Synthesis and structure of (H2O)(12-crown-4)-Co(II)(Co(II)Cl3)(μ-Cl) isolated from a liquid clathrate medium

The crystal structure of (H₂O)(12-crown-4)Co(II)(Co(II)Cl₃)(μ-Cl)1 is reported. Crystal data for1: monoclinic, space groupP2 ₁/m, a=7.958(8) Å,b=12.006(1) Å,c=69.017(9) Å, β=107.896(2)⁰, D_c=1.84 g cm^?3,Z=2,R1=0.025,wR2=0.059. The crown ether acts as a tetradentate ligand and partially completes the binding sphere of the Co(II) ion which also includes one water oxygen atom and a bridging chloride ligand, the latter of which may be regarded to originate from a [CoCl₄]^2? ion.     

Preparation and X-ray structure of [H3O+·18-crown-6]-[(H5O 2 + )(Cl−)2], a compound containing both H3O+ and H5O 2 + crystallized from aromatic solution

The title compound was synthesized by the reaction of [H₃O⁺·18-crown-6][Cl-H-Cl^–]·3.8 C₆H₅Me with two equivalents of H₂O. Colorless crystals, which slowly deposited from the corresponding liquid clathrate, belong to the monoclinic space group P2₁/n witha=10.648(6),b=9.571(2),c=20.801(6) Å,=98.67(5)°, andD _c=1.24 g cm^–3 forZ=4. Refinement based on 1609 observed reflections led to a finalR value of 0.072. In the crystal structure the [H₃O⁺·18-crown-6]⁺ cations are packed in layers separated by puckered sheets of [(H₅O ₂ ⁺ )(Cl^–)₂]^–.     

Air-stable liquid clathrates. 1. Crystal structure of [NBu4][Br3] and reactivity of the [NBu4][Br3]·5 C6H6 liquid clathrate

[NBu₄][Br₃] interacts with C₆H₆ to form an air-stable liquid clathrate. The tribromide anion reacts with phenol to give para-bromophenol in>95% yield. The HBr which is generated in the reaction combines with the Br^– anion to form [Br-H-Br]^–. The latter forms the basis for a new liquid clathrate, [NBu₄][Br-H-Br]·n C₆H₆. The parent salt, [NBu₄][Br₃], crystallizes in the monoclinic space group C2/c witha=12.983(5),b=10.380(7),c=16.222(6) Å,=93.93(3)°, andD _c =1.47 g cm^–3 forZ=4. The final R value is 0.068 based on 787 observed reflections.     

Crystal and molecular structure of complex compound [Fe3O(CH3COO)6(H2O)3]2[ZnCl4] ⋅ 2H2O

The X-ray crystal structure of trinuclear iron acetate [Fe₃O(CH₃COO)₆(H₂O)₃]₂ [ZnCl₄] ? 2H₂O was determined. The crystal has a ionic structure. It is monoclinic, a = 25.363(7), b = 14.533(4), c = 15.692(4) Å, β = 103.11(2)°, space group _C2/c, and R = 0.0685. The structure of the cationic complex [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ is typical of trinuclear iron(III) compounds containing a μ₃-O bridge: the iron atoms are situated at the vertices of an almost equilateral triangle with the O atom at the center. Each Fe atom is coordinated by four O atoms of bridging carboxy groups, the μ₃-bridging O atom, and the water molecule in the trans position to the latter O atom. Mössbauer spectroscopy evidence indicates the high-spin state (_S = 5/2) of the iron(III) ions.     

Synthesis and X-ray structure of [H3O+·18-crown-6] [Br−Br−Br−]; a compound containing both H3O+ and a linear and symmetrical Br 3 t- ion crystallized from aromatic solution

[H₃O⁺·18-crown-6][Br–Br–Br^–] crystallizes in the triclinic space group P 1 witha=6.105(1),b=8.658(1),c=11.072(1)Å, =71.35(1), =77.58(1), =71.09(1)⁰, andD _c=1.68 g cm^–3 forZ=1. Refinement based on 1112 observed reflections led toR=0.044. The cation exhibits a planar oxonium ion bonded symmetrically to the 18-crown-6 (O(oxonium) resides 0.092 Å out of the plane of the crown ether oxygen atoms). The anion also resides on a center of inversion with Br–Br=2.530(1)Å.     

Crystal and molecular structure of 7-hydroxyflavone monohydrate, C14H10O3·H2O

The X-ray crystal structure of 7-hydroxyflavone monohydrate, C₁₄H₁₀O₃ · H₂O, is determined. The compound crystallizes in the monoclinic space group, P2₁/n with a = 3.801(3), b = 19.665(4), c = 16. 039(6), = 93.69(3)°, and = 0.68 mm^–1 for Z = 4. The phenyl ring of the flavone moiety is rotated 18.6(1)° out of the penzopyran plane, which is a typical value for flavones. In the crystal lattice, there are wide channels which are lined mainly by C–H groups. The water molecules enclosed in these channels are severely disordered.     

Synthesis and structure of (H2O·HBF4)2(18-crown-6)

The title compound has been prepared by the addition of fluoroboric acid to 18-crown-6 in toluene. The compound crystallizes in the triclinic space group P¯1 witha=7.341(2),b=8.364(2),c=10.631(3)Å,=71.48(2),=67.91(2), =67.94(2)°, andD _c =1.44 g cm^–3 forZ=1. The final conventionalR value was 0.079 based on 1575 observed reflections. The molecule resides on a center of inversion. The (H₂O·HBF₄) moieties are best viewed as fluoroboric acid monohydrate molecules hydrogen bonded to the crown ether, one above and one below the plane of the crown. The FO(water) hydrogen bond separation is 2.474(5)Å, and the O(crown)O(water) separations are 2.834(5) and 2.841(6) Å. The oxygen atoms of the crown ether are planar to 0.23 Å.     

Crystal structure of N-benzylmethylammonium dihydrogen-monophosphate monohydrate, [C6H5CH2NH2CH3]H2PO4·H2O

The salt N-benzylmethylammonium dihydrogenmonophosphate monohydrate is monoclinic with the following unit cell dimensions: a = 6.356(1)Å, b = 8.385(7)Å, c = 11.472(5)Å, = 104.32(1)°, space group P2₁ with Z = 2. The structure consists of infinite parallel two-dimensional [110] planes built of mutually connected ions and water molecules by strong O–H···O and N–H···O hydrogen bonding. There are no contacts other than normal van der Waals interactions between the layers.     

Synthesis and crystal structure of [Y(NO3)3(OH2)3]·(Me2-16-crown-5)·H2O

The complex [Y(NO₃)₃(OH₂)₃]·(Me₂-16-crown-5)·H₂O has been prepared and its crystal and molecular structure determined using single crystal X-ray diffraction. The colorless crystals belong to the monoclinic space group P2₁/n with Z = 4. Lattice parameters are a = 10.420(1), b = 17.257(3), c = 14.646(2) Å, = 96.79(1)°, V = 2615.1(6) ų. The yttrium(III) ion is nine-coordinate, bonded to three bidentate nitrate groups and three water molecules. The average Y–O(nitrate) and Y–O(water) distances are 2.42(3) and 2.33(1) Å, respectively. The average HO–H···O hydrogen bonded separation is 2.767Å.     

Crystal and molecular structure of [Cu2(3,5-dihydroxybenzoate)4 (acetonitrile)2] ⋅ 8H2O

The crystal and molecular structure of the title compound, [Cu₂(3,5-dihydroxybenzoate)₄ (acetonitrile)₂] 8H₂O 1, is reported. Crystal data for 1: tetragonal, space group I 4/m, a = 11.720(2) Å, c = 15.304(3) Å, V = 2102.4(6), and D _c = 1.53 g/cm³, for Z = 2. The metal and organic components crystallize to form a Cu paddle-wheel complex, of idealized D_4h symmetry, that assembles in the solid-state, along with eight equivalents of water, to form a 3D hydrogen-bonded network held together by O–H O hydrogens bonds. The metal complexes pack to form a 2D layered structure.     

Hydrothermal crystallization and X-ray structure determination of a new decavanadate with mixed cations [Mn(H2O)6]2[N(CH3)4]2[V10O28]·2H2O

A new decavanadate with mixed cations, [Mn(H₂O)₆]₂[N(CH₃)₄]₂[V₁₀O₂₈]·2H₂O (1), was crystallized from a hydrothermal reaction between MnCO₃ and V₂O₅ in the presence of N(CH₃)₄Br at 100°C. The structure of 1, as determined by x-ray single crystal analysis, consists of cations and anions of hexa-aqua manganese [Mn(H₂O)₆]²⁺, tetramethyl ammonium [N(CH₃)₄]⁺ and decavanadate [V₁₀O₂₈]^6–. The extended H-bonding between the [Mn(H₂O)₆]²⁺ and [V₁₀O₂₈]^6– ions gives rise to a pseudo- two-dimensional network in the crystal lattice x-ray crystallographic data for 1: monoclinic P2₁/n, a = 9.1499(5), b = 12.8725(7), c = 18.625(1) Å, = 92.252(1)°, V = 2192.0(2) ų, MZ = 2, and D _calcd = 2.22 g cm^–3.     

Hydrothermal Synthesis and Characterization of a New Strandberg-type Diphosphopentamolybdate (C6N3H18)2[P2Mo5O23] · 6H2O

Crystallography Reports - An inorganic-organic hybrid material formulated as (C6N3H18)2[P2Mo5O23] · 6H2O, has been hydrothermally synthesized and characterized by single crystal X-ray...     

Synthesis and crystal structure of a new lithium cyclohexaphosphate hydrate: Li6P6O18·10H2O

The synthesis and crystal structure of a novel hydrate of lithium cyclohexaphosphate are reported. Li₆P₆O₁₈·10H₂O crystallizes in the space group C2/c with a = 15.113(5), b = 12.006(2), c = 15.892(2) Å, = 122.85(2)°, and Z = 4. The structure consists of P₆O₁₈ ring layers stacked along the c direction in between which are located the lithiumions and water molecules. Two LiO₄ tetrahedra share common edges with LiO₅ pseudosquare pyramids to form two independant Li₃O₉ units. About 50% of the water molecules have fractional occupancy rates and form fragments of molecules. A linear relationship is established between the relative cell volume V/Z and the hydration degree, n, for all the known hydrates: Li₆P₆O₁₈·nH₂O.     

Crystal structure of triaquamaleatostrontium(II) monohydrate, [Sr(C4H2O4)(OH2)3]·H2O

[Sr(C₄H₂O₄)(OH₂)₃]·H₂O is monoclinic, P2₁/n, witha=11.476(2),b=7.027(1),c=12.344(2) Å, =115.74(3)°,V=896.67 ų,Z=4. The Sr atom is surrounded by nine oxygen atoms which come from four different maleate anions and three water molecules. The Sr–O distances range from 2.546(2) to 2.808(2) Å. The C–O distances are equal within the standard deviation 1.263(3) to 1.258(3) Å). In the maleate anion, the planes that contain the carboxylate groups form an angle of 74.44(9)°. Both carboxylate groups deviate significantly from planarity. The different coordination modes of the carboxylate group and the extensive hydrogen bonding present are responsible for the polymeric nature of the structure.     

Crystal structure of [Co(bipy)(maleato) (H2O)3]·H2O (bipy = 2,2′-bipyridine)

Preparation of the mononuclear cobalt(II) complex, [Co(bipy)(maleato) (H₂O)₃]·H₂O (1) where bipy = 2,2-bipyridine, were accomplished by reaction of an aqueous solution containing sodium maleate and an ethanolic solution of Co(NO₃)₂·6H₂O and bipy. The crystal structure of complex (1) was determined by X-ray crystallography. The complex crystallizes in the monoclinic space group P2₁/n with a = 9.477(3), b = 7.660(2), c =23.526 (3) Å, = 97.64(2)°, V = 1692.6(6) ų, and Z = 4. The structure consists of discrete mononuclear cobalt molecules. The cobalt atom is six-coordinate and presents a slightly distorted octahedral geometry, which consists of the two imine N atoms of bipy, a terminal carboxylate O atom from maleato ligand, and a water O atom in the basal plane with Co—N bond distances of 2.116(2) and 2.124(3) Å and Co—O distances of 2.075(2) and 2.088(2) Å, respectively. The relatively shorter Co—O distances are due to the trans effect of the bipy ligand. The octahedral coordination is completed the other two water molecules. The coordinate and the lattice water molecules were identified by TG study.     

Refined crystal structure of lovozerite Na2CaZr[Si6O12(OH,O)6] · H2O

The structure of Na,Ca,Zr-silicate lovozerite, Na₂CaZr[Si₆O₁₂(OH,O)₆] · H₂O, from the Khibiny alkaline massif (the Kola Peninsula) was refined by single-crystal X-ray diffraction analysis (Syntex $P\bar 1$ diffractometer, λMoK _α radiation, 2θ/θ scanning technique). The refinement (R _hkl = 0.077, 1531 independent reflections; anisotropic thermal parameters) confirmed the trigonal system proposed for the mineral earlier (sp. gr. R3; a = 10.18(1) Å, c = 13.13(2) Å, Z = 3) and revealed the presence of two additional positions (C and B) statistically occupied by Ca and Na atoms (and partly by Mn) and H₂O molecules, respectively.     

Synthesis and crystal structure of hexaaquamagnesium hydrogen phosphododecatungstate tetrahydrate [Mg(H2O)6][HPW12O40]·4H2O

Crystals suitable for X-ray structure analysis were obtained after the slow evaporation of the reaction mixture containing equimolar quantities of magnesium chloride and dodecatungstophosphoric acid aqueous solution insuring pH of the solution between 1.0 and 1.2. This simple synthetic route yielded stability of Keggin anion and high quality [Mg(H₂O)₆][HPW₁₂O₄₀]·4H₂O single crystals. The obtained compound belongs to the group of heteropoly compounds and its structure is composed of Keggin [PW₁₂O₄₀]^3– anions, [Mg(H₂O)₆]²⁺ cations and lattice water molecules. Zigzag arrangement of Keggin anions along c-axis creates irregular channels occupied by [Mg(H₂O)₆]²⁺ cations and lattice H₂O molecules. The calculation of the total potential solvent volume indicated the presence of 4.1 lattice H₂O lattice molecules per formula unit, which is in agreement with the here presented structural model. The position of one lattice water molecule is well defined, while each of three other molecules is statistically distributed over two locations. Hydrogen bonds involve all coordinated and lattice H₂O molecules, as well as some oxygen atoms from the Keggin anion. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of a new mineral lahnsteinite Zn4(SO4)(OH)6 · 3H2O

A sample of a new mineral from the oxidation zone of the hydrothermal Pb, Zn, Ag Friedrichssegen deposit (Rhineland-Palatinate, Germany) was studied by single-crystal X-ray diffraction. The parameters of the triclinic (pseudoorthorhombic) unit cell are found to be a = 8.312(1) ?, b = 14.545(1) ?, c = 18.504(2) ?, ?? = 89.71 (1)°, ?? = 90.05(1)°, ?? = 90.13(1)°, and V = 2237.3(3) ?³. The structure is solved by direct methods into the sp. gr. P1 and refined to an R factor of 10.7% using 3788 reflections with |F| > 3??(F) in the isotropic-anisotropic approximation. The crystallochemical formula of lahnsteinite (Z = 8) is [(Zn_2.6Fe_0.3Cu_0.1)^VI(OH)₃][Zn^IV(OH)₃(H₂O)][SO₄] · 2H₂O, where the compositions of the layer composed of Zn octahedra and isolated Zn and S tetrahedra are given in square brackets. The mineral under study is chemically and structurally similar to namuwite and is a natural analog of synthetic zinc hydroxide sulfate trihydrate.     

Complexation between tungsten(VI) and citrate: The crystal and molecular structure of a dinuclear complex,Na6[W2O5(cit)2]·10H2O

The crystals of the title compound are monoclinic, space groupP2₁/c witha=9.014(1),b=9.8668(5)c=17.5000(3) Å,=91.50(1)°,V=1556(1) ų. The structure was determined by Patterson methods and refined by least squares toR=0.038 for 3829 observed reflections and 224 parameters. There are two tungsten dimers in the unit cell, each formed by a bridging oxygen lying on a center of symmetry. Each tungsten has five more coordination sites; two occupied by terminal oxygens and the remaining three by citrate oxygens. Waters of crystallization are distributed throughout the cell and together with various of the anion oxygens, make the sodium cations either five-or six-coordinate.