/c, a = 16.195 Å, b = 11.382 Å, c = 16.646 Å, = 117.01°, Z = 4. The structure was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.069 for 4278 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains complex cation [Sr(ClO₄)L(H₂O)₂]⁺ of the host–guest type. The Sr²⁺ cation (coordination number 9) is coordinated to all six O atoms of the L podand, O atom of a disordered ClO₄ ^– ligand, and two O atoms of two water molecules. The coordination polyhedron of Sr²⁺ is irregular; in a rough approximation, it can be described as a face-centered cube. The crystal structure of I contains an infinite three-dimensional network of the O–H···O hydrogen bonds joining the complex cations, ClO₄ ^– anions, and molecules of crystallization water.     

Vergleichbare Kraftfelder vieratomiger Formylverbindungen

Comparable force fields for HCOO^–, HFCO, HClCO and HDCO have been calculated on the basis of internal coordinates. Linear relations between (i) the carbonyl bond order and the carbonyl stretching force constant, (ii) the sum of the three in-plane bending force constants and the hydrogen out-of-plane force constantf , (iii) a combination of orbital electronegativities andf , have been obtained. The observed in-plane vibrational frequencies have been calculated with an average error of 6.3 cm^–1 or 0.4%.

     

ξ-potential and surface dye-ability of poly(vinyl alcohol) fiber with different degree of formalization in a cationic dye solution

Summary The surface dyeability of the poly(vinyl alcohol) fiber with different degree of formalization was studied by measuring -potential of the fiber in alkaline aqueous solutions (pH 10) of a cationic dye Methylene Blue. With the increase in the dye concentration, the sign of the -potential of the fiber changed from negative to positive and thereafter the positive value approximated to saturated value, and the amount of dye adsorbed (expressed in mol/cm²-fiber) increased also. These results may possibly be attributed to the formation of the electrostatic bond between the fiber and the dye. The linear relations were found between and logC _d and its slope did not change with rise of temperature. The free energy of dyeing G (negative) calculated from the slope of the -logC _id curve, etc. increased with increasing the degree of formalization of the fiber. This fact corresponds to the increase in the surface dye adsorption with increasing the degree of formalization. With increasing the degree of formalization, the heat of dyeing H (negative) increased and the entropy of dyeing S (positive) decreased. The positive value of S for each fiber, suggests the formation of hydrophobic bond as a driving force to the dyeing of Methylene blue on the fiber surface in addition to the electrostatic bond.This paper is Part XXVII in a series on Studies on -potentials and Surface Dyeability of Natural and Synthetic Fibers in Dye Solution. Part XXVI: T. Suzawa andK. Kawakami, Nippon Kagaku Kaishi1975, No. 7,1134.     

Synthesis and Crystal Structure of Tetraamminelithium-Rubidiumtriselenide, Li(NH3)4RbSe3, and Pentaamminesodium-Rubidiumtriselenide-Ammonia(1/3), Na(NH3)5RbSe3 · 3NH3

Summary. The ammoniates Li(NH₃)₄RbSe₃ and Na(NH₃)₅RbSe₃·3NH₃ were prepared by the reduction of Rb₂Se₅ with lithium or sodium in liquid ammonia. Single crystals were isolated and characterized by X-ray structure analysis using low temperature techniques. Both compounds contain triselenide anions Se₃^2–, which coordinate to rubidium cations forming ¹[RbSe₃]^– or ¹[Rb(NH₃)₂Se₃]^– chains. The chains are separated in the crystal structures by the homoleptic ammine complexes Li(NH₃)₄⁺ and Na(NH₃)₅⁺.