Synthesis and structure of 4,7,13,16-tetraoxa-1,10-diaza-5,6-benzocyclooctadeca-11,18-dione monohydrate

4,7,13,16-tetraoxa-1,10-diaza-5,6-benzocyclooctadeca-11,18-dione, C₁₆H₂₂N₂O₆·H₂O, (3) was synthesized under thermal conditions, starting from ,-diamine (1) and ,-diester (2). The hydrate of compound (3) was investigated in the solid state by X-ray structural analysis. Crystal data: monoclinic system, space group P2₁/c,a=12.342(4) Å,b=15.978(7) Å,c=8.960(3) Å, =96.72(3)°,Z=4. The structure was solved by direct methods and refined to finalR=0.056,R _w=0.069 for 1962 observed reflections. The structure exhibits internal hydrogen bonds between the etheral O(16) atom and the neighboring amide group. The water molecule connects diamide molecules by one strong hydrogen bond with carbonyl oxygen, and four weak hydrogen bonds with the amide groups and etheral oxygen atoms.     

The crystal structure of calcium succinate monohydrate

The crystal structure of calcium succinate monohydrate, Ca(C₄H₄O₄)·H₂O, has been determined by single crystal X-ray diffraction. The crystals are monoclinic witha=11.952(2),b=9.691(2),c=11.606(2)Å, =108.81(1)°, space group C2/c,Z=8,V=1272.49 ų,d _m =1.80, andd _c =1.818 Mg m^–3. The structure was refined by full-matrix least-squares techniques toR=0.027,R _w =0.040, for 829 reflections with13(I). Ca is coordinated to seven oxygen atoms, and the coordination polyhedron is best described as a pentagonal bipyramid. One carboxylate group in the succinate ion is bonded to three different Ca ions, forming a four-membered chelate ring with one Ca ion is bonded to three different Ca ions, forming a four-membered chelate ring with one Ca ion and unidentate bridge bonds to two other Ca ions. The other carboxylate group is bonded to two Ca ions through unidentate bonds. The structure is highly polymeric. The general structural features are nearly identical to those of calcium adipate monohydrate.Certain commercial materials and equipment are identified in this paper to specify the experimental procedure. In no instance does such identification imply recommendation or endorsement by the National Institute of Standards and Technology or the ADA Health Foundation or that the material or equipment identified is necessarily the best available for the purpose.     

Crystal structure of 1,2;5,6-di-O-isopropylidene-3-O-(phenylacetyl)-D-glucofuranose

The synthesis and X-ray crystal structure of 1,2;5,6-di-O-isopropylidene-3-O-(phenylacetyl)-D-glucofuranose is reported. It crystallizes in the orthorhombic system with space group P2₁2₁2₁ (No. 19); a = 9.9313(12) Å, b = 10.0657(12) Å, c = 20.343(2) Å, and Z = 4. The solid state structure is discussed in terms of the use of the title compound for further chemistry.     

Synthesis,crystal and molecular structure and vibrational characterization of N,N-dimethyl-oxathioamidate monohydrate

The title compound (SO₂NC₄H₆) has been prepared and characterized by X-ray diffraction and infra-red and Raman spectra. The structure has been refined using single-crystal X-ray diffraction data measured at 295K [MoK-radiation with =0.71073 Å]. The crystals are monoclinic, space groupP2₁/n,Z=4,a=6.240(2),b=6.786(2),c=19.988(1)Å, =108.47(2)°,V=802.8(7)ų.D _calc.=1.566 Mg m^–3,F(000)=392, =8.582 cm^–1. The final agreement factors for 1906 observed refections [I>3(I)] were:R=0.030 andR _w=0.043. The dihedral angle between de C–C–S–N plane and the C–C–O–O plane is 88.31(4). The potassium atom within the title compound structure has a slightly distorted trigonal bipyramidal coordination. Infrared and Raman spectra of the normal CH₃/CD₃ and H₂O/D₂O isotopes and the waterfree compounds at different temperatures made it possible to perform isotopes complete vibrational analysis and clearly shows the very special hydrogen bonded water molecule in the crystal.     

The molecular and crystal structure of endo-2-methyl-7-hydroxy-7-oxo-N-phenyl-7-phosphabicyclo-[2.2.1] hept-2-ene-5,6-dicarboximide

The structure of the title compound1 has been determined by X-ray crystallography analysis. The following crystal data were found: orthorhombic,Pca2_l,a=9.60691),b=16.356(1),c=8.686(1) . Both the phospholane and phospholene rings involved in the 7-phosphabicyclo-[2.2.1] hept-2-ene system have almost regular envelope conformations, and the cyclohexene ring has a significantly deformed boat conformation. The low value of the C–P–C angle, 84.2(2)°, reflects the steric strain around the phosphorus bridge and may be responsible for the reactivity of esters and amides derived from1 in the O-insertion reaction with m-chloro-perbenzoic acid. The dihedral angle between the plane of the benzene and succinimide rings is 82.4(2)°.     

Molecular structure of isopropyl 1-phenyl-4-phenylhydrazono-5-oxo-3-pyrazolecarboxylate

The new azopyrazolone dye has been synthesized and its crystal structure has been investigated. Crystals of C₁₉H₁₈N₄O₃ are triclinic: ,a=7.484(1),b=10.646 (1),c=11.897(1) Å, =82.28(1), =72.86(1), =86.83(1)°,Z=2. The structure has been solved by direct methods and refined by full-matrix least-squares techniques toR=0.050 for 2622 unique reflections. The tautomeric form of the molecules has been determined as a hydrazo form. Delocalization of the C5=O3 and C4=N3 -electrons and delocalization of the lone-pair electrons of N1, N3, and N4 atoms has been observed. The intramolecular N–H...O hydrogen bond forms the six-membered ring C₂N₂H...O condensed with the pyrazolone ring. The molecules are connected by intramolecular C–H...O hydrogen bonds.     

X-ray structure of 2,6-dimethoxy-7-methylpurine

The title compound (C₈H₁₀N₄O₂) is monoclinic, with a = 7.740(2), b = 17.044(7), c = 6.992(3) Å, = 100.60(1)°, and space group P2₁/c. Two O-methyl groups are coplanar with the pyrimidine ring. Whereas, the O(6)-methyl group is directed away from the imidazole ring toward the N(1) atom, the O(2)-methyl is pointed away from the N(1) atom toward the N(3) atom. Two intermolecular hydrogen bonds H(8)···N(1) and H(711)···O(2) of 2.48(2) and 2.58(3) Å make a linear arrangement of the molecules. The conformation of the O-methyl groups explains some results of thermal rearrangement of 2,6-dialkoxy-7-methylpurines and differences in alkylations of 2,4-dialkoxypyrimidines and 2,6-dialkoxy-7-methylpurines.     

Molecular structure ofrac-(4R*,4aS*,10aS*)-4-nitro-1,2,3,4,4a,9,10,10a-octahydrophenanthren-4a-ol,an unusual by-product of nitration of a crude 9,10-dihydrophenanthrene

A new nitro-octahydrophenanthrenol has been isolated by nitration of a crude 9,10-dihydrophenanthrene, which was identified by nmr and X-ray diffraction analysis. Crystallographic and molecular structure confirmed the compound as therac-(4R^*,4aS^*,10aS^*)-4-Nitro-1,2,3,4,4a,9,10,10a-octahydrophenanthren-4a-ol. The crystal was triclinic, ,a=10.549(3),b=8.530(3),c=7.131(1)Å, =107.07(3), =91.62(3), =96.27(4)°. Cyclohexane and cyclohexene rings aretrans-fused and have chair and half-chair conformations, respectively. The molecules are associated by hydrogen bridge between the hydroxyl oxygen and both nitro oxygens.     

X-ray structure and NMR assignment of 4,4′-[3-oxa-1,5-pentanedi(ylthio)]-3,3′-diquinolinyl sulfide

The title compound (C₂₂H₁₈N₂OS₃) is monoclinic, with a=20.7446(5), b=8.332(1), c=24.393(7)°, β=112.12(1)° and space group P2₁/n. There are two independent molecules in the unit cell. Two quinoline moieties are nearly perpendicular to each other (76.9(1)°) and (72.0(2)°). Both S-methylene fragments are trans-orientated with respect to the C(3)−S(1)−C(13) plane. Two pairs of sulfur atoms in ortho-positions are in very close contact with sulfide preserving a skew conformation. The central 12-membered ring adopts an unusual conformation. Part XLIII in the series of Azinyl Sulfides. Part XLII: Maślankiewicz, M.J.; Maślankiewicz, A.J. Heterocycl. Chem. 1996,33, 1989.     

Preparation,spectral studies and X-ray crystal structure of 1,3,5-triphenyl-1,5-pentanedione,C23H20O2

1,3,5-triphenyl-1,5-pentanedione, C₂₃H₂₀O₂, has been prepared and characterized by spectroscopic methods and single crystal X-ray analysis. Crystals are monoclinic, space groupP2₁/n, a=28.124(4),b=5.997(1),c=10.434(1)Å, -98.42(1)Å,Z=4. The structure has been refined to a finalR-value of 0.040 for 1625 reflections withF _o>3(F _o). The compound contains the two carbonyl groups in a mutuallycis arrangement.     

Synthesis and Single Crystal X-Ray Structure of [Na(H2O)2(C18H15O6SO3)]2

Abstract  [Na(H₂O)₂(C₁₈H₁₅O₆SO₃)]₂ was synthesized by sulfated 5-hydroxy-6,7,4′-trimethoxyisoflavone with concentrated sulfuric acid. Single-crystal X-ray diffraction study indicates that it is a dimeric centrosymmetric species. The coordination polyhedron of each Na(I) atom exhibits a distorted trigonal bipyramidal geometry. The dimeric units are linked by intermolecular hydrogen bonds C–H⋯π, C–H⋯O and O–H⋯O to result in a three-dimensional framework. Graphical Abstract  [Na(H₂O)₂(C₁₈H₁₅O₆SO₃)]₂ was synthesized by sulfated 5-hydroxy-6,7,4′-trimethoxyisoflavone with concentrated sulfuric acid. The coordination polyhedron of each Na(I) atom exhibits a distorted trigonal bipyramidal geometry. The dimeric centrosymmetric units are linked by intermolecular hydrogen bonds C–H⋯π, C–H⋯O and O–H⋯O to result in a three-dimensional framework. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Theoretical studies of the spin Hamiltonian parameters and the local structures for the tetragonal Cu centers in the LKB glasses

The spin Hamiltonian parameters (g factors g_∥, g_⊥ and the hyperfine structure constants A_∥, A_⊥) for the Cu²⁺ centers in the lithium potassium borate (LKB) glasses xLi₂O·(30 − x)·K₂O·70B₂O₃ (0 ≤ x ≤ 25) were theoretically studied using the high-order perturbation formulas of these parameters for a 3d⁹ ion in a tetragonally elongated octahedron. The [CuO₆]¹⁰⁻ clusters in the LKB glasses are found to suffer the relative elongations of about 3% along the tetragonal axis due to the Jahn-Teller effect. The concentration dependences of the g factors are illustrated by the approximately linear decrease of the cubic field parameter Dq as well as the increases of the covalency factor N and the relative elongation ratio ρ due to the slight expansion of the cell volume or bond lengths with increasing the Li₂O concentration x. Meanwhile, the slow non-linear increases of the hyperfine structure constants are described as the rough exponential increase of the core polarization constant κ with x due to the increase of the tetragonality of the systems. The theoretical spin Hamiltonian parameters and their concentration dependences show good agreement with the experimental data. To evaluate validity and applicability of the present theoretical model and formulas, the EPR results of the Cu²⁺ centers in similar lithium sodium borate (LNB) xLi₂O·(30 − x)·Na₂O·70B₂O₃ (5 ≤ x ≤ 25 mol%) glasses are also analyzed and compared with those in the LKB systems using the uniform model and formulas.     

Crystal and molecular structure of a cobalt(II) complex with bis(benzimidazol-2-ylmethyl)-methylamine (L)

The reaction product of Co(II) chloride and the title ligand L, formulated as CoLCl₂·CH₃OH, was prepared and characterized by means of structural and spectroscopic measurements. The violet crystals are orthorhombic, (space groupP2₁2₁2₁) witha=8.093(2),b=14.883(3),c=16.831(3) Å, andZ=4. The structure consists of discrete molecules with pseudo-, noncrystallographic twofold symmetry in which the Co atom is coordinated in trigonal bipyramidal geometry by three nitrogen and two chlorine atoms. The ligand L is coordinated to the Co atom in afac mode and two chlorine atoms are incis-positions. The structure was confirmed by IR-spectra.     

Synthesis and crystal structure of [Ni(H2O)6](C19H17O9S)2·2H2O

A water soluble flavonoid sulfate, [Ni(H₂O)₆](C₁₉H₁₇O₉S)₂·2H₂O was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. The crystal of it belongs to triclinic crystal system, space group P–1. The results show that the title compound consists of [Ni(H₂O)₆]²⁺, C₁₉H₁₇O₆SO₃ ⁻ and H₂O. Ni(II) is located on the symmetry center and octahedrally coordinated by six water molecules. A variety of hydrogen bonds among [Ni(H₂O)₆]²⁺, C₁₉H₁₇O₆SO₃ ⁻ and the lattice water molecules build a hydrophilic region. Aromatic π–π stacking interactions assemble isoflavone skeletons into a column and the columns form a hydrophobic region of the title compound. The sulfo-groups bridge the hydrophilic regions and the hydrophobic regions as well as the inorganic components and organic components. Hydrogen bonds, stacking interactions and the electrostatic interactions between cation [Ni(H₂O)₆]²⁺ and anion sulfonate C₁₉H₁₇O₆SO₃ ⁻ lead the moieties to a three-dimensional structure.     

X-ray structure of 6-phenyldiquino[3,2-b;5,6-b′] [1,4]thiazine

The title compound (C₂₄H₁₅N₃S) is monoclinic, with a = 10.816(1), b = 8.193(1), c = 10.892(1), = 104.20(1)° and space group P2₁. The molecule is folded with the central ring in a boat conformation. It can also be considered as folded around the C—C axis between the thiazine and pyridine rings. The butterfly folding angle between the two quinoline planes is 20.5(1)° and between the planes of the two halves of the thiazine ring is 30.6(1)°. The phenyl substituent is in an equatorial location with respect to the thiazine ring with the C—N···S angle of 163.0(2)°. The phenyl plane nearly bisects the pentacyclic ring system and is nearly perpendicular to the C(2), C(3), C(12), C(13) plane.     

Synthesis and Photocatalytic Properties of TiO2 Intercalated H4Nb6O17

Abstract

TiO₂ intercalated H₄Nb₆O₁₇ has been synthesized by the reactions of H₄Nb₆O₁₇ with a titanyl acylate complex followed by UV irradiation. The gallery height, specific surface area and Ti content of the sample synthesized by using titanyl acylate complex were larger than that using TiO₂ sol solution. Furthermore, the photocatalytic activity of the TiO₂ pillared H₄Nb₆O₁₇ prepared using a titanyl acylate precursor was twice larger than that fabricated using a TiO₂ sol solution.     

Crystal structure, vibrational spectra, and thermal decomposition and nitrogen adsorption behaviour of a new tetramanganese(II) dipyrophosphate decahydrate, Mn4(P2O7)2·10H2O

A new manganese(II) pyrophosphate, Mn₄(P₂O₇)₂·10H₂O, has been synthesized and characterized by single-crystal X-ray diffraction [orthorhombic space group Pnma, with unit cell parameters of a=9.3288(3) ?, b=25.9532(9) ?, c=8.4783(3) ?; Z=4]. All the pyrophosphate anions show non-linear P–O–P bonds with an average angle of 128.60°. The framework of this new pyrophosphate is made up of packed layers of MnO₆ octahedra connected by double-tetrahedra P₂O₇ groups and a layer of Mn(H₂O)₆ units. The [P₂O₇]⁴⁻ anions adopt a bent, near-staggered conformation. The absence of coincidences for the majority of the IR and Raman bands is in accord with the centrosymmetric structure of the material. The vibrational spectra have been interpreted in part on the basis of factor group effects. The structural changes occurring during heating have been investigated by TG-ATD. When Mn₄(P₂O₇)₂ ^.10H₂O is gradually heated, it decomposes into an intermediate hydrated salt at 96°C and then to anhydrous Mn₂P₂O₇ at 325°C. This thermal behaviour is different from that of Zn₄(P₂O₇)₂·10H₂O. The crystal structure of the new managenese(II) pyrophosphate is compared with the known structures of Zn₄(P₂O₇)₂·10H₂O, Mn₂P₂O₇·2H₂O and anhydrous Mn₂P₂O₇. The adsorption and desorption isotherms of Mn₄(P₂O₇)₂·10H₂O, Zn₄(P₂O₇)₂·10H₂O and MnKHP₂O₇·2H₂O have been investigated by BET measurements and the results show that the capacity for N₂ sorption of the Mn(II) salt is two times lower than is that of the Zn(II) isotype and two or three times higher than is that of MnKHP₂O₇·2H₂O.     

Redetermination of the crystal structure of [Na4(H2O)14]SnS4: a compound containing a novel chain of aquated sodium ions

[Na₄(H₂O)₁₄]SnS₄ is obtained by the reaction of Na₂S·9H₂O with SnCl₄·5H₂O in aqueous solution at 21°C. It crystallizes in the space group Cc with a = 8.621(2) Å, b = 23.543(5) Å, c = 11.358(2) Å, = 110.58(3)° and V = 2158.2 ų with Z = 2. Refinement of 3826 unique reflections from a racemically twinned crystal yielded a final value of R₁ = 0.0464 (|F| > 4) and wR₂ = 0.104 and a goodness of fit of 1.125. The structure consists of a Na⁺/H₂O network supporting the tetrahedral SnS₄ ^4– anions. Water molecules or sulfide ions octahedrally coordinate each of the four crystallographically independent Na⁺ ions. The dominant feature of the structure is the existence of zigzag chains of edgeshared Na octahedra. These chains are tied together into a three-dimensional network by bridging Na(H₂O)₆ octahedra and individual H₂O molecules.