Tris(5-bromo-2-methoxyphenyl)bismuth dicarboxylates [(C<Subscript>6</Subscript>H<Subscript>3</Subscript>(Br-5)(MeO-2)]<Subscript>3</Subscript>Bi[OC(O)CHal<Subscript>3</Subscript>]<Subscript>2</Subscript> (Hal = F,Cl): synthesis and structure

Tris(5-bromo-2-methoxyphenyl)bismuth dicarboxylates [(C₆H₃(Br-5)(MeO-2)]₃Bi[OC(O)CHal₃]₂, Hal = F (II) and Cl (III), have been synthesized by the reaction between tris(5-bromo-2-methoxyphenyl)bismuth (I) and trifluoroacetic acid and thrichloroacetic acid, respectively, in the presence of hydrogen peroxide in ether. According to X-ray diffraction data, a crystal of complex I contains two types of crystallographically independent molecules (a and b) both with a trigonal pyramid configuration. The bismuth atoms in complexes II and III have a distorted trigonal bipyramidal coordination with carboxylate substituents in axial positions. Axial OBiO angles are 166.3(3)° (II) and 171.6(2)° (III); equatorial CBiC angles are 118.0(3)°–123.1(3)° (II) and 113.6(3)°–127.4(3)° (III). Bi–C bond lengths are 2.189(7)–2.200(8) Å (II) and 2.190(8)–2.219(7) Å (III), and Bi–О distances are 2.280(6), 2.459(16) Å (II) and 2.264(5), 2.266(5) Å (III). Intramolecular contacts between the central atom and the oxygen atoms of carbonyl groups (Bi···O 3.028(9), 3.162(9) Å (II); 3.117(9), 3.202(9) Å (III)) are observed at maximum equatorial angles. The oxygen atoms of methoxy groups are coordinated to the bismuth atom. The Bi···O distances in complexes II and III (3.028(16), 3.157(16), 3.162(16) and 3.17(16), 3.143(16), 3.202(16) Å, respectively) are slightly longer than in complex I (3.007(9)–3.136(4) Å).     

Uranyl cyanoacetate [UO<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>(NCCH<Subscript>2</Subscript>COO)<Subscript>2</Subscript>]: Synthesis,crystal structure,and absorption spectra

The U(VI) complex with cyanoacetic acid, [UO₂(H₂O)₂(NCCH₂COO)₂] (I), was synthesized from an aqueous solution, and its X-ray diffraction analysis was carried out. The crystals are orthorhombic: space group Pca2 ₁, a = 25.9605(7) Å, b = 6.7634(2) Å, c = 6.3398(2) Å, V = 1113.15(6) ų at 100 K, and Z = 4. The coordination polyhedron of the uranium atom is a distorted pentagonal bipyramid. The cations UO ₂ ²⁺ are bound into infinite zigzag chains by the bridging carboxyl groups of one of the anions of cyanoacetic acid. The carboxyl oxygen atom of the second anion, which is not involved in coordination, and the nitrogen atoms of the cyano groups form hydrogen bonds with the coordination water molecules. The layer structure of the compound is formed through the hydrogen bonds. The absorption spectra in the visible and infrared ranges of the crystalline compound are measured and analyzed.     

Three- and four-coordinated silver(I) ions in the coordination polymers [Ag(Me<Subscript>4</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript> and [Ag(2,3-Et<Subscript>2</Subscript>Pyz)<Subscript>2</Subscript>]PF<Subscript>6</Subscript>

The coordination polymers [AgPF₆(Me₄Pyz)₂] (I) and [AgPF₆(2,3-Et₂Pyz)₂] (II) were synthesized, and their structures were determined. Crystals of I are monoclinic, space group C2/c, a = 10.213(2) Å, b = 16.267(3) Å, c = 12.663(3) Å, β = 92.90(3)°, V = 2102.1(7) ų, ρ_calcd = 1.660 g/cm³, Z = 4. The structure of I is built of polymeric zigzag [Ag(C₈H₁₂N₂)] _∞ ⁺ chains and octahedral [PF₆] anions. The coordination polyhedron of the Ag⁺ ion is a flat triangle. Crystals of II are tetragonal, space group P \(\bar 4\)2(1)/c,a = b = 10.641(1) Å, c = 18.942(1) Å, V = 2144.6(2) ų, ρ_calcd = 1.627 g/cm³, Z = 4. In the structure of II, 2D cationic layers of fused square rings exist; the rings consist of four Ag⁺ cations linked by four bridging ligands of diethylpyrazine Et₂Pyz. The coordination polyhedron of the Ag⁺ ion is an irregular four-vertex polyhedron.     

Syntheses and crystal structures of (2.2.2-cryptand)potassium chloride and (2.2.2-cryptand)ammonium bromide<Subscript>(0.75)</Subscript>chloride<Subscript>(0.25)</Subscript> hydrates

Two new complexes were synthesized, namely, 7: 2 (2.2.2-cryptand)potassium chloride and (2.2.2-cryptand)ammonium bromide_(0.75)chloride_(0.25) hydrates: [M(Crypt-222)]⁺ · Hal^? · 3.5H₂O, where M = K, Hal = Cl (I) and M = NH₄, Hal = Br_0.75Cl_0.25 (II). The structures of two isomorphous crystals were studied by X-ray diffraction analysis. Trigonal (space group P \(\bar 3\), Z = 2) structures I (a = 11.763 Å, c = 11.262 Å) and II (a = 11.945 Å, c = 11.337 Å) were solved by direct methods and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.057 (I) and 0.065 (II) for all 2626 (I) and 1654 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). In structures I and II, the host-guest [M(Crypt-222)]⁺ complex cation lies on the threefold crystallographic axis and has the approximate D ₃ symmetry. In complex I, the coordination polyhedron of the K⁺ cation (CN = 8) is a bicapped trigonal prism somewhat distorted toward an antiprism. Complexes I and II contain H-bonded disordered cubes of the water molecules and the Cl^? or Br^? anions.     

Molecular and crystal structures of adducts (Cp<Subscript>2</Subscript>YCl)<Subscript>2</Subscript>L (L = 2THF,DME, 1,4-dioxane)

The adducts [Cp₂Y(μ-Cl)]₂ · 2THF (5), {[Cp₂Y(μ-Cl)]₂ · 1,4-dioxane}_n (6), and Cp₂Y(DME)(μ-Cl)(Cl)YCp₂ (7) have been synthesized and studied by X-ray crystallography. In 5, the (Cp₂YCl)₂ moiety is coordinated to two THF molecules (d _(Y-O) = 2.478 Å); in 6 the (Cp₂YCl)₂ dimers are linked by 1,4-dioxane to form a polymer chain (d _(Y-O) = 2.601 Å). In asymmetric adduct 7, the DME molecule is bound through both O atoms to the same Y atom (d _(Y-O) = 2.382 and 2.448 Å), and one of the chlorine atoms is bridging and the other chlorine atom is terminal.     

Synthesis and crystal structure of (1<Emphasis Type="Italic">H</Emphasis>-Benzo[<Emphasis Type="Italic">d</Emphasis>]imidazol-2-yl)(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)methanone (L). complex formation of copper(II) and cobalt(II) chlorides with L

(1H-Benzo[d]imidazol-2-yl)(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)methanone (L) and its complexes with copper and cobalt chlorides [CuLCl₂] (I) and [CoLCl₂] (II) are synthesized and studied by IR spectroscopy. The structure of molecule L is determined by X-ray diffraction analysis. Molecule L crystallizes as a cis-trans isomer. The dihydroisoquinoline (A) and benzimidazole (B) fragments lie in the mutually perpendicular planes. The N-C bond lengths of fragment A (double bond N(1)-C(1) 1.278(3) Å, ordinary bond N(1)-C(9) 1.490(3) Å) differ noticeably. The N-C bond lengths in fragment B range from 1.327(4) to 1.389(4) Å. The C=O bond is 1.218(3) Å According to the data of IR spectroscopy and X-ray diffraction analysis, complexes I and II are assumed to have different structures with different coordination modes to the metal atom of molecule L: through the imine atoms N(1) and N(2) of fragments A and B in I and through the N(1) atom of the dihydroisoquinoline fragment and the O atom of the carbonyl group in II.     

Palladium clusters Pd<Subscript>4</Subscript>(SR)<Subscript>4</Subscript>(OAc)<Subscript>4</Subscript> and Pd<Subscript>6</Subscript>(SR)<Subscript>12</Subscript> (R = Bu,Ph): Structure and properties

The structures of the Pd₄(SBu)₄(OAc)₄ (I) and Pd₆ (SBu)₁₂ (II) palladium clusters are determined by the X-ray diffraction method. For cluster I: a = 8.650(2), b = 12.314(2), c = 17.659(4) Å, α = 78.03(3)°, β = 86.71(2)°, γ = 78.13(3)°, V = 1800.8(7) ų, ρcalcd = 1.878 g/cm³, space group P \(\bar 1\), Z = 4, N = 3403, R = 0.0468; for structure II: a = 10.748(2), b = 12.840(3), c = 15.233(3) Å, α = 65.31(3)°, β = 70.10(3)°, γ = 72.91(3)°, V = 1767.4(6) ų, ρ calcd = 1.605 g/cm³, space group P \(\bar 1\), Z = 1, N = 3498, R = 0.0729. In cluster I, four Pd atoms form a planar cycle. The neighboring Pd atoms are bound by two acetate or two mercaptide bridges (Pd…Pd 2.95–3.23 Å, Pd…Pd angles 87.15°–92.85°). In cluster II, the Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.09–3.14 Å, the PdPdPd angles being 118.95°–120.80°. The Pd atoms are linked in pairs by two mercaptide bridges. The formation of clusters I and II in solution is proved by IR spectroscopy and calorimetry. Analogous clusters are formed in solution upon the reaction of palladium(II) diacetate with thiophenol.     

Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.     

Structural investigation of [Au(en)<Subscript>2</Subscript>]Cl(ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> and [Au(en)<Subscript>2</Subscript>](ReO<Subscript>4</Subscript>)<Subscript>3</Subscript> complexes

Novel complex salts [Au(en)₂]Cl(ReO₄)₂ (I) and [Au(en)₂](ReO₄)₃ (II), en = ethylenediamine, are obtained. Their crystal structures are determined by single crystal X-ray diffraction. Complex I crystallizes in the triclinic crystal system: a = 6.2172(7) Å, b = 7.1644(8) Å, c = 8.8829(8) Å, α = 96.605(4)°, β = 110.000(4)°, γ = 97.802(4)°, P-1 space group, Z = 1, d _x = 3.905 g/cm³; complex II crystallizes in the monoclinic crystal system: a = 15.244(2) Å, b = 7.6809(8) Å, c = 9.3476(12) Å, β = 127.004(3)°, C2 space group, Z = 4, d _x = 4.057 g/cm³.     

Iron(II) complexes [Fe(DfgH)<Subscript>2</Subscript>(3-CONH<Subscript>2</Subscript>-Py)<Subscript>2</Subscript>] and [Fe(DfgH)<Subscript>2</Subscript>(4-COOC<Subscript>2</Subscript>H<Subscript>5</Subscript>-Py)<Subscript>2</Subscript>]: Synthesis and structures

The complexes [Fe(DfgH)₂(3-CONH₂-Py)₂] (I) and [Fe(DfgH)₂(4-COOC₂H₅-Py)₂] (II), where DfgH₂ is α-benzyl dioxime, were obtained and examined by X-ray diffraction analysis. The equatorial planes of the coordination octahedra of the metal ions consist of two monodeprotonated α-benzyl dioxime residues united through intramolecular hydrogen bonds O-H…O into a pseudomacrocyclic system. The neutral molecules 3-CONH₂-Py and 4-COOC₂H₅-Py are coordinated to the Fe²⁺ ion through the N atom of the heterocycle. Structure I is layered and structure II is molecular. Intermolecular interactions N-H…O are responsible for the formation of layers in crystal structure I.     

Cobalt(II) and copper(II) complexes with chiral pyrazolylquinoline,a derivative of terpenoid (+)-3-carene. Catalytic activity in ethylene polymerization reaction

Coordination compounds [CoLCl₂] (I), [CuLCl(NO₃)] (II), CuL(NO₃)₂ (III), and CuLCl₂ (IV) (where L is a chiral pyrazolylquinoline—a derivative of terpenoid (+)-3-carene) were synthesized. X-ray diffraction data showed that crystal structures I and II are built of mononuclear acentric molecules. In the molecule of complex I, the Co₂₊ ion coordinates two N atoms of bidentate cycle-forming ligand L and two Cl atoms. The coordination polyhedron of Cl₂N₂ is a distorted tetrahedron. For complex I, μ_eff = 4.50 μ_B, which corresponds to a high-spin configuration d ⁷. In the molecules of II(1), II(2) (which are diastereoisomers of complex II), each Cu²⁺ ion coordinates two N atoms of bidentate cycle-forming ligand L, the Cl atom, and two O atoms of bidentate cyclic NO ₃ ^? ion. The ClN₂O₂ coordination polyhedra are tetragonal pyramids with different degrees of distortion. The structure of complex II consists of supramolecular clusters, i.e., isolated chains incorporating the molecules of II(1) and II(2). The values of μ_eff for II–IV correspond to the d ⁹ configuration. The results of EPR and IR study suggest that complex III contains the O₄N₂ polyhedron, whereas complex IV contains the Cl₂N₂ polyhedron. Complexes I and IV were found to show a high catalytic activity in ethylene polymerization reaction.     

Crystal structures of triphenylamylphosphonium iodide [Ph<Subscript>3</Subscript>AmP]I and triphenylamylphosphonium tetraiodide [Ph<Subscript>3</Subscript>AmP]I<Subscript>4</Subscript>

By reaction of triphenylamylphosphonium iodide [Ph₃AmP]I (I) with antimony iodide in acetone, triphenylamylphosphonium tetraiodide [Ph₃AmP]₂I₄ (II) was synthesized. Crystals of I consist of triphenylamylphosphonium cations and iodine anions. Compound II contains two types of tetrahedral triphenylamylphosphonium cations, iodine anions, and [I₃]^? anions. Atoms P have a distorted tetrahedral coordination in cations I and II (the CPC angles are 106.48(12)°–111.25(12)° in I and 107.05(9)°–112.62(10)° in II). The centrosymmetric trinuclear [I₃]^? anion in II is nearly linear (the I(2)I(1)I(3) angle is 178.65°, the I(1)–I(2) and I(1)–I(3) bond lengths are 2.8925(2) Å and 2.9281(2) Å, respectively).     

Structure of arsenic 8-mercaptoquinolinate: Synthesis and crystal structure of arsenic 4-methoxy-8-mercaptoquinolinate As[C<Subscript>9</Subscript>H<Subscript>5</Subscript>(OCH<Subscript>3</Subscript>)NS]<Subscript>3</Subscript>

Arsenic 4-methoxy-8-mercaptoquinolinate As[C₉H₅(4-OCH₃)NS]₃ (I) was synthesized and studied by X-ray diffraction. Crystals are trigonal: space group R3, a = b = 13.9867(4) Å, c = 12.4991(5) Å, γ = 120°, V = 2117.58(12) ų, ρ = 1.519 g/cm³, Z = 3. An arsenic atom in the crystal structure occupies a special position on axis 3. The structural unit of the crystal (neutral complex I) has symmetry C3. 4-Methoxy-8-mercaptoquinoline acts as a bidentate (N,S-) ligand. The coordination polyhedron of the arsenic atom is a symmetric octahedron (3S + 3N) or, with allowance for the lone electron pair, ψ-one-capped octahedron (3S + 3N + E). Bond lengths are as follows: As-S, 2.3179(7)Å; As…N 2.688(3) Å. The geometries of coordination polyhedra of arsenic atoms are compared in the crystal structures of As(C₉H₆NS)₃, As[C₉H₅(2-CH₃)NS]₃, and As[C₉H₅(4-CH₃)NS]₃.     

Dynamic in situ solvothermal reactions between ZnX<Subscript>2</Subscript> (X = Cl,ClO<Subscript>4</Subscript>) and a heterocyclic disulfide

Solvothermal reactions of 2-ppds (2-ppds = di[4-(pyridin-2-yl)pyrimidinyl]disulfide) with ZnX₂ (X = Cl, ClO₄) in mixed CH₃OH–CH₂Cl₂ solvent have been investigated. To better understand these reactions, solution analysis was conducted in parallel with single-crystal X-ray diffraction analysis of the in situ generated coordination complexes. At 120 °C, solvothermal reaction of 2-ppds with ZnCl₂ resulted in a discrete mononuclear coordination complex formulated as [ZnCl₂(L1)] (1), in which the zwitterion L1 (1-methyl-4-(pyridin-2-yl)pyrimidin-1-ium-2-olate) was formed in situ from 2-ppds, and solution analyses based on TLC and ESI–MS further showed that the reaction solution also contains in situ transformed products of L2 (bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane) and L3 (2-methoxy-4-(pyridin-2-yl)pyrimidine). At 90 °C, solvothermal reaction between 2-ppds and Zn(ClO₄)₂ led to a discrete mononuclear coordination complex formulated as [Zn(SH)(L2)]ClO₄ (2) that features a terminally bound –SH group, while the reaction solution was also found to contain a library of in situ reaction products of 2-ppds including L1, L2, L3 and L4 ((4-(pyridin-2-yl)pyrimidin-2-yl) 4-(pyridin-2-yl)pyrimidine-2-sulfonothioate). Thus, the heterocyclic disulfide 2-ppds is transformed in situ into various organic products in a series of reactions involving C–S/S–S bond cleavage.     

Synthesis and crystal structures of Schiff base oxovanadium(V) complexes [VO(Bhm)(OCH<Subscript>3</Subscript>)(CH<Subscript>3</Subscript>OH)] and [VO<Subscript>2</Subscript>(Bpp)]

Compound [VO(acac)₂] reacts with the Schiff bases N′-(5-bromo-2-hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide (H₂Bhm) and 4-bromo-2-[(2-piperidin-1-ylethylimino)methyl]phenol (HBpp) in absolute methanol to give the oxovanadium(V) complexes [VO(Bhm)(OCH₃)(CH₃OH)] (I) and [VO₂(Bpp)] (II), respectively. Both complexes were characterized by elemental analysis, IR spectra, and single-crystal X-ray determination. The crystal of I crystallizes in the triclinic space group \(P\bar 1\) with a = 7.625(2), b = 11.240(3), c = 12.156(4) Å, α = 77.404(5)°, β = 75.770(4)°, γ = 79.922(5)°, V = 977.4(5) ų, Z = 2. The crystal of II crystallizes in the monoclinic space group P2/c with a = 26.760(3), b = 6.655(1), c = 17.570(2) Å, β = 100.335(2)°, V = 3078.2(7) ų, Z = 8. The V atom in I is in an octahedral coordination, and those in II are intervenient between square pyramidal and trigonal bipyramidal coordination.     

Cobalt(II) and nickel(II) cloride complexes with 4,5-(<Emphasis Type="Italic">n</Emphasis>-pyridylethylene)-dithio-1,3-dithiol-2-thiones (<Emphasis Type="Italic">n</Emphasis> = 2, 4)

The NiCl₂ and CoCl₂ complexes with 4,5-(2-pyridylethylene)-dithio-1,3-dithiol-2-thione (L¹) and 4,5-(4-pyridylethylene)-dithio-1,3-dithiol-2-thione (L²) were described. The L¹ ligand shows bidentate coordination through the pyridyl N atoms and the thiol S atoms in a tetrahedral [CoCl₂(L¹)] complex (I) and in an octahedral [NiCl₂(L¹)₂](MeCN)₂ complex (II). The L² ligand exhibits monodentate coordination through the pyridyl N atom in tetrahedral complexes [CoCl₂(L²)₂ (III) and [NiCl₂(L²)₂] (IV). Complexes I, III, IV in crystal state are octahedral due to extra coordination of the thione S atoms or the chloride bridges responsible for the polymeric structure. The structure of the complex II · CH₂Cl₂ was determined by X-ray diffraction analysis. The crystals are monoclinic, space group P2₁/c, a = 11.895(2) Å, b = 13.374(3) Å, c = 21.873(4) Å, β = 95.30(3)°, Z = 2. The Ni atom has quasi-tetrahedral surrounding due to two chloride ions and two L¹ ligands coordinated through the pyridyl N atoms and the thiol S atoms.     

Syntheses and crystal structures of [Bi(DMSO)<Subscript>8</Subscript>][Fe(NCS)<Subscript>6</Subscript>] and [Al(DMSO)<Subscript>6</Subscript>][Al(NCS)<Subscript>6</Subscript>]

New complexes of composition [Bi(DMSO)₈][Fe(NCS)₆] (1) and [Al(DMSO)₆][Al(NCS)₆] (2) have been prepared, and an octahedral hexarodanoaluminate anion has been structurally characterized for the first time. Crystals of compound 1 are triclinic, space group \(P\bar 1\), a = 11.2368(4) Å, b = 11.4063(4) Å, c = 21.0711(9) Å, α = 92.9520(10)°, β = 99.9430(10)°, γ = 111.9290(10)°, V = 2447.69(16) ų, Z = 2, ρ_calc = 1.680 g/cm³, R ₁ = 0.0564; crystals of compound 2 are cubic, space group \(Pa\bar 3\), a = 15.8201(4) Å, V = 3959.39(17) ų, Z = 4, ρ_calc = 1.462 g/cm³, R ₁ = 0.0475. The bismuth coordination polyhedron BiO₈ in compound 1 is a distorted square antiprism with broken square faces (Bi-O, 2.368-2.582 Å). In the structure of 2, the cation disordered in a complex manner has an octahedral configuration (Al-O, 1.888(11)-1.912(11) Å).     

Crystal structures of two copper(II) complexes with <Emphasis Type="Italic">N,N</Emphasis>-diethylbenzhydrazide

The copper(II) complexes with N,N-diethylbenzhydrazide, [Cu(C₆H₅CONHN(C₂H₅)₂)]Cl₂ (I) and Cu(C₆H₅CONN(C₂H₅)₂)₂ (II), have been studied by X-ray diffraction analysis. In the both compounds, the reactant acts as a bidentate (O, N(2)) ligand, forming five-membered chelate rings with copper. In cationic complex I, the O→Cu and N→Cu bond lengths are 1.954(2) and 2.070(3) Å, respectively, and the O(1)CuN(2) chelate angle is 81.89(10°. The Cl^? ions are in the coordination sphere of copper (Cu-Cl, 2.1974(11) and 2.2178(10) Å). The chelate ring has an envelope conformation with the copper atom in the flap position. The coordination polyhedron of the copper atom is a strongly distorted tetrahedron. Neutral complex II is an inner complex salt. The reactant forms with copper two planar chelate rings. The Cu-O and N→Cu bond lengths are 1.8901(9) and 2.0175(11) Å, respectively, and the O(1)CuN(2) chelate cycle is 83.70(4)°. Complex II is planar, and the coordination polygon of the copper atom is a parallelogram. The thermal stability of complexes I and II has been studied.     

Crystal and Molecular Structure of Aqua[1,2-bis(2-(o-hydroxyphenoxy)ethoxy)ethane](isothiocyanato)sodium

The crystals of the hydrated complex of a podand 1,2-bis(2-(o-hydroxyphenoxy)ethoxy)ethane (L) with sodium thiocyanate of the composition [Na(NCS)L(H₂O)] (I) were prepared and studied by X-ray diffraction analysis. The structure of I (space group P2₁/n, a = 12.128 Å, b = 14.221 Å, c = 13.594 Å, β = 113.82°, Z = 4) was solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.055 over all 2970 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). The individual host–guest type molecules are connected in crystal I by hydrogen bonds. The coordination polyhedron of the Na⁺ cation is a distorted pentagonal bipyramid whose base consists of five O atoms of the podand L and whose axial positions are occupied by the O atom of water and the N atom of SCN^–. The sixth O atom of the podand L is not involved in Na⁺ coordination.     

Crystal structures of <Emphasis Type="Italic">trans</Emphasis>-[Re<Subscript>6</Subscript>S<Subscript>8</Subscript>(CN)<Subscript>2</Subscript>L<Subscript>4</Subscript>] complexes,L = pyridine or 4-methylpyridine

The structures of three novel octahedral rhenium cluster compounds [Re₆S₈(CN)₂(py)₄]·H₂O (1), [Re₆S₈(CN)₂(4-Mepy)₄] (2), [Re₆S₈(CN)₂(4-Mepy)₄]·4-Mepy (3) (py = pyridine, 4-Mepy = 4-methylpyridine) are determined by X-ray crystallography. Crystal data are: C2/m space group, a = 14.813(1) Å, b = 14.772(1) Å, c = 9.2122(6) Å, β = 119.085(2)°, V = 1761.7(2) ų, d _x = 3.318 g/cm³, R = 0.0585 (1); I4₁/amd space group, a = 16.0018(3) Å, c = 14.7186(5) Å, V = 3768.81(16) ų, d _x = 3.169 g/cm³, R = 0.0489 (2); P2₁/c space group, a = 9.0452(4) Å, b = 15.8065(7) Å, c = 15.2951(6) Å, β = 103.700(2)°, V = 2124.57(16) ų, d _x = 2.957 g/cm³, R = 0.0245 (3). Molecular cluster complexes interact via π-π stacking affording 3D frameworks in 1 and 2 and chains in 3.