f-Element/crown ether complexes. 20. Synthesis and structure of [Y(NO3)3(OH2)3]·1.5(15-crown-5)·Me2O

The title complex was prepared by the addition of 15-crown-5, dissolved in acetone, to a solution of Y(NO₃)₃·nH₂O in the same solvent. The crystal structure of this complex, determined by single-crystal X-ray diffraction using counter methods, was carried out on a crystal grown by slow evaporation of the reaction mixture at room temperature. [Y(NO₃)₃(OH₂)₃]·1.5(15-crown-5) Me₂CO crystallizes in the acentric space group, P2₁, with unit cell dataa=15.900(5),b=16.530(6),c=11.821(5) Å,=92.12(3)°,D _calc=1.53 g cm^–3 forZ=4. Each unit cell consists of two dimers of the formula unit. One crown molecule bridges two [Y(NO₃)₃(OH₂)₃] units via hydrogen bonding with one water molecule of each. The two remaining water molecules per metal moiety form three hydrogen bonds to another 15-crown-5 molecule and one to an acetone molecule. The average bonding parameters in the nine-coordinate metal complexes are Y-O(NO₃)=2.43(4) Å and Y-O(OH₂)=2.34(5) Å.For Part 19 see Rogers, 1987.     

The synthesis and crystal structure of [La(OH2)5(phen)2]Cl3·4H2O·phen

[La(OH₂)₅(phen)₂]Cl₃·4H₂O·phen is centric, Pnna, witha=19.946(7),b=16.458(5),c=12.207(4)Å andD _calc=1.57 g cm^–3 forZ=4. The La(III) ion resides on a crystallographic twofold axis and is coordinated to four nitrogen atoms (from two phen molecules) and five water molecules resulting in a distorted tricapped trigonal prismatic geometry. An uncoordinated phen molecule, two chloride anions, and four uncoordinated water molecules are hydrogen bonded to the coordinated water molecules. The coordinated and uncoordinated phen molecules -stack diagonally through the unit cell.     

Synthesis and structure of [Ca(triethyleneglycol)2](NO3)2·H2O

Crystallization of calcium nitrate from a toluene solution of triethyleneglycol (= 2,2-[1,2-ethanediylbis(oxy)]-bisethanol) resulted in the formation of the 1:2 solvate [Ca(triethyleneglycol)₂](NO₃)₂·H₂O. [Ca(C₆H₁₄O₄)₂](NO₃)₂·H₂O is monoclinic, P2₁/c, a = 15.775(1), b = 8.660(2), c = 16.342(1) Å, = 91.239(7)°, V = 2232.1(6) ų, Z = 4, and D _c = 1.429 g cm^–3. The eight-coordinate calcium has square antiprismatic geometry with two triethyleneglycol molecules straddling the metal center. The nitrate anions and water of crystallization are involved in hydrogen bonding with the alcoholic hydrogen atoms.     

Synthesis and crystal structure of (CN3H6)2[UO2(OH)2(NCS)]NO3 and β-Cs3[UO2(NCS)5]

Compounds (CN₃H₆)₂[UO₂(OH)₂(NCS)]NO₃ (I) and β-Cs₃[UO₂(NCS)₅] (II) are synthesized and studied by IR spectroscopy and single-crystal X-ray diffraction. I and II crystallize in the orthorhombic system. For I, a = 12.2015(13) Å, b = 7.3295(8) Å, c = 16.310(2) Å, space group Pnma, Z = 4, and R = 0.0327; for II, a = 21.7891(6) Å, b = 13.5120(3) Å, c = 6.8522(2) Å, space group Pnma, Z = 4, and R = 0.0268. In structure I, complex groups form infinite chains [UO₂(OH)₂(NCS)] _n ^n? belonging to the AM ₂ ² M ¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , M ² = OH^?, and M ¹ = NCS^?). The main structural elements of crystals II are mononuclear [UO₂(NCS)₅]^3? groups belonging to the AM ₅ ¹ group of uranyl complexes (A = UO ₂ ²⁺ and M ¹ = NCS^?). In I and II, uranium-containing complexes are connected with outer-sphere cations by electrostatic interactions, and in I a system of hydrogen bonds also contributes to their binding. Specific features of the packing of complex [UO₂(NCS)₅]^3? groups in the structures of two modifications of Cs₃[UO₂(NCS)₅] are discussed.     

The crystal structure and supramolecular chain of [La(NO3)3(OH2)2(phen)] ⊙ 15-crown-5

[La(NO₃)₃(OH₂)₂(phen)] · 15-crown-5 is hexagonal,P6₅, witha=10.955(2),c=43.769(9), andD _calc =1.668 g cm^–3 for Z=6. In the complex, two nitrogen atoms (from phen) and eight oxygen atoms (six from three bidentate nitrate anions and two from water molecules) are coordinated to the central La(III) ion, forming a coordination polyhedron which is approximately a bicapped square antiprism. The coordinated water molecules donate hydrogen bonds to the oxygen atoms of the crown ether, forming polymeric hydrogen bonded chains which wrap helically along the unit cell directionc.     

The crystal structure analysis of iron nitroprusside,Fe[Fe(CN)5NO]·3H2O

The crystal structure of iron(II) pentacyanonitrosylferrate trihydrate has been determined from three dimensional, single-crystal X-ray diffraction data. Fe[Fe(CN)₅NO]·3H₂O crystallizes in the monoclinic space group P2₁/n with lattice constants,a=7.205(1),b=14.641(2),c=10.680(1) Å,=91.14(1)° andZ=4,D _m =1.89(1) g cm^–3 andD _x =1.92 g cm^–3. Final full-matrix least-squares refinement of 1691 unique reflections yieldedR=0.024 andR _w =0.028. Both iron atomic centers have distorted octahedral symmetries. The cation iron center is coordinated by five cyanide ligands and one water molecule, while the second iron center is coordinated by five cyanide ligands and one nitrosyl group. Cyanide bridging links the metal centers. Two uncoordinated water molecules, O(2) and O(3), are hydrogen bonded to the coordinated water molecule, O(1), and occupy channels in the crystal lattice. Important mean bond distances for iron nitroprusside are: Fe(cation)-N=2.159(17), Fe-C=1.936(4) and C=N=1.144(6) Å. Other notable bond lengths include: Fe-O(1)=2.152(2), Fe-NO=1.669(2) and NO=1.131(3) Å. The distances between the coordinated water molecule and two uncoordinated water molecules are 2.855(3) and 2.740(3) Å.     

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.     

Synthesis and X-ray structure of [(H3O)(C14H20O5)2][Me2NH2]2 [PMo12O40] · 2C14H20O5 (C14H20O5 = benzo-15-crown-5; Me2NH = dimethylamine)

[(H₃O)(C₁₄H₂₀O₅)₂][Me₂NH₂]₂ [PMo₁₂O₄₀] · 2C₁₄H₂₀O₅ 1 was synthesized from benzo-15-crown-5 and H₃PMo₁₂O₄₀·24H₂O in N,N-dimethylformamide for the first time. 1 crystallizes in the monoclinic space group C2/c with a = 18.583(4), b = 25.510(5), c = 19.904(4) Å, = 94.66(3)° D _c = 2.124 mg/m³ for Z = 4. Refinement based on 7358 observed reflections led to a R1(wR2) = 0.0378(0.0761). The complex cation, [(H₃O)(C₁₄H₂₀O₅)₂]⁺, exhibits a sandwich structure by hydrogen-bonding in the mean distance of 2.955 Å. The anion, PMo₁₂O₄₀ ^3–, is a -Keggin structure.     

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.     

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)     

Structure of [La(NO3)3(OH2)2(OHMe)(bipy)]·15-crown-5

[La(NO₃)₃(OH₂)₂(OHMe)(bipy)·15-crown-5 is monoclinic,P2_t/n, witha=11.239(6),b=19.302(7),c=14.458(8) , =92.47(5)°, andD _calc=1.63 g cm^–3 forZ=4. In the complex, two nitrogen atoms (from bipy) and nine oxygen atoms (six from three bidentate nitrate anions, two from water molecules, and one from a methanol molecule) coordinate to the La(III) ion forming a coordination polyhedron which approximates a skewed trigonal prism with an interpenetrating pentagon. The coordinated methanol and water molecules donate hydrogen bonds to the oxygen atoms of the crown ether forming polymeric hydrogen bonded chains which propagate along theac diagonal in the unit cell.     

Synthesis and crystal structure of [Co(phen)(H2O)4](SO4)⋅2(H2O)

The title complex, [Co(phen)(H₂O)₄](SO₄)2(H₂O) (phen = 1,10-phenanthroline) was prepared in aqua tert-butylperoxohydrogen solution. X-ray single crystal structure determination reveals that the complex consists of a phenanthrolinatocobalt(II)tetrahydrate dication, two uncoordinated water molecules and a sulfate anion. It crystallizes in the orthorhombic space group Pbca with a = 8.856(1), b = 18.318(3), c =21.918(5) Å, V = 3555.6(11) ų. The coordination geometry at each cobalt(II) atom is a slightly distorted octahedron.     

Synthesis and structure of (NH4)3[UO2(C3H2O4)2(NCS)] · 2H2O

Malonate-thiocyanate complex (NH₄)₃[UO₂(C₃H₂O₄)₂(NCS)] · 2H₂O is synthesized and studied by X-ray diffraction. The compound crystallizes in the monoclinic system: a = 13.9983(4) Å, b = 8.1947(2) Å, c = 16.4678(4) Å, β = 100.846(1)°, space group Cc, Z = 4, and R = 0.0158. The main structural units of the crystal are mononuclear [UO₂(C₃H₂O₄)₂(NCS)]^3? groups belonging to the AB ₂ ⁰¹ M ₁ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₂O ₄ ^2? , M ¹ = NCS^?). Discrete uranium-containing groups are connected by electrostatic interactions with ammonium ions and by hydrogen bonds. Some specific structural features of crystals containing [UO₂(L)₂(NCS)]^3? complexes, where L is the oxalate or malonate ion, are discussed.     

Seven-coordinated chelate [Cd(SCZ)3·H2O](HTNR)2(H2O)2: Synthesis,crystal structure and energetic properties

To deepen the study on heptacoordinate transition metal coordination complexes, a novel seven-coordinated coordination compound [Cd(SCZ)₃·H₂O](HTNR)₂(H₂O)₂ (1, SCZ = semicarbazide, H₂TNR = styphnic acid) was synthesized and characterized by elemental analysis and FTIR spectroscopy. Single-crystal X-ray diffraction analysis revealed that 1 crystallizes in the triclinic space group P-1. The thermal decomposition mechanism of 1 was studied by differential scanning calorimetry (DSC). The non-isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa-Doyle's method, respectively. Sensitivity tests revealed that 1 is insensitive to mechanical stimuli. The heat of combustion was measured by oxygen bomb calorimetry and the enthalpy of formation was calculated.     

Crystal and molecular structure of [H3O·18-crown-6]2-[ReCl6] isolated from a liquid clathrate medium

The crystal and molecular structure of [H₃O·18-crown-6]₂[ReCl₆]1 is reported. Crystal data for1: trigonal, space group R ,a=13.857(2) Å,c=10.154(2) Å,D _c =2.85 g/cm³,Z=3,R _f =0.073,R _w =0.064. The oxonium ion is observed to be crystallographically disordered lying 0.37 Å on both sides of the plane defined by the crown ether oxygen atoms. The anion resides on a crystallographic position forming a slightly distorted octahedron.     

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.     

Synthesis and crystal structure of a new bimetallic complex of diethylenetriamine pentaacetic acid: [YbAg2(dtpa)(H2O)]·3H2O

The reaction between Yb(III) nitrate, Ag(I) nitrate, and the diethylenetriamine pentaacetate (dtpa) ligand gives rise to a bimetallic complex. [YbAg₂(dtpa)(H₂O)]·3H₂O is triclinic, space group P-1, with a = 8.768 (3), b = 9.862 (2), c = 13.055 (2) Å, = 75.40 (1), = 83.00 (2) and = 87.46 (2)°. Each dtpa is coordinated to one ytterbium and six silver atoms. The resulting crystal structure can be described as 2D packing. In the layers, the ytterbium atoms are connected through [Ag(COO)]₂ dimers. Strong hydrogen bonds, involving the noncoordinated water molecules, ensure crystal cohesion.     

Synthesis and structure determination of 3β-hydroxyandrost-5-en-17-one (C19H28O2·CH3OH)

3-Hydroxyandrost-5-en-17-one (C₁₉H₂₈O₂.CH₃OH) has been prepared for undertaking its crystallographic analysis and to investigate the role of intra- and intermolecular interactions in steroids. The title compound crystallizes in the orthorhombic space group C222₁ with unit cell parameters a = 6.7892(17), b = 12.624(2), and c = 41.136(5) Å; V = 3525.7(12) ų and Z = 8. The three-dimensional structure has been solved by direct methods. The final reliability index for the computed structure is 0.050 for 1088 observed reflections. Ring A exist in chair conformation, Ring B in half-chair conformation, and the Ring C assumes a distorted chair conformation. The five-membered Ring D adopts half-chair conformation. The A/B ring junction is quasi-trans while as B/C and C/D are trans-fused. The oxygen atom of the solvent molecule (CH₃OH) is involved in O–H···O intermolecular interaction.     

Synthesis and crystal and molecular structure of the [MoO2(L)(H2O)] · H2O complex (L 2− is the anion of 2-[N-(hydroxynaphtylidene)amino]propan-1,2,3-triol)

A new compound of dioxomolybdenum(VI)—[MoO₂(L)(H₂O)] · H₂O, where L ^2? = 2-[N-(hydroxynaphtylidene)amino]propan-1,2,3-triol)—is synthesized. Its structure is determined by X-ray diffraction. The Mo atom has an octahedral coordination formed by two oxo ligands located cis with respect to one another, two O atoms and the N atom of the tridentate bis(chelate) L ^2? ligand, and the O atom of a water molecule. The crystallization water molecule is connected with two complex molecules by O-H…O hydrogen bonds.